CN114583200B - High-performance ultrathin porous membrane for flow battery and preparation and application thereof - Google Patents
High-performance ultrathin porous membrane for flow battery and preparation and application thereof Download PDFInfo
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- 239000012528 membrane Substances 0.000 title claims abstract description 60
- 238000002360 preparation method Methods 0.000 title abstract description 9
- 229920005989 resin Polymers 0.000 claims abstract description 58
- 239000011347 resin Substances 0.000 claims abstract description 58
- 239000002904 solvent Substances 0.000 claims abstract description 28
- 239000007791 liquid phase Substances 0.000 claims abstract description 23
- 239000002994 raw material Substances 0.000 claims abstract description 21
- 239000003431 cross linking reagent Substances 0.000 claims abstract description 12
- 238000000034 method Methods 0.000 claims abstract description 9
- 229920000642 polymer Polymers 0.000 claims abstract description 7
- 239000002131 composite material Substances 0.000 claims abstract description 4
- IMNFDUFMRHMDMM-UHFFFAOYSA-N N-Heptane Chemical compound CCCCCCC IMNFDUFMRHMDMM-UHFFFAOYSA-N 0.000 claims description 24
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Chemical compound BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 claims description 12
- 229910052720 vanadium Inorganic materials 0.000 claims description 10
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 10
- 239000004693 Polybenzimidazole Substances 0.000 claims description 8
- 229920002480 polybenzimidazole Polymers 0.000 claims description 8
- 229920001223 polyethylene glycol Polymers 0.000 claims description 8
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 7
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 claims description 7
- UHOVQNZJYSORNB-UHFFFAOYSA-N benzene Substances C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 claims description 7
- 229910052725 zinc Inorganic materials 0.000 claims description 7
- 239000011701 zinc Substances 0.000 claims description 7
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 claims description 6
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 6
- FXHOOIRPVKKKFG-UHFFFAOYSA-N N,N-Dimethylacetamide Chemical compound CN(C)C(C)=O FXHOOIRPVKKKFG-UHFFFAOYSA-N 0.000 claims description 6
- 229910052794 bromium Inorganic materials 0.000 claims description 6
- 239000011148 porous material Substances 0.000 claims description 6
- 239000002202 Polyethylene glycol Substances 0.000 claims description 5
- 150000001263 acyl chlorides Chemical group 0.000 claims description 5
- LEONUFNNVUYDNQ-UHFFFAOYSA-N vanadium atom Chemical compound [V] LEONUFNNVUYDNQ-UHFFFAOYSA-N 0.000 claims description 5
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 4
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 4
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 claims description 4
- OFBQJSOFQDEBGM-UHFFFAOYSA-N Pentane Chemical compound CCCCC OFBQJSOFQDEBGM-UHFFFAOYSA-N 0.000 claims description 4
- -1 aromatic organic compound Chemical class 0.000 claims description 4
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 claims description 4
- TVMXDCGIABBOFY-UHFFFAOYSA-N octane Chemical compound CCCCCCCC TVMXDCGIABBOFY-UHFFFAOYSA-N 0.000 claims description 4
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 claims description 3
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 claims description 3
- 229910052804 chromium Inorganic materials 0.000 claims description 3
- 239000011651 chromium Substances 0.000 claims description 3
- PNDPGZBMCMUPRI-UHFFFAOYSA-N iodine Chemical compound II PNDPGZBMCMUPRI-UHFFFAOYSA-N 0.000 claims description 3
- 229910052742 iron Inorganic materials 0.000 claims description 3
- VMZCDNSFRSVYKQ-UHFFFAOYSA-N 2-phenylacetyl chloride Chemical compound ClC(=O)CC1=CC=CC=C1 VMZCDNSFRSVYKQ-UHFFFAOYSA-N 0.000 claims description 2
- MFEILWXBDBCWKF-UHFFFAOYSA-N 3-phenylpropanoyl chloride Chemical compound ClC(=O)CCC1=CC=CC=C1 MFEILWXBDBCWKF-UHFFFAOYSA-N 0.000 claims description 2
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 claims description 2
- 239000004372 Polyvinyl alcohol Substances 0.000 claims description 2
- 229920002125 Sokalan® Polymers 0.000 claims description 2
- FYXKZNLBZKRYSS-UHFFFAOYSA-N benzene-1,2-dicarbonyl chloride Chemical compound ClC(=O)C1=CC=CC=C1C(Cl)=O FYXKZNLBZKRYSS-UHFFFAOYSA-N 0.000 claims description 2
- FDQSRULYDNDXQB-UHFFFAOYSA-N benzene-1,3-dicarbonyl chloride Chemical compound ClC(=O)C1=CC=CC(C(Cl)=O)=C1 FDQSRULYDNDXQB-UHFFFAOYSA-N 0.000 claims description 2
- PASDCCFISLVPSO-UHFFFAOYSA-N benzoyl chloride Chemical compound ClC(=O)C1=CC=CC=C1 PASDCCFISLVPSO-UHFFFAOYSA-N 0.000 claims description 2
- 229910052740 iodine Inorganic materials 0.000 claims description 2
- 239000011630 iodine Substances 0.000 claims description 2
- 239000004584 polyacrylic acid Substances 0.000 claims description 2
- 229920002451 polyvinyl alcohol Polymers 0.000 claims description 2
- 229920000036 polyvinylpyrrolidone Polymers 0.000 claims description 2
- 239000001267 polyvinylpyrrolidone Substances 0.000 claims description 2
- 235000013855 polyvinylpyrrolidone Nutrition 0.000 claims description 2
- 230000008569 process Effects 0.000 claims description 2
- LXEJRKJRKIFVNY-UHFFFAOYSA-N terephthaloyl chloride Chemical compound ClC(=O)C1=CC=C(C(Cl)=O)C=C1 LXEJRKJRKIFVNY-UHFFFAOYSA-N 0.000 claims description 2
- 238000004519 manufacturing process Methods 0.000 claims 11
- 125000003118 aryl group Chemical group 0.000 claims 1
- 229940113088 dimethylacetamide Drugs 0.000 claims 1
- 239000005416 organic matter Substances 0.000 claims 1
- 239000002952 polymeric resin Substances 0.000 abstract description 15
- 239000000126 substance Substances 0.000 abstract description 7
- 238000010382 chemical cross-linking Methods 0.000 abstract description 4
- 238000004132 cross linking Methods 0.000 abstract description 3
- 229920003002 synthetic resin Polymers 0.000 abstract description 3
- 150000002500 ions Chemical class 0.000 description 32
- 239000010408 film Substances 0.000 description 30
- 238000002156 mixing Methods 0.000 description 21
- 230000000052 comparative effect Effects 0.000 description 12
- 229920000620 organic polymer Polymers 0.000 description 12
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 6
- 229910001456 vanadium ion Inorganic materials 0.000 description 5
- 238000007790 scraping Methods 0.000 description 4
- 238000003756 stirring Methods 0.000 description 4
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical group [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 3
- 238000004146 energy storage Methods 0.000 description 3
- 238000005516 engineering process Methods 0.000 description 3
- 238000005342 ion exchange Methods 0.000 description 3
- 239000003014 ion exchange membrane Substances 0.000 description 3
- 230000015572 biosynthetic process Effects 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 239000003792 electrolyte Substances 0.000 description 2
- 230000010220 ion permeability Effects 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 239000003960 organic solvent Substances 0.000 description 2
- 229910052684 Cerium Inorganic materials 0.000 description 1
- KRHYYFGTRYWZRS-UHFFFAOYSA-M Fluoride anion Chemical group [F-] KRHYYFGTRYWZRS-UHFFFAOYSA-M 0.000 description 1
- 229920000557 Nafion® Polymers 0.000 description 1
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 1
- 238000003917 TEM image Methods 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- UWCPYKQBIPYOLX-UHFFFAOYSA-N benzene-1,3,5-tricarbonyl chloride Chemical compound ClC(=O)C1=CC(C(Cl)=O)=CC(C(Cl)=O)=C1 UWCPYKQBIPYOLX-UHFFFAOYSA-N 0.000 description 1
- 230000000903 blocking effect Effects 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- GWXLDORMOJMVQZ-UHFFFAOYSA-N cerium Chemical compound [Ce] GWXLDORMOJMVQZ-UHFFFAOYSA-N 0.000 description 1
- 230000008094 contradictory effect Effects 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
- 230000005611 electricity Effects 0.000 description 1
- 238000012983 electrochemical energy storage Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- UQSQSQZYBQSBJZ-UHFFFAOYSA-N fluorosulfonic acid Chemical compound OS(F)(=O)=O UQSQSQZYBQSBJZ-UHFFFAOYSA-N 0.000 description 1
- 229910002804 graphite Inorganic materials 0.000 description 1
- 239000010439 graphite Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 230000007246 mechanism Effects 0.000 description 1
- 238000000614 phase inversion technique Methods 0.000 description 1
- 238000000053 physical method Methods 0.000 description 1
- 239000000523 sample Substances 0.000 description 1
- 239000012488 sample solution Substances 0.000 description 1
- 238000012216 screening Methods 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 238000002791 soaking Methods 0.000 description 1
- 230000007480 spreading Effects 0.000 description 1
- 238000003892 spreading Methods 0.000 description 1
- 235000011149 sulphuric acid Nutrition 0.000 description 1
- 230000001360 synchronised effect Effects 0.000 description 1
- 239000010409 thin film Substances 0.000 description 1
Classifications
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M8/00—Fuel cells; Manufacture thereof
- H01M8/02—Details
- H01M8/0202—Collectors; Separators, e.g. bipolar separators; Interconnectors
- H01M8/023—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
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M2300/00—Electrolytes
- H01M2300/0017—Non-aqueous electrolytes
- H01M2300/0065—Solid electrolytes
- H01M2300/0082—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
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P70/00—Climate change mitigation technologies in the production process for final industrial or consumer products
- Y02P70/50—Manufacturing or production processes characterised by the final manufactured product
Abstract
A high-performance ultrathin porous membrane for a flow battery and preparation and application thereof, wherein the method comprises the following steps: paving a liquid phase raw material dissolved with resin X and resin Y on a device capable of preparing a planar film, immersing the liquid phase raw material dissolved with resin in a liquid phase system containing a cross-linking agent, and standing to form a film I; the resin Y is water-soluble resin; the liquid phase raw material comprises good solvents of resin X and resin Y; the liquid phase system comprises a poor solvent A of the resin X and the resin Y; transferring the film I into a poor solvent A or a poor solvent B of the resin X and the resin Y, and standing to obtain a composite film containing the film I and the film II; after the membrane II is stripped, a high-performance ultrathin porous membrane is obtained, and a chemical crosslinking polymer chain formed by crosslinking reaction between the organic high polymer resin X and the organic high polymer resin Y ensures high ion selectivity of the membrane, good chemical stability and mechanical strength, and meets the requirement of battery assembly.
Description
Technical Field
The invention relates to the research field of flow batteries, in particular to application of a high-performance ultrathin porous membrane in a flow battery.
Background
The flow battery is a large-scale electrochemical energy storage technology, has the advantages of long cycle life, high safety, mutually independent power and capacity and the like, and can be widely applied to renewable energy sources such as wind energy, solar energy and the like for generating electricity and storing energy, thereby realizing the large-scale application of the renewable energy sources. The all-vanadium redox flow battery (VFB) energy storage technology is one of the preferred technologies for large-scale efficient energy storage due to the characteristics of high safety, long service life, large output power and energy storage capacity, good charge-discharge cycle performance, environmental friendliness and the like.
The film is one of the key materials of the VFB, plays a role in blocking cross blending of vanadium ions in positive and negative electrolyte and simultaneously transmitting hydrogen ions to form a battery loop, and the performance of the battery loop directly influences the performance of a battery system. The ideal membrane should have the characteristics of high ion selectivity, high ion conductivity, high chemical stability and low cost. Currently, the most widely used commercial membrane is the perfluorosulfonic acid ion exchange membrane (Nafion) produced by dupont, usa. However, the problems of poor ion selectivity, high price and the like limit the industrial application. The non-fluoride ion exchange membrane becomes a research hot spot because of the advantages of low cost, good thermal stability and mechanical stability, high ion selectivity and the like. But the chemical stability of the membrane is greatly reduced due to the introduction of the ion exchange groups. The ion conduction membrane utilizes the aperture screening mechanism and the charge rejection effect, realizes the selective separation of vanadium ions and protons, breaks through the limitation of the traditional ion exchange membrane, gets rid of the dependence on ion exchange groups, and fundamentally solves the problem of poor membrane stability caused by the introduction of the ion exchange groups.
There is a contradictory relationship between ion selectivity and ion conductivity of the membrane. Dense membranes tend to have high ion selectivity but low ion conductivity, while porous membranes tend to have high ion conductivity but low ion selectivity. The ultrathin film is beneficial to further reducing the internal resistance of the film and improving the ionic conductivity, but can influence the chemical stability and the mechanical strength of the film. Therefore, designing a new preparation method for preparing the ultrathin porous membrane is a bottleneck for improving the ion conductivity of the membrane and synchronously improving the ion selectivity, chemical stability and mechanical strength of the membrane.
Disclosure of Invention
Aiming at the contradiction relation between the ion selectivity and the ion conductivity of the all-vanadium redox flow battery membrane, the invention provides a novel method for preparing a high-performance ultrathin porous membrane, which has the advantages of simple preparation method, environment-friendly process, good chemical stability, excellent ion selectivity, good ion conductivity and good mechanical property.
In one aspect, the invention provides a method for preparing a porous ion-conducting membrane, comprising the steps of:
step (1) paving a liquid phase raw material dissolved with resin X and resin Y on a device capable of preparing a planar film, immersing the liquid phase raw material dissolved with resin in a liquid phase system containing a cross-linking agent, and standing to form a film I;
the resin Y is water-soluble resin;
the liquid phase raw material comprises good solvents of resin X and resin Y;
the liquid phase system comprises a poor solvent A of the resin X and the resin Y;
transferring the film I into a poor solvent A or a poor solvent B of the resin X and the resin Y, and standing to obtain a composite film containing the film I and the film II;
and (3) stripping the membrane II to obtain the porous ion conducting membrane.
The stripping is typically performed by conventional physical methods.
Preferably, in the step (1), the good solvent of the resin X and the resin Y is at least one of dimethyl sulfoxide (DMSO), N-Dimethylacetamide (DMAC), N-methylpyrrolidone (NMP), and N, N-Dimethylformamide (DMF).
Preferably, in the step (1), the mass ratio of the cross-linking agent to the resin is more than or equal to 0.01;
in the liquid phase system, the ratio of the poor solvent A to the crosslinking agent is (0.001-15) 100g/ml.
Preferably, in step (1), the resin X is a polybenzimidazole-based polymer;
at least one of polyethylene glycol, polyacrylic acid, polyvinylpyrrolidone and polyvinyl alcohol serving as the resin Y;
the mass ratio of the resin X to the resin Y is 1: (0.01-3); preferably 1: (0.6-1.5);
preferably, the concentration of the resin X in the liquid phase raw material is 5-30wt%; preferably, the concentration is 10-20wt%, and the concentration of the resin Y in the liquid phase raw material is 5-30wt%; the preferred concentration is 6 to 30wt%.
Preferably, in the step (1), the cross-linking agent is at least one aromatic organic compound containing acyl chloride functional groups;
preferably, the aromatic organic compound containing acyl chloride functional group is at least one of benzoyl chloride, phthaloyl chloride, isophthaloyl chloride, terephthaloyl chloride, 1,3, 5-benzene tricarboxylic acid chloride, phenylacetyl chloride and phenylpropionyl chloride.
Preferably, the poor solvent A is at least one of n-hexane, n-heptane, n-octane, n-pentane and cyclohexane;
the poor solvent B is at least one of water, ethanol, isopropanol or acetone.
The invention also provides the porous ion conducting membrane obtained by the preparation method, which is characterized in that the membrane thickness is less than or equal to 10 mu m; preferably, the film thickness is 5 μm or less.
Preferably, the elongation at break of the film is greater than or equal to 14%; the tensile strength is more than or equal to 41MPa; the elastic modulus is more than or equal to 643MPa; VO (VO) 2 + The permeation rate is less than or equal to 2.31 multiplied by 10 -6 cm 2 /h; the area resistance is less than or equal to 0.041 ohm/cm 2 The method comprises the steps of carrying out a first treatment on the surface of the The pore diameter is 300-1000nm.
The invention also provides application of the porous ion conducting membrane in a flow battery.
Preferably, the flow battery comprises an all-vanadium flow battery, a zinc/bromine flow battery, a zinc/iodine flow battery, an iron/chromium flow battery, or a vanadium/bromine flow battery.
Advantageous effects
1. The invention provides a method for preparing a high-performance ultrathin porous membrane, which is simple to operate, easy to amplify and engineer and has a very high application prospect.
2. The high-performance ultrathin porous membrane prepared by the invention ensures high ion selectivity, good chemical stability and higher mechanical property of the membrane by the chemical crosslinking polymer chain formed by the crosslinking reaction between the organic high polymer resin X and the crosslinking agent, and meets the requirement of battery assembly.
3. The high-performance ultrathin porous membrane prepared by the invention has the advantages that the organic polymer resin Y is completely dissolved in water, a large number of pore structures are formed on the surface and in the membrane, but chemical crosslinking polymer chains formed are not damaged, so that the ionic conductivity of the membrane is greatly improved, and the high ionic selectivity of the membrane is maintained.
4. The preparation method provided by the invention has universality and can be widely used for preparing various polymer porous membranes.
5. The high-performance ultrathin porous membrane prepared by the invention can be applied to a flow battery, and can obtain excellent battery performance, in particular higher voltage efficiency.
Drawings
FIG. 1 is a cross-sectional TEM image of a high performance ultrathin porous membrane.
Detailed Description
The preparation process of the ultrathin film comprises the steps of dissolving raw materials of organic polymer resin X and organic polymer resin Y in an organic solvent, spreading the raw materials on a flat plate, immersing the raw materials in poor solvent bath A of the organic polymer resin X and the organic polymer resin Y containing cross-linking agents for a certain time, transferring the raw materials into poor solvent bath B of the organic polymer resin X and the organic polymer resin Y for curing, transferring the raw materials into water after the raw materials are completely cured, dissolving the organic polymer resin B to form a pore structure, and preparing the ultrathin porous film.
The ion conducting membrane is prepared by the following steps:
(1) Dissolving organic polymer resin X and Y in an organic solvent, fully stirring for 5-24 hours at the temperature of 10-50 ℃ to prepare a uniform blending solution, and standing for 6-48 hours at normal temperature to remove bubbles in the blending solution;
(2) Pouring the blending solution prepared in the step (1) on one side of a flat plate, volatilizing the solvent for 0-60 s, scraping the blending solution on the flat plate by using a scraper with the thickness of 5-50 mu m, and immersing the blending solution into a poor solvent A of resin containing a cross-linking agent at the temperature of-20-70 ℃ for 10 s-100 min; and then transferred to poor solvent B of the resin until it is completely cured.
(3) Transferring the film completely solidified in the step (2) into water, completely dissolving the organic polymer resin Y, forming a pore structure on the surface of the film and in the film, and finally forming an ultrathin porous film with the thickness of 1-10 mu m;
the ultrathin porous membrane can be used in flow batteries including, but not limited to, all-vanadium, zinc/bromine, zinc/iodine, iron/chromium, vanadium/bromine, or zinc/cerium flow batteries.
Example 1
The ion conducting membrane is prepared by the following steps:
(1) Dissolving polybenzimidazole and polyethylene glycol in DMAc, fully stirring for 24 hours at the temperature of 20 ℃ to prepare a uniform blending solution, and standing for 24 hours at normal temperature to remove bubbles in the blending solution; wherein the PBI concentration is 12wt% and the PEG concentration is 12wt%.
(2) Pouring the blending solution prepared in the step (1) on one side of a flat plate, volatilizing the solvent for 10s, scraping the blending solution on the flat plate by using a 10 mu m scraper, and immersing the blending solution into n-heptane solution containing 1,3, 5-benzene trimethyl chloride at 20 ℃ for 10s, wherein each 100mL of n-heptane contains 0.01g of 1,3, 5-benzene trimethyl chloride; then transferring the mixture into water to be solidified into a film. The formed membrane is an ultrathin porous membrane with a double-layer structure of a crosslinked layer and a supporting layer, wherein the thickness of the crosslinked layer is 100nm, the aperture is 500nm, and the membrane thickness is 2 mu m.
Examples 2 to 14
The parameters in Table 1 below were changed and the other conditions were the same as in example 1.
Comparative example 1
Commercially available Nafion212 membranes.
Comparative example 2
The ion conducting membrane is prepared by the following steps:
(1) Dissolving polybenzimidazole and polyethylene glycol in DMAc, fully stirring for 24 hours at the temperature of 20 ℃ to prepare a uniform blending solution, and standing for 24 hours at normal temperature to remove bubbles in the blending solution; wherein the PBI concentration is 20wt% and the PEG concentration is 0.1wt%.
(2) Pouring the blending solution prepared in the step (1) on one side of a flat plate, volatilizing the solvent for 10s, scraping the blending solution on the flat plate by using a 10 mu m scraper, and immersing the blending solution into n-heptane solution containing 1,3, 5-benzene trimethyl chloride at 20 ℃ for 10s, wherein each 100mL of n-heptane contains 0.01g of 1,3, 5-benzene trimethyl chloride; then transferring the mixture into water to be solidified into a film. The formed film is an ultrathin compact film with a double-layer structure of a crosslinked layer and a supporting layer, wherein the thickness of the crosslinked layer is 130nm, and the film thickness is 2 mu m.
Comparative example 3
The ion conducting membrane is prepared by the following steps:
(1) Dissolving polybenzimidazole and polyethylene glycol in DMAc, fully stirring for 24 hours at the temperature of 20 ℃ to prepare a uniform blending solution, and standing for 24 hours at normal temperature to remove bubbles in the blending solution; wherein the PBI concentration is 10wt% and the PEG concentration is 60deg.C.
(2) Pouring the blending solution prepared in the step (1) on one side of a flat plate, volatilizing the solvent for 10s, scraping the blending solution on the flat plate by using a 10 mu m scraper, and immersing the blending solution into n-heptane solution containing 1,3, 5-benzene trimethyl chloride at 20 ℃ for 10s, wherein each 100mL of n-heptane contains 0.01g of 1,3, 5-benzene trimethyl chloride; then transferred to water where no film formation was found.
TABLE 1 preparation parameters of high Performance ultrathin porous films
TABLE 2 Properties of high Performance ultrathin porous films
Ultra-thin film assembled vanadium redox flow battery with ultra-high mechanical strength prepared by reaction induced phase inversion method, wherein the catalytic layer is activated carbon felt, the bipolar plate is graphite plate, and the effective area of the film is 48cm 2 The current density was 80mA.cm -2 The concentration of vanadium ions in the electrolyte is 1.50mol L -1 H2SO4 concentration of 3mol L -1 . From the aspect of battery performance, the coulombic efficiency, the voltage efficiency and the energy efficiency of the embodiment are all higher than those of the comparative example, which shows that the composite membrane can realize synchronous improvement of ion selectivity and ion conductivity, and is more suitable for a flow battery system. Comparative example 1 has low coulombic efficiency and poor ion selectivity. Comparative example 2 formed a dense film with high coulombic efficiency and high ion selectivity but low voltage efficiency and low ionic conductivity. Comparative example 3PEG content was too high and film formation was impossible after dissolution in water. From the mechanical point of view, the examples have a high tensile strength, a high modulus of elasticity and a high elongation at break at the same time. This is brought about by the double layer structure of the crosslinked layer and the support layer that the ion-conducting membrane has.
Selecting VO stable in air 2+ The ion selectivity of the comparative and examples was evaluated. The test comprises two chambers separated by a membrane with an effective area of 3×3, and a left chamber filled with 80ml1.5mol L -1 VOSO 4 +3.0mol L -1 H 2 SO 4 The right chamber was filled with 80ml of 1.5mol L solution -1 MgSO 4 +3.0mol L -1 H 2 SO 4 A solution. During the test, 3mL of sample solution was taken out of the right chamber at 24 hours intervals, and at the same time 3mL of 1.5mol L was added to the right chamber while the sample was taken out -1 MgSO 4 +3.0mol L -1 H 2 SO 4 The solution was kept constant in volume.
The ionic conductivity of the comparative examples and examples can be evaluated for the area resistance and tested by an ac impedance tester. The test pool is divided into two chambers by a circular membrane with the effective diameter of 1cm, and the chambers are filled with 3.0mol L -1 H 2 SO 4 The solution, the conductivity of which was measured. Test cell before test, comparative example and example were at 3.0mol L -1 H 2 SO 4 Soaking in the solution thoroughly.
The vanadium ion permeability and sheet resistance test results are shown in Table 3. The results show that the vanadium resistance of the examples is far greater than that of the comparative examples, and the surface resistance is far smaller than that of the comparative examples, because the prepared high-performance ultrathin porous membrane is ensured by chemical crosslinking polymer chains formed by crosslinking reaction between the organic polymer resin A and the organic matters A. Meanwhile, the organic polymer resin B is completely dissolved in water, a large number of pore structures are formed on the surface and in the membrane, and the ion conductivity of the membrane can be further improved while the high ion selectivity is maintained.
TABLE 3 vanadium ion permeability and sheet resistance of high Performance ultrathin porous films
Claims (17)
1. A method for preparing a porous ion conducting membrane, comprising the steps of:
step (1) paving a liquid phase raw material dissolved with resin X and resin Y on a device capable of preparing a planar film, immersing the liquid phase raw material dissolved with resin in a liquid phase system containing a cross-linking agent, and standing to form a film I;
the resin Y is water-soluble resin;
the liquid phase raw material comprises good solvents of resin X and resin Y;
the liquid phase system comprises a poor solvent A of the resin X and the resin Y;
transferring the film I into a poor solvent A or a poor solvent B of the resin X and the resin Y, and standing to obtain a composite film containing the film I and the film II;
step (3) peeling the membrane II to obtain the porous ion conducting membrane;
in the step (1), the resin X is a polybenzimidazole polymer;
the resin Y is at least one of polyethylene glycol, polyacrylic acid, polyvinylpyrrolidone and polyvinyl alcohol.
2. The method of manufacturing according to claim 1, characterized in that:
in the step (1), the good solvent of the resin X and the resin Y is at least one of dimethyl sulfoxide, dimethyl acetamide, N-methyl pyrrolidone and N, N-dimethylformamide.
3. The method of manufacturing according to claim 1, characterized in that:
in the step (1), the mass ratio of the cross-linking agent to the total mass of the resin X and the resin Y is more than or equal to 0.01;
in the liquid phase system, the ratio of the poor solvent A to the cross-linking agent is (0.001-15) g/100 ml.
4. The method of manufacturing according to claim 1, characterized in that:
the mass ratio of the resin X to the resin Y is 1: (0.01-3).
5. The method of manufacturing according to claim 1, characterized in that:
the mass ratio of the resin X to the resin Y is 1: (0.6-1.5).
6. The method of manufacturing according to claim 1, characterized in that:
the concentration of the resin X in the liquid phase raw material is 5wt% -30 wt%.
7. The method of manufacturing according to claim 1, characterized in that:
the concentration of the resin X in the liquid phase raw material is 10wt% -20 wt%.
8. The method of manufacturing according to claim 1, characterized in that:
the concentration of the resin Y in the liquid phase raw material is 5-30 wt%.
9. The method of manufacturing according to claim 1, characterized in that:
the concentration of the resin Y in the liquid phase raw material is 6-30 wt%.
10. The method of manufacturing according to claim 1, characterized in that:
in the step (1), the cross-linking agent is at least one aromatic organic compound containing acyl chloride functional groups.
11. The method of manufacturing according to claim 10, wherein:
the aromatic organic matter containing acyl chloride functional group is at least one of benzoyl chloride, phthaloyl chloride, isophthaloyl chloride, terephthaloyl chloride, 1,3, 5-benzene trimethyl acyl chloride, phenylacetyl chloride and phenylpropionyl chloride.
12. The method of manufacturing according to claim 1, characterized in that:
the poor solvent A is at least one of n-hexane, n-heptane, n-octane, n-pentane and cyclohexane;
the poor solvent B is at least one of water, ethanol, isopropanol or acetone.
13. A porous ion-conducting membrane obtainable by the process according to any one of claims 1 to 12, characterized in that: the thickness of the film is less than or equal to 10 mu m.
14. The porous ion conducting membrane of claim 13, wherein:
the thickness of the film is less than or equal to 5 mu m.
15. The porous ion conducting membrane of claim 13, wherein the elongation at break of the membrane is greater than or equal to 14%; the tensile strength is more than or equal to 41MPa; the elastic modulus is more than or equal to 643MPa; VO (VO) 2 + The permeation rate is less than or equal to 2.31 multiplied by 10 -6 cm 2 /h; the area resistance is less than or equal to 0.041 ohm/cm 2 The method comprises the steps of carrying out a first treatment on the surface of the The pore diameter is 300-1000nm.
16. Use of the porous ion conducting membrane of claim 15 in a flow battery.
17. The use of claim 16, wherein the flow battery comprises an all-vanadium flow battery, a zinc/bromine flow battery, a zinc/iodine flow battery, an iron/chromium flow battery, or a vanadium/bromine flow battery.
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| CN107913600A (en) * | 2017-09-29 | 2018-04-17 | 中国科学院重庆绿色智能技术研究院 | There is compound forward osmosis membrane of proton exchange and preparation method thereof and purposes |
| CN111082117A (en) * | 2018-10-18 | 2020-04-28 | 中国科学院大连化学物理研究所 | Molecular sieve composite membrane and preparation method and application thereof |
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| CN111082117A (en) * | 2018-10-18 | 2020-04-28 | 中国科学院大连化学物理研究所 | Molecular sieve composite membrane and preparation method and application thereof |
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