CN117820719A - Ion exchange membrane, preparation method thereof and flow battery - Google Patents
Ion exchange membrane, preparation method thereof and flow battery Download PDFInfo
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- CN117820719A CN117820719A CN202311821005.6A CN202311821005A CN117820719A CN 117820719 A CN117820719 A CN 117820719A CN 202311821005 A CN202311821005 A CN 202311821005A CN 117820719 A CN117820719 A CN 117820719A
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- porous support
- exchange membrane
- ion exchange
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- 239000003014 ion exchange membrane Substances 0.000 title claims abstract description 28
- 238000002360 preparation method Methods 0.000 title claims abstract description 9
- 239000000243 solution Substances 0.000 claims abstract description 129
- 238000000576 coating method Methods 0.000 claims abstract description 66
- 239000011248 coating agent Substances 0.000 claims abstract description 63
- 239000000178 monomer Substances 0.000 claims abstract description 39
- 239000003085 diluting agent Substances 0.000 claims abstract description 33
- 239000000463 material Substances 0.000 claims abstract description 22
- 238000000034 method Methods 0.000 claims abstract description 20
- 238000005266 casting Methods 0.000 claims abstract description 13
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 claims abstract description 10
- 239000007864 aqueous solution Substances 0.000 claims abstract description 9
- 238000001192 hot extrusion Methods 0.000 claims abstract description 8
- 150000001263 acyl chlorides Chemical class 0.000 claims abstract description 7
- 238000006116 polymerization reaction Methods 0.000 claims abstract description 3
- 150000002500 ions Chemical class 0.000 claims description 31
- 239000004695 Polyether sulfone Substances 0.000 claims description 30
- 229920006393 polyether sulfone Polymers 0.000 claims description 30
- 238000001816 cooling Methods 0.000 claims description 25
- RWCCWEUUXYIKHB-UHFFFAOYSA-N benzophenone Chemical compound C=1C=CC=CC=1C(=O)C1=CC=CC=C1 RWCCWEUUXYIKHB-UHFFFAOYSA-N 0.000 claims description 20
- 229920002492 poly(sulfone) Polymers 0.000 claims description 17
- 239000012965 benzophenone Substances 0.000 claims description 16
- 125000003277 amino group Chemical group 0.000 claims description 14
- -1 polypropylene Polymers 0.000 claims description 10
- NGNBDVOYPDDBFK-UHFFFAOYSA-N 2-[2,4-di(pentan-2-yl)phenoxy]acetyl chloride Chemical compound CCCC(C)C1=CC=C(OCC(Cl)=O)C(C(C)CCC)=C1 NGNBDVOYPDDBFK-UHFFFAOYSA-N 0.000 claims description 6
- YEJRWHAVMIAJKC-UHFFFAOYSA-N 4-Butyrolactone Chemical compound O=C1CCCO1 YEJRWHAVMIAJKC-UHFFFAOYSA-N 0.000 claims description 4
- NIQCNGHVCWTJSM-UHFFFAOYSA-N Dimethyl phthalate Chemical compound COC(=O)C1=CC=CC=C1C(=O)OC NIQCNGHVCWTJSM-UHFFFAOYSA-N 0.000 claims description 4
- ZFOZVQLOBQUTQQ-UHFFFAOYSA-N Tributyl citrate Chemical compound CCCCOC(=O)CC(O)(C(=O)OCCCC)CC(=O)OCCCC ZFOZVQLOBQUTQQ-UHFFFAOYSA-N 0.000 claims description 4
- 150000001491 aromatic compounds Chemical class 0.000 claims description 4
- FLKPEMZONWLCSK-UHFFFAOYSA-N diethyl phthalate Chemical compound CCOC(=O)C1=CC=CC=C1C(=O)OCC FLKPEMZONWLCSK-UHFFFAOYSA-N 0.000 claims description 4
- 238000002844 melting Methods 0.000 claims description 4
- 230000008018 melting Effects 0.000 claims description 4
- QPJVMBTYPHYUOC-UHFFFAOYSA-N methyl benzoate Chemical compound COC(=O)C1=CC=CC=C1 QPJVMBTYPHYUOC-UHFFFAOYSA-N 0.000 claims description 4
- OSWPMRLSEDHDFF-UHFFFAOYSA-N methyl salicylate Chemical compound COC(=O)C1=CC=CC=C1O OSWPMRLSEDHDFF-UHFFFAOYSA-N 0.000 claims description 4
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- URAYPUMNDPQOKB-UHFFFAOYSA-N triacetin Chemical compound CC(=O)OCC(OC(C)=O)COC(C)=O URAYPUMNDPQOKB-UHFFFAOYSA-N 0.000 claims description 4
- 229920013636 polyphenyl ether polymer Polymers 0.000 claims description 3
- 230000008569 process Effects 0.000 claims description 3
- YBBRCQOCSYXUOC-UHFFFAOYSA-N sulfuryl dichloride Chemical group ClS(Cl)(=O)=O YBBRCQOCSYXUOC-UHFFFAOYSA-N 0.000 claims description 3
- LTMRRSWNXVJMBA-UHFFFAOYSA-L 2,2-diethylpropanedioate Chemical compound CCC(CC)(C([O-])=O)C([O-])=O LTMRRSWNXVJMBA-UHFFFAOYSA-L 0.000 claims description 2
- FPZWZCWUIYYYBU-UHFFFAOYSA-N 2-(2-ethoxyethoxy)ethyl acetate Chemical compound CCOCCOCCOC(C)=O FPZWZCWUIYYYBU-UHFFFAOYSA-N 0.000 claims description 2
- QZCLKYGREBVARF-UHFFFAOYSA-N Acetyl tributyl citrate Chemical compound CCCCOC(=O)CC(C(=O)OCCCC)(OC(C)=O)CC(=O)OCCCC QZCLKYGREBVARF-UHFFFAOYSA-N 0.000 claims description 2
- 239000002033 PVDF binder Substances 0.000 claims description 2
- 239000004693 Polybenzimidazole Substances 0.000 claims description 2
- 239000004698 Polyethylene Substances 0.000 claims description 2
- 229920000491 Polyphenylsulfone Polymers 0.000 claims description 2
- 239000004743 Polypropylene Substances 0.000 claims description 2
- 150000007824 aliphatic compounds Chemical class 0.000 claims description 2
- 235000010290 biphenyl Nutrition 0.000 claims description 2
- 239000004305 biphenyl Substances 0.000 claims description 2
- JBSLOWBPDRZSMB-FPLPWBNLSA-N dibutyl (z)-but-2-enedioate Chemical compound CCCCOC(=O)\C=C/C(=O)OCCCC JBSLOWBPDRZSMB-FPLPWBNLSA-N 0.000 claims description 2
- FBSAITBEAPNWJG-UHFFFAOYSA-N dimethyl phthalate Natural products CC(=O)OC1=CC=CC=C1OC(C)=O FBSAITBEAPNWJG-UHFFFAOYSA-N 0.000 claims description 2
- 229960001826 dimethylphthalate Drugs 0.000 claims description 2
- OEIWPNWSDYFMIL-UHFFFAOYSA-N dioctyl benzene-1,4-dicarboxylate Chemical compound CCCCCCCCOC(=O)C1=CC=C(C(=O)OCCCCCCCC)C=C1 OEIWPNWSDYFMIL-UHFFFAOYSA-N 0.000 claims description 2
- ROORDVPLFPIABK-UHFFFAOYSA-N diphenyl carbonate Chemical compound C=1C=CC=CC=1OC(=O)OC1=CC=CC=C1 ROORDVPLFPIABK-UHFFFAOYSA-N 0.000 claims description 2
- 239000001087 glyceryl triacetate Substances 0.000 claims description 2
- 235000013773 glyceryl triacetate Nutrition 0.000 claims description 2
- 150000002576 ketones Chemical class 0.000 claims description 2
- 229940095102 methyl benzoate Drugs 0.000 claims description 2
- 229960001047 methyl salicylate Drugs 0.000 claims description 2
- ZUOUZKKEUPVFJK-UHFFFAOYSA-N phenylbenzene Natural products C1=CC=CC=C1C1=CC=CC=C1 ZUOUZKKEUPVFJK-UHFFFAOYSA-N 0.000 claims description 2
- 229920002239 polyacrylonitrile Polymers 0.000 claims description 2
- 229920002480 polybenzimidazole Polymers 0.000 claims description 2
- 229920000573 polyethylene Polymers 0.000 claims description 2
- 229920001155 polypropylene Polymers 0.000 claims description 2
- 229920002981 polyvinylidene fluoride Polymers 0.000 claims description 2
- RUOJZAUFBMNUDX-UHFFFAOYSA-N propylene carbonate Chemical compound CC1COC(=O)O1 RUOJZAUFBMNUDX-UHFFFAOYSA-N 0.000 claims description 2
- 230000035484 reaction time Effects 0.000 claims description 2
- 239000007858 starting material Substances 0.000 claims description 2
- HXJUTPCZVOIRIF-UHFFFAOYSA-N sulfolane Chemical compound O=S1(=O)CCCC1 HXJUTPCZVOIRIF-UHFFFAOYSA-N 0.000 claims description 2
- 229960002622 triacetin Drugs 0.000 claims description 2
- STCOOQWBFONSKY-UHFFFAOYSA-N tributyl phosphate Chemical compound CCCCOP(=O)(OCCCC)OCCCC STCOOQWBFONSKY-UHFFFAOYSA-N 0.000 claims description 2
- DQWPFSLDHJDLRL-UHFFFAOYSA-N triethyl phosphate Chemical compound CCOP(=O)(OCC)OCC DQWPFSLDHJDLRL-UHFFFAOYSA-N 0.000 claims description 2
- LSNNMFCWUKXFEE-UHFFFAOYSA-M Bisulfite Chemical compound OS([O-])=O LSNNMFCWUKXFEE-UHFFFAOYSA-M 0.000 claims 1
- 239000012528 membrane Substances 0.000 abstract description 29
- 238000012695 Interfacial polymerization Methods 0.000 abstract description 4
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- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 72
- 239000008346 aqueous phase Substances 0.000 description 45
- 239000012071 phase Substances 0.000 description 42
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 26
- 238000001035 drying Methods 0.000 description 23
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 20
- HVBSAKJJOYLTQU-UHFFFAOYSA-N 4-aminobenzenesulfonic acid Chemical compound NC1=CC=C(S(O)(=O)=O)C=C1 HVBSAKJJOYLTQU-UHFFFAOYSA-N 0.000 description 18
- 239000002904 solvent Substances 0.000 description 18
- 239000000203 mixture Substances 0.000 description 15
- WZCQRUWWHSTZEM-UHFFFAOYSA-N 1,3-phenylenediamine Chemical compound NC1=CC=CC(N)=C1 WZCQRUWWHSTZEM-UHFFFAOYSA-N 0.000 description 10
- 239000008367 deionised water Substances 0.000 description 10
- 229910021641 deionized water Inorganic materials 0.000 description 10
- 239000008213 purified water Substances 0.000 description 10
- 238000005406 washing Methods 0.000 description 10
- 229940018564 m-phenylenediamine Drugs 0.000 description 9
- 229950000244 sulfanilic acid Drugs 0.000 description 9
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 8
- 238000012360 testing method Methods 0.000 description 7
- 238000004132 cross linking Methods 0.000 description 6
- ALIQZUMMPOYCIS-UHFFFAOYSA-N benzene-1,3-disulfonyl chloride Chemical compound ClS(=O)(=O)C1=CC=CC(S(Cl)(=O)=O)=C1 ALIQZUMMPOYCIS-UHFFFAOYSA-N 0.000 description 5
- 230000000052 comparative effect Effects 0.000 description 5
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 4
- 125000003118 aryl group Chemical group 0.000 description 4
- 238000004519 manufacturing process Methods 0.000 description 4
- 230000035699 permeability Effects 0.000 description 4
- 230000005501 phase interface Effects 0.000 description 4
- 229920000642 polymer Polymers 0.000 description 4
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- 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 3
- 238000006243 chemical reaction Methods 0.000 description 3
- 239000002131 composite material Substances 0.000 description 3
- 239000002826 coolant Substances 0.000 description 3
- 238000004146 energy storage Methods 0.000 description 3
- 230000006872 improvement Effects 0.000 description 3
- 239000007788 liquid Substances 0.000 description 3
- 230000001105 regulatory effect Effects 0.000 description 3
- 239000000523 sample Substances 0.000 description 3
- 229910052720 vanadium Inorganic materials 0.000 description 3
- LEONUFNNVUYDNQ-UHFFFAOYSA-N vanadium atom Chemical compound [V] LEONUFNNVUYDNQ-UHFFFAOYSA-N 0.000 description 3
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 description 2
- 229920002873 Polyethylenimine Polymers 0.000 description 2
- 230000032683 aging Effects 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- 238000003490 calendering Methods 0.000 description 2
- 229910052799 carbon Inorganic materials 0.000 description 2
- 230000001276 controlling effect Effects 0.000 description 2
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- 238000000157 electrochemical-induced impedance spectroscopy Methods 0.000 description 2
- 239000003792 electrolyte Substances 0.000 description 2
- IIEWJVIFRVWJOD-UHFFFAOYSA-N ethylcyclohexane Chemical compound CCC1CCCCC1 IIEWJVIFRVWJOD-UHFFFAOYSA-N 0.000 description 2
- 238000000643 oven drying Methods 0.000 description 2
- 238000005191 phase separation Methods 0.000 description 2
- 238000006068 polycondensation reaction Methods 0.000 description 2
- 239000011148 porous material Substances 0.000 description 2
- 125000000542 sulfonic acid group Chemical group 0.000 description 2
- PSDQQCXQSWHCRN-UHFFFAOYSA-N vanadium(4+) Chemical compound [V+4] PSDQQCXQSWHCRN-UHFFFAOYSA-N 0.000 description 2
- HEAHMJLHQCESBZ-UHFFFAOYSA-N 2,5-diaminobenzenesulfonic acid Chemical compound NC1=CC=C(N)C(S(O)(=O)=O)=C1 HEAHMJLHQCESBZ-UHFFFAOYSA-N 0.000 description 1
- LTPSRQRIPCVMKQ-UHFFFAOYSA-N 2-amino-5-methylbenzenesulfonic acid Chemical compound CC1=CC=C(N)C(S(O)(=O)=O)=C1 LTPSRQRIPCVMKQ-UHFFFAOYSA-N 0.000 description 1
- ZMCHBSMFKQYNKA-UHFFFAOYSA-N 2-aminobenzenesulfonic acid Chemical compound NC1=CC=CC=C1S(O)(=O)=O ZMCHBSMFKQYNKA-UHFFFAOYSA-N 0.000 description 1
- RXCMFQDTWCCLBL-UHFFFAOYSA-N 4-amino-3-hydroxynaphthalene-1-sulfonic acid Chemical compound C1=CC=C2C(N)=C(O)C=C(S(O)(=O)=O)C2=C1 RXCMFQDTWCCLBL-UHFFFAOYSA-N 0.000 description 1
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 1
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 description 1
- 238000012696 Interfacial polycondensation Methods 0.000 description 1
- 239000002202 Polyethylene glycol Substances 0.000 description 1
- 229910000831 Steel Inorganic materials 0.000 description 1
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 150000001450 anions Chemical class 0.000 description 1
- 239000012752 auxiliary agent Substances 0.000 description 1
- 229950005499 carbon tetrachloride Drugs 0.000 description 1
- 230000015556 catabolic process Effects 0.000 description 1
- 150000001768 cations Chemical class 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 229960001701 chloroform Drugs 0.000 description 1
- 238000004140 cleaning Methods 0.000 description 1
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- 230000007423 decrease Effects 0.000 description 1
- 238000006731 degradation reaction Methods 0.000 description 1
- 238000001739 density measurement Methods 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- 238000009792 diffusion process Methods 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 239000008151 electrolyte solution Substances 0.000 description 1
- 238000005538 encapsulation Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 235000011187 glycerol Nutrition 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 230000010354 integration Effects 0.000 description 1
- 239000011229 interlayer Substances 0.000 description 1
- 238000005342 ion exchange Methods 0.000 description 1
- 230000010220 ion permeability Effects 0.000 description 1
- 239000011244 liquid electrolyte Substances 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- LNOPIUAQISRISI-UHFFFAOYSA-N n'-hydroxy-2-propan-2-ylsulfonylethanimidamide Chemical compound CC(C)S(=O)(=O)CC(N)=NO LNOPIUAQISRISI-UHFFFAOYSA-N 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 229920001223 polyethylene glycol Polymers 0.000 description 1
- 239000002861 polymer material Substances 0.000 description 1
- 238000010094 polymer processing Methods 0.000 description 1
- 229920000036 polyvinylpyrrolidone Polymers 0.000 description 1
- 239000001267 polyvinylpyrrolidone Substances 0.000 description 1
- 235000013855 polyvinylpyrrolidone Nutrition 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 230000036632 reaction speed Effects 0.000 description 1
- 238000006479 redox reaction Methods 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 239000010959 steel Substances 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 238000005728 strengthening Methods 0.000 description 1
- 229910052717 sulfur Inorganic materials 0.000 description 1
- 239000011593 sulfur Substances 0.000 description 1
- 230000002195 synergetic effect Effects 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- VZGDMQKNWNREIO-UHFFFAOYSA-N tetrachloromethane Chemical compound ClC(Cl)(Cl)Cl VZGDMQKNWNREIO-UHFFFAOYSA-N 0.000 description 1
- 238000002145 thermally induced phase separation Methods 0.000 description 1
- 229910001456 vanadium ion Inorganic materials 0.000 description 1
Classifications
-
- 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
- Manufacture Of Porous Articles, And Recovery And Treatment Of Waste Products (AREA)
Abstract
The invention discloses an ion exchange membrane, a preparation method thereof and a flow battery, which comprises the following steps: s1, mixing raw materials of a porous support layer, and obtaining the porous support layer through a hot extrusion casting method, S2, coating an aqueous solution of an amino-containing monomer and an oil phase solution of an acyl chloride-containing monomer on the porous support layer for polymerization reaction to form an ion selective conductive layer, wherein the raw materials for preparing the porous support layer comprise a porous support layer main body material, an auxiliary material and a diluent. The ion exchange membrane provided by the invention has the advantages that the lower layer provides mechanical support and sealing strength for the high-porosity support layer, and the upper layer is a nano-or submicron-level ion selective conductive layer prepared by adopting interfacial polymerization, so that the problem of low ion conductivity caused by excessive thickness of the traditional membrane material is effectively solved.
Description
Technical Field
The invention relates to the field of research of flow batteries, in particular to an ion exchange membrane, a preparation method thereof and a flow battery.
Background
Flow batteries are an important electric energy storage technology and have been widely used in the fields of energy storage, renewable energy integration, electric vehicles and the like. In flow batteries, the storage and release of energy occurs through redox reactions, a process involving the conduction of an electrolyte in which ion-conducting membranes play a critical role. Ion-conducting membranes are a special material that allows ions (usually cations or anions) to move between the positive and negative electrodes, thereby enabling the cell to operate.
However, despite the potential of flow batteries in the energy storage field, there are still some key technical challenges, mainly related to the preparation and performance of ion conducting membranes. First, ion-conducting membranes are typically formed by phase separation and post-crosslinking, which results in a membrane thickness that is difficult to achieve on a nanoscale or submicron scale, limiting the improvement in ionic conductivity. Second, the uniformity and efficiency of crosslinking during post-crosslinking is difficult to control and improve, which can lead to instability and performance degradation in production. Finally, existing bulk crosslinked ion conductive membranes often suffer from insufficient ductility, which affects service life and performance in devices such as flow batteries.
Therefore, it is urgent to develop an ion exchange membrane.
Disclosure of Invention
The present invention aims to solve at least one of the technical problems existing in the prior art. Therefore, the invention provides a preparation method of an ion exchange membrane, and the prepared ion exchange membrane solves the problem of low ion conductivity of the traditional ion conduction membrane.
The inventive concept of the present invention is as follows:
the ion exchange membrane body prepared by the invention adopts a two-layer composite structure, the lower layer is a high-porosity support layer (porous support layer), the thickness is in the micron level, and the problems of mechanical strength, thermal stability, piezoresistance and membrane wettability of the membrane are mainly solved; the upper layer is a nano-or submicron-level ion selective conducting layer prepared by adopting interfacial polymerization, and mainly solves the problem of improving the ion conductivity and ion selectivity of the membrane material on the nano scale; the membrane material is formed by manufacturing a multi-porous support layer by hot extrusion casting, and then preparing an ion selective conducting layer with a highly cross-linked wholly aromatic structure on the support layer by rapid monomer reaction, wherein in the process of preparing the multi-porous support layer, the charge density of the support layer is improved by the synergistic effect of a main material and an auxiliary material, the ion selective conducting capability of the ion exchange membrane is improved by the auxiliary ion conducting layer, and the ion selective conducting layer is prepared by polycondensation reaction of uniformly coating an aqueous phase monomer and an oil phase monomer solution on the support layer.
A method for preparing an ion exchange membrane according to an embodiment of the first aspect of the present invention includes the steps of:
s1, extruding a casting piece from a main material, an auxiliary material and a diluent through heat to obtain a porous support layer;
s2, coating an aqueous solution of an amino-containing monomer and an oil phase solution of an acyl chloride-containing monomer on the porous support layer for polymerization reaction to form an ion-selective conductive layer;
the main body material of the porous support layer comprises at least one of polysulfone, polyethersulfone, polyvinylidene fluoride, polyphenylsulfone, polyacrylonitrile, naphthyridine diphenyl polyethersulfone ketone, polybenzimidazole, polypropylene and polyethylene;
the auxiliary material comprises at least one of sulfonated polyethersulfone, sulfonated polysulfone, sulfonated polyphenyl ether and sulfonated polytetrafluoroethylene;
the amino group-containing monomer includes an amino group main monomer; the amino group main monomer includes an aromatic compound or an aliphatic compound having at least two amino groups.
1. According to the invention, high-efficiency low-cost mass production can be realized through the hot extrusion casting sheet, meanwhile, the pore diameter of the prepared porous support body layer is small and dense, and on the other hand, the polymer processing concentration can be improved through the hot extrusion casting sheet method, so that the support body layer with higher mechanical strength is obtained, and an additional mechanical strengthening layer is not needed. The hot extrusion casting sheet forming method is also called a thermally induced phase separation film forming method, and the polymer and the diluent are melted at high temperature to obtain polymer molten liquid, and then the molten liquid is cooled, solidified and formed after rapid cooling. The method can obtain the porous support layer with high concentration, which is beneficial to improving the mechanical strength and the stability of the membrane body of the support layer.
2. The invention adopts the mode of carrying out interfacial polymerization of two monomers at an oil-water phase interface by adopting an aqueous solution of an amino-containing monomer and an oil-phase solution of an acyl chloride-containing monomer to prepare the ion selective conducting layer, and rapidly carries out polycondensation reaction to form the ion conducting layer with a high cross-linking structure. Since the oil phase interface and the water phase interface are generally on the nanometer scale in thickness, the thickness of the ion-selective conductive layer formed by the oil-water phase interface reaction is also on the nanometer scale.
3. The ion exchange membrane prepared by the invention fully plays the functional characteristics of each layer of structure, so that the flow battery has higher coulombic efficiency, voltage efficiency and energy efficiency; the preparation method is simple, high pollution auxiliary agent is not needed, the production cost is low, the raw material price is low, and the reaction speed is high.
According to some embodiments of the invention, the amino-based monomer comprises at least one of meta-phenylenediamine and polyethyleneimine.
According to some embodiments of the invention, the content of the auxiliary material in the porous support layer is 0.1 to 10wt%.
According to some embodiments of the invention, the porous support layer is prepared from a starting material further comprising a pore former comprising at least one of polyethylene glycol, polyvinylpyrrolidone, and glycerin.
According to the invention, the porosity of the support layer can be effectively regulated and controlled by regulating and controlling the concentration of the diluent and the pore-forming agent and the cooling speed.
According to some embodiments of the invention, the diluent comprises at least one of sulfolane, dimethyl phthalate, diphenyl carbonate, tributyl citrate, glyceryl triacetate, tributyl phosphate, triethyl phosphate, propylene carbonate, gamma-butyrolactone, benzophenone, methyl benzoate, diethyl phthalate, methyl salicylate, diethyl malonate, tributyl acetylcitrate, dibutyl maleate, dioctyl terephthalate, 1-butyl-3-methylimidazolium hexafluorophosphate, and carbitol acetate.
According to some preferred embodiments of the invention, the step of the hot extrusion casting method comprises melting the raw material of the porous support layer and cooling and solidifying the same.
According to some preferred embodiments of the invention, the melting temperature is 80-200 ℃.
According to some preferred embodiments of the invention, the step of the hot extrusion casting method comprises: dispersing the main body material and the auxiliary material of the porous support layer into a diluent to obtain a support layer containing the diluent, heating to 80-200 ℃ to form casting liquid, cooling at 5-60 ℃ after vacuum defoaming, and removing the diluent.
According to some embodiments of the invention, the polymer concentration in the casting solution is 5 to 50wt%.
The improvement of the polymer concentration in the casting solution is beneficial to improving the mechanical strength and the film stability of the support body layer.
According to some embodiments of the invention, the auxiliary material is present in the diluent-containing support layer in an amount of 0.1 to 10wt%.
According to some embodiments of the invention, the step of removing the diluent comprises introducing the diluent-containing support layer into a solvent, rinsing to remove the diluent.
According to some embodiments of the invention, the solvent comprises at least one of tetrachloromethane, trichloromethane, methanol, and ethanol.
According to some embodiments of the invention, the removing the diluent further comprises drying the removed solvent, wherein the drying temperature is 50-100 ℃.
According to some embodiments of the invention, the step of cooling comprises coating a cooling medium via a slot-coating die, the cooling medium having a temperature of 5-60 ℃.
According to some embodiments of the invention, the cooling medium comprises at least one of a temperature controlled steel strip or a cast sheet roll.
According to some embodiments of the invention, the solute of the oil phase solution of the acid chloride-containing monomer comprises an aromatic compound containing at least two acid chloride or at least two sulfonyl chloride groups.
According to some embodiments of the invention, the acid chloride-containing monomer comprises at least one of 1, 3, 5 triazine-2, 4, 6-triacyl chloride, trimesoyl chloride, and 1, 3-benzenedisulfonyl chloride.
According to some embodiments of the invention, the amino monomers further comprise amino auxiliary monomers comprising sulfonic acid amino compounds.
According to some embodiments of the invention, the amino-containing auxiliary monomer comprises at least one of sulfanilic acid, 4-amino-3-hydroxy-1-naphthalene sulfonic acid, 2-aminobenzenesulfonic acid, 4-aminotoluene-3-sulfonic acid, 2, 5-diaminobenzenesulfonic acid, sulfamic acid, and para-aminoanisole-3-sulfonic acid.
According to some embodiments of the invention, the aqueous solution comprising the amino group-containing main monomer has a concentration of 0.1 to 5wt%.
According to some embodiments of the invention, the concentration of the amino-containing auxiliary monomer is 0.1 to 1wt%.
According to some embodiments of the invention, the acid chloride containing monomer has a concentration of 0.05 to 0.5wt% of the oil phase solution.
According to some embodiments of the invention, the solvent of the oil phase solution comprises at least one of ISOPAR G, ISOPAR E, ISOPAR L, cyclohexane, white oil, naphtha, and ethylcyclohexane.
According to some embodiments of the invention, in step S2, the coating amount of the amino group-containing monomer in the aqueous solution coating process is 10 to 120mL/m 2 。
According to some embodiments of the invention, in step S2, the reaction time is 10 to 200S.
According to some embodiments of the invention, step S2 comprises: dissolving an amino group-containing monomer into water at room temperature to obtain an aqueous phase solution; and dissolving the monomer containing the acyl chloride in an oil phase solvent to prepare an oil phase solution. Then coating the aqueous phase solution on the polysulfone supporting layer, wherein the temperature of the solution is 25-30 ℃, and the coating weight is 35-55 mL/m 2 Standing in air for 100s, and removing residual aqueous phase solution by adopting an air knife; coating the oil phase solution on a supporting layer containing aqueous phase solution, wherein the temperature of the solution is 25-30 ℃, and the coating weight is 35-50 mL/m 2 Standing in air for 120s, oven drying at 70deg.C to remove residual oil phase solvent, aging with sodium hydroxide solution with concentration of 0.1wt%, and washing with deionized water to remove residual sodium hydroxide to obtain ion exchange productAnd (5) film changing.
According to the preparation method of the ion exchange membrane, the ion exchange membrane is prepared by compounding the ion selective conducting layer loaded on the porous support layer, and the thickness of the ion selective conducting layer of the ion exchange membrane is 50-300 nm.
The ductility of the ion-conducting membrane is mainly solved through the membrane thickness and the elastic deformation degree of the membrane body, and generally, the thicker the membrane is, the stronger the elastic deformation capability of the membrane body is, and the stronger the encapsulation calendaring sealing capability is. However, in the case of a bulk crosslinked ion conductive membrane, the membrane body becomes thicker and then reduces the ion conductivity, and it is difficult to achieve an efficient balance between the piezoresistance and the ion conductivity. The invention solves the problems through a two-layer composite form, firstly, the support body layer mainly provides calendaring performance, is made of polymer materials and has good calendarability, and secondly, the ductility of the film body is improved by regulating and controlling the thickness and the porosity of the support body. The conductive layer is selected to mainly provide ion conduction capability, so that ultrathin design can be realized, and the conduction efficiency is improved.
According to some embodiments of the invention, the conductive layer is a highly crosslinked wholly aromatic structure.
The high-crosslinking wholly aromatic structure has higher temperature resistance due to the wholly rigid nature thereof; secondly, the highly crosslinked wholly aromatic structure enables the ion conducting layer to have more regular intermolecular free volume distribution, and better ion selectivity can be obtained.
According to some preferred embodiments of the invention, the step S2 includes: coating an amino-containing monomer aqueous solution on a porous supporting layer, removing the residual aqueous solution on the surface of the supporting layer, coating an acyl chloride-containing monomer oil phase solution on the porous supporting layer, carrying out interfacial polycondensation reaction, standing at room temperature for 10-200 s, removing the residual oil phase solvent on the membrane surface, and drying to obtain the ionic membrane for the composite flow battery.
According to some embodiments of the invention, the drying further comprises curing with sodium hydroxide solution.
According to some embodiments of the invention, the sodium hydroxide solution concentration is between 0.1 and 0.5wt%.
Use of an ion exchange membrane according to an embodiment of the third aspect of the invention in a flow battery.
Detailed Description
Embodiments of the present invention are described in detail below, examples of which are shown below, wherein the same or similar reference numerals refer to the same or similar materials or materials having the same or similar functions throughout. The following examples are given by way of illustration only and are not to be construed as limiting the invention. The specific conditions are not noted in the examples and are carried out according to conventional conditions or conditions recommended by the manufacturer. The reagents or apparatus used were conventional products commercially available without the manufacturer's attention.
Example 1
The ion exchange membrane is prepared by the following steps:
s1: dissolving polyethersulfone and sulfonated polyphenyl ether into diphenyl ketone at 140 ℃ to obtain a solution with 15wt%, carrying out vacuum defoamation on the sulfonated polyethersulfone in the mixture with the content of 0.6wt% in-80 Kpa, coating the solution on a cooling roller with the temperature of 20 ℃ through a slit coating die head, cooling to obtain a supporting layer containing a diluent, rinsing with ethanol to remove diphenyl ketone in the supporting layer, and drying the supporting layer without the diluent at 40 ℃ to obtain a porous supporting layer;
s2: 30g of m-phenylenediamine and 4g of sulfanilic acid are dissolved into 1000g of purified water at room temperature to obtain an aqueous phase solution; 10G of 1, 3, 5 triazine-2, 4, 6-triacyl chloride was dissolved in 1000mL of ISOPAR G to prepare an oil phase solution. Then the aqueous phase solution is evenly coated on the polysulfone supporting layer, the temperature of the solution is 30 ℃, and the coating weight is 35mL/m 2 Standing in air for 100s, and removing residual aqueous phase solution by adopting an air knife; coating the oil phase solution on a supporting layer containing aqueous phase solution at 25deg.C with a coating weight of 35mL/m 2 Standing in air for 120s, oven drying to remove residual oil phase solvent, aging at 70deg.C with sodium hydroxide solution with concentration of 0.1wt%, and cleaning with deionized waterRemoving residual sodium hydroxide, thereby preparing the ion exchange membrane.
Example 2
S1: dissolving a mixture of polyether sulfone and sulfonated polyether sulfone into benzophenone at 140 ℃ to obtain a 15wt% solution, wherein the content of sulfonated polyether sulfone in the mixture is 0.5wt%, coating the solution on a cooling roller with the temperature of 20 ℃ through a slit coating die head after-80 KPa vacuum defoamation, cooling to obtain a supporting layer containing a diluent, rinsing with ethanol to remove benzophenone in the supporting layer, removing the supporting layer of the diluent, and drying at 40 ℃ to obtain a porous supporting layer;
s2: 30g of m-phenylenediamine and 4g of sulfanilic acid are dissolved into 1000g of purified water at room temperature to obtain an aqueous phase solution; 10G of 1, 3, 5 triazine-2, 4, 6-triacyl chloride was dissolved in 1000mL of ISOPAR G to prepare an oil phase solution. Then the aqueous phase solution is evenly coated on the polysulfone supporting layer, the temperature of the solution is 25 ℃, and the coating weight is 35mL/m 2 Standing in air for 100s, and removing residual aqueous phase solution by adopting an air knife; coating the oil phase solution on a supporting layer containing aqueous phase solution at 25deg.C with a coating weight of 35mL/m 2 Standing in air for 120s, drying in an oven to remove residual oil phase solvent, curing at 70deg.C with sodium hydroxide solution with concentration of 0.1wt%, and washing with deionized water to remove residual sodium hydroxide.
Example 3
S1: dissolving a mixture of polysulfone and sulfonated polysulfone into benzophenone at 140 ℃ to obtain an 18wt% solution, wherein the content of sulfonated polyethersulfone in the mixture is 0.5wt%, coating the solution on a cooling roller with the temperature of 20 ℃ through a slit coating die head after-80 KPa vacuum defoamation, cooling to obtain a supporting layer containing a diluent, rinsing with ethanol to remove benzophenone in the supporting layer, removing the supporting layer of the diluent, and drying at 40 ℃ to obtain a porous supporting layer;
s2: 30g of m-phenylenediamine and 4g of sulfanilic acid are dissolved into 1000g of purified water at room temperature to obtain an aqueous phase solution; 10g of 1, 3, 5 triazine-2,4. 6-Triacyl chloride was dissolved in 1000mL of ISOPAR G to prepare an oil phase solution. Then the aqueous phase solution is evenly coated on the polysulfone supporting layer, the temperature of the solution is 25 ℃, and the coating weight is 35mL/m 2 Standing in air for 100s, and removing residual aqueous phase solution by adopting an air knife; coating the oil phase solution on a supporting layer containing aqueous phase solution, wherein the temperature of the solution is 25-30 ℃ and the coating weight is 35mL/m 2 Standing in air for 120s, drying in an oven to remove residual oil phase solvent, curing at 70deg.C with sodium hydroxide solution with concentration of 0.1wt%, and washing with deionized water to remove residual sodium hydroxide.
Example 4
S1: dissolving a mixture of polyether sulfone and sulfonated polyether sulfone into benzophenone at 140 ℃ to obtain a 15wt% solution, wherein the content of sulfonated polyether sulfone in the mixture is 0.5wt%, coating the solution on a cooling roller with the temperature of 20 ℃ through a slit coating die head after-80 KPa vacuum defoamation, cooling to obtain a supporting layer containing a diluent, rinsing with ethanol to remove benzophenone in the supporting layer, removing the supporting layer of the diluent, and drying at 40 ℃ to obtain a porous supporting layer;
s2: 30g of m-phenylenediamine and 1.0-5.0 g of sulfanilic acid are dissolved into 1000g of purified water at room temperature to obtain aqueous phase solution; 10G of 1, 3, 5-triazine-2, 4, 6-triacyl chloride and 1.0G of 1, 3-benzenedisulfonyl chloride were dissolved in 1000mL of ISOPAR G to prepare an oil phase solution. Then the aqueous phase solution is evenly coated on the polysulfone supporting layer, the temperature of the solution is 25 ℃, and the coating weight is 55mL/m 2 Standing in air for 100s, and removing residual aqueous phase solution by adopting an air knife; coating the oil phase solution on a supporting layer containing aqueous phase solution at 25deg.C with a coating weight of 35mL/m 2 Standing in air for 120s, drying in an oven to remove residual oil phase solvent, curing at 70deg.C with sodium hydroxide solution with concentration of 0.1wt%, and washing with deionized water to remove residual sodium hydroxide.
Example 5
S1: dissolving a mixture of polyether sulfone and sulfonated polyether sulfone into benzophenone at 140 ℃ to obtain a 15wt% solution, wherein the content of sulfonated polyether sulfone in the mixture is 0.5wt%, coating the solution on a cooling roller with the temperature of 20 ℃ through a slit coating die head after-80 KPa vacuum defoamation, cooling to obtain a supporting layer containing a diluent, rinsing with ethanol to remove benzophenone in the supporting layer, removing the supporting layer of the diluent, and drying at 40 ℃ to obtain a porous supporting layer;
s2: 30g of m-phenylenediamine and 1.0g of sulfanilic acid are dissolved into 1000g of purified water at room temperature to obtain an aqueous phase solution; 2G of trimesoyl chloride was dissolved in 1000mL of ISOPAR G to prepare an oil phase solution. Then the aqueous phase solution is evenly coated on the polysulfone supporting layer, the temperature of the solution is 25 ℃, and the coating weight is 35mL/m 2 Standing in air for 100s, and removing residual aqueous phase solution by adopting an air knife; coating the oil phase solution on a supporting layer containing aqueous phase solution at 25deg.C with a coating weight of 35mL/m 2 Standing in air for 120s, drying in an oven to remove residual oil phase solvent, curing at 70deg.C with sodium hydroxide solution with concentration of 0.1wt%, and washing with deionized water to remove residual sodium hydroxide.
Example 6
S1: dissolving a mixture of polyether sulfone and sulfonated polyether sulfone into benzophenone at 140 ℃ to obtain a 15wt% solution, wherein the content of sulfonated polyether sulfone in the mixture is 0.5wt%, coating the solution on a cooling roller with the temperature of 20 ℃ through a slit coating die head after-80 KPa vacuum defoamation, cooling to obtain a supporting layer containing a diluent, rinsing with ethanol to remove benzophenone in the supporting layer, removing the supporting layer of the diluent, and drying at 40 ℃ to obtain a porous supporting layer;
s2: 30g of m-phenylenediamine is dissolved into 1000g of purified water at room temperature to obtain an aqueous phase solution; 2G of trimesoyl chloride and 0.5G of 1, 3-benzenedisulfonyl chloride were dissolved in 1000mL of ISOPAR G to prepare an oil phase solution. Then the aqueous phase solution is evenly coated on the polysulfone supporting layer, the temperature of the solution is 25 DEG CCoating weight 35mL/m 2 Standing in air for 100s, and removing residual aqueous phase solution by adopting an air knife; coating the oil phase solution on a supporting layer containing aqueous phase solution at 25deg.C with a coating weight of 35mL/m 2 Standing in air for 120s, drying in an oven to remove residual oil phase solvent, curing at 70deg.C with sodium hydroxide solution with concentration of 0.1wt%, and washing with deionized water to remove residual sodium hydroxide.
Example 7
S1: dissolving a mixture of polyether sulfone and sulfonated polyether sulfone into benzophenone at 140 ℃ to obtain a 15wt% solution, wherein the content of sulfonated polyether sulfone in the mixture is 0.5wt%, coating the solution on a cooling roller with the temperature of 20 ℃ through a slit coating die head after-80 KPa vacuum defoamation, cooling to obtain a supporting layer containing a diluent, rinsing with ethanol to remove benzophenone in the supporting layer, removing the supporting layer of the diluent, and drying at 40 ℃ to obtain a porous supporting layer;
s2: 30g of m-phenylenediamine and 1.0g of sulfanilic acid are dissolved into 1000g of purified water at room temperature to obtain an aqueous phase solution; 1.5G of 1, 3-benzenedisulfonyl chloride was dissolved in 1000mL of ISOPAR G to prepare an oil phase solution. Then the aqueous phase solution is evenly coated on the polysulfone supporting layer, the temperature of the solution is 25 ℃, and the coating weight is 35mL/m 2 Standing in air for 100s, and removing residual aqueous phase solution by adopting an air knife; coating the oil phase solution on a supporting layer containing aqueous phase solution, wherein the temperature of the solution is 25-30 ℃ and the coating weight is 35mL/m 2 Standing in air for 120s, drying in an oven to remove residual oil phase solvent, curing at 70deg.C with sodium hydroxide solution with concentration of 0.1wt%, and washing with deionized water to remove residual sodium hydroxide.
Example 8
S1: dissolving a mixture of polyether sulfone and sulfonated polyether sulfone into benzophenone at 140 ℃ to obtain a 15wt% solution, wherein the content of sulfonated polyether sulfone in the mixture is 0.5wt%, coating the solution on a cooling roller with the temperature of 20 ℃ through a slit coating die head after-80 KPa vacuum defoamation, cooling to obtain a supporting layer containing a diluent, rinsing with ethanol to remove benzophenone in the supporting layer, removing the supporting layer of the diluent, and drying at 40 ℃ to obtain a porous supporting layer;
s2: 25g of polyethyleneimine (molecular weight of 1000-20000) and 1.0g of sulfanilic acid are dissolved into 1000g of purified water at room temperature to obtain an aqueous phase solution; 10-50G of 1, 3, 5-triazine-2, 4, 6-triacyl chloride and 0.5-1.5G of 1, 3-benzene disulfonyl chloride are dissolved in 1000mL of ISOPAR G to prepare an oil phase solution. Then the aqueous phase solution is evenly coated on the polysulfone supporting layer, the temperature of the solution is 25 ℃, and the coating weight is 25mL/m 2 Standing in air for 100s, and removing residual aqueous phase solution by adopting an air knife; coating the oil phase solution on a supporting layer containing aqueous phase solution at 25deg.C with a coating weight of 40mL/m 2 Standing in air for 120s, drying in an oven to remove residual oil phase solvent, curing at 70deg.C with sodium hydroxide solution with concentration of 0.1wt%, and washing with deionized water to remove residual sodium hydroxide.
Comparative example 1
The comparative example prepared an ion exchange membrane, which was prepared by:
s1: dissolving polyethersulfone into diphenyl ketone at 140 ℃ to obtain 15wt% solution, coating the solution on a cooling roller with the temperature of 20 ℃ through a slit coating die head after-80 Kpa vacuum defoamation, cooling to obtain a supporting layer containing a diluent, rinsing with ethanol to remove diphenyl ketone in the supporting layer, and drying the supporting layer with the diluent at 40 ℃ to obtain a porous supporting layer;
s2: 30g of m-phenylenediamine is dissolved into 1000g of purified water at room temperature to obtain an aqueous phase solution; 10G of 1, 3, 5 triazine-2, 4, 6-triacyl chloride was dissolved in 1000mL of ISOPAR G to prepare an oil phase solution. Then the aqueous phase solution is evenly coated on the polysulfone supporting layer, the temperature of the solution is 25 ℃, and the coating weight is 35mL/m 2 Standing in air for 100s, and removing residual aqueous phase solution by adopting an air knife; oil phase is addedThe solution is coated on a supporting layer containing aqueous phase solution, the temperature of the solution is 25-30 ℃, and the coating weight is 35mL/m 2 Standing in air for 120s, drying in an oven to remove residual oil phase solvent, curing at 70deg.C with sodium hydroxide solution with concentration of 0.1wt%, and washing with deionized water to remove residual sodium hydroxide.
Comparative example 2
The porous support layer is prepared by adopting a non-solvent induced phase separation method in the comparative example, and comprises the following specific steps:
s1: dissolving polyethersulfone and sulfonated polyethersulfone into DMF at 80 ℃ to obtain 15wt% solution, coating the solution on a cooling roller with the temperature of 20 ℃ through a slit coating die head after-80 KPa vacuum defoamation, rinsing with pure water to remove DMF in the supporting layer, and drying to obtain a porous supporting layer;
s2: 30g of m-phenylenediamine is dissolved into 1000g of purified water at room temperature to obtain an aqueous phase solution; 10G of 1, 3, 5 triazine-2, 4, 6-triacyl chloride was dissolved in 1000mL of ISOPAR G to prepare an oil phase solution. Then the aqueous phase solution is evenly coated on the polysulfone supporting layer, the temperature of the solution is 25 ℃, and the coating weight is 35mL/m 2 Standing in air for 100s, and removing residual aqueous phase solution by adopting an air knife; coating the oil phase solution on a supporting layer containing aqueous phase solution, wherein the temperature of the solution is 25-30 ℃ and the coating weight is 35mL/m 2 Standing in air for 120s, drying in an oven to remove residual oil phase solvent, curing at 70deg.C with sodium hydroxide solution with concentration of 0.1wt%, and washing with deionized water to remove residual sodium hydroxide.
Test example 1
And (3) testing:
a. conductivity of
The in-plane conductivity of the films was measured using the four probe Electrochemical Impedance Spectroscopy (EIS) method using a swiss ten-thousand electrochemical workstation at a frequency range from 1Hz to 50 kHz. The film sample was fixed into the 4-electrode measuring head of the measurement. The conductivity of the membrane was calculated using the following equation:
where d is the distance between the two internal probes, l is the film thickness, w is the film width, and R m is the ohmic resistance as determined by fitting, the conductivity is performed at room temperature.
b. Permeability to vanadium
The crossover of vanadium (IV) was measured using a PermeGear "side-by-side" direct osmosis cell. The cell has two chambers with a volume of 45mL separated by the membrane under test. The temperature of the chamber was adjusted to 25℃with a circulating water bath. Typical test experiments contained 1.5M VOSO in 2.6M sulfuric acid in a donor room 4 And 1.5M MgSO in 2.6M sulfuric acid in the acceptor chamber 4 . Vanadium (IV) has strong absorption properties at 248 nm; by taking advantage of this property, the concentration of the receptor compartment was measured at different time intervals using a Shimadzu UV-2450UV/Vis spectrometer. The vo2+ permeability is calculated using the feik's law of diffusion, as follows,
wherein: c r (t) is the acceptor VOSO at time t 4 Concentration c r (0) is donor initial VOSO 4 Concentration, V, is donor and acceptor solution volume, d is film thickness, a is effective area of the film, and P s is salt permeability.
c. Vanadium test cell:
VRB test batteries are assembled to 24cm 2 And an interdigitated flow field is utilized for processing the liquid electrolyte solution into a carbon plate. During use, the membrane was sandwiched between identical commercial carbon paper electrodes that had been previously heat treated in air to 400 ℃ for 30 hours and lined with Polytetrafluoroethylene (PTFE) membrane. Each side of the cell was equipped with two reservoirs of 100mL of electrolyte solution consisting of 1.60M vanadium species with an average oxidation state of 3.55 and a total sulfur content of 4.2M. Electrolyte was pumped through two acid-resistant membrane pumps at 120mLA constant flow per min is circulated through the cell. Charge/discharge cycle performance was measured at a rate of from 72mA/cm using a multichannel potentiostat (model BT2000, arbin Instruments Inc, college Station, TX) 2 Up to 484mA/cm 2 Constant current density measurement over a range of (2). The results are shown in Table 1.
TABLE 1 results of membrane vanadium ion permeability test
As can be seen from table 1: in examples 4, 6, 7 and 8, a sulfonated component was introduced into the support layer, and sulfanilic acid and sulfonyl chloride were further used as monomers for synthesizing the ion conductive layer in the interfacial polymerization, thereby greatly increasing the number of sulfonic acid groups in the ion exchange membrane of the present invention and increasing the conductivity of the membrane body. The nanoscale thickness characteristics of the ion conducting layer are advantageous in reducing the intra-and inter-layer resistance. Meanwhile, the introduction of the sulfonated component and the monomer containing sulfonic acid groups strengthens the bonding force between the ion conducting layer and the supporting layer and the crosslinking density of the ion conducting layer, so VO 2+ The permeability decreases.
TABLE 2 results of diaphragm Performance test
According to the data in Table 2, the coulombic efficiency of the ion exchange membrane for the flow battery is as high as 98.52%, the voltage efficiency is as high as 98.81%, and the ion exchange membrane is far higher than that of a comparative example, and is mainly derived from the improvement of the conductivity of the ion exchange membrane of the example.
Claims (10)
1. A method for preparing an ion exchange membrane, comprising the steps of:
s1, extruding a casting piece from a main material, an auxiliary material and a diluent through heat to obtain a porous support layer;
s2, coating an aqueous solution of an amino-containing monomer and an oil phase solution of an acyl chloride-containing monomer on the porous support layer for polymerization reaction to form an ion-selective conductive layer;
the main body material of the porous support layer comprises at least one of polysulfone, polyethersulfone, polyvinylidene fluoride, polyphenylsulfone, polyacrylonitrile, naphthyridine diphenyl polyethersulfone ketone, polybenzimidazole, polypropylene and polyethylene;
the auxiliary material comprises at least one of sulfonated polyethersulfone, sulfonated polysulfone, sulfonated polyphenyl ether and sulfonated polytetrafluoroethylene;
the amino group-containing monomer includes an amino group main monomer; the amino group main monomer includes an aromatic compound or an aliphatic compound having at least two amino groups.
2. The method of claim 1, wherein the amino group-containing monomer further comprises an amino group-containing auxiliary monomer comprising a sulfonic acid-based amino compound.
3. The method according to claim 1, wherein the diluent comprises at least one of sulfolane, dimethyl phthalate, diphenyl carbonate, tributyl citrate, glyceryl triacetate, tributyl phosphate, triethyl phosphate, propylene carbonate, gamma-butyrolactone, benzophenone, methyl benzoate, diethyl phthalate, methyl salicylate, diethyl malonate, tributyl acetyl citrate, dibutyl maleate, dioctyl terephthalate, 1-butyl-3-methylimidazolium hexafluorophosphate, and carbitol acetate.
4. The method of claim 1, wherein the solute of the oil phase solution of the acid chloride-containing monomer comprises an aromatic compound containing at least two acid chloride groups or at least two sulfonyl chloride groups.
5. The method of claim 1, wherein the step of hot extrusion casting comprises melting the starting materials of the porous support layer and cooling to solidify.
6. The method according to claim 5, wherein the melting temperature is 80 to 200 ℃.
7. The process according to claim 1, wherein in step S2, the coating amount of the amino group-containing monomer in the aqueous solution coating process is 10 to 120mL/m 2 The coating weight of the oil phase solution coating process of the monomer containing acyl chloride is 10-50 mL/m 2 。
8. The method according to claim 1, wherein the reaction time is 10 to 200 seconds in step S2.
9. An ion exchange membrane prepared by the preparation method according to any one of claims 1 to 8, wherein the ion exchange membrane is formed by compositing an ion selective conductive layer supported on the porous support layer, and the thickness of the ion selective conductive layer of the ion exchange membrane is 50-300 nm.
10. Use of the ion exchange membrane according to claim 9 in a flow battery.
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