CN117855541A - 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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- CN117855541A CN117855541A CN202311702187.5A CN202311702187A CN117855541A CN 117855541 A CN117855541 A CN 117855541A CN 202311702187 A CN202311702187 A CN 202311702187A CN 117855541 A CN117855541 A CN 117855541A
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- 239000003014 ion exchange membrane Substances 0.000 title claims abstract description 40
- 238000002360 preparation method Methods 0.000 title abstract description 8
- 239000003963 antioxidant agent Substances 0.000 claims abstract description 16
- 230000003078 antioxidant effect Effects 0.000 claims abstract description 16
- 239000012528 membrane Substances 0.000 claims description 42
- -1 3, 5-di-tert-butyl-4-hydroxyphenyl Chemical group 0.000 claims description 23
- 229920005989 resin Polymers 0.000 claims description 19
- 239000011347 resin Substances 0.000 claims description 19
- FPYJFEHAWHCUMM-UHFFFAOYSA-N maleic anhydride Chemical compound O=C1OC(=O)C=C1 FPYJFEHAWHCUMM-UHFFFAOYSA-N 0.000 claims description 12
- 239000004626 polylactic acid Substances 0.000 claims description 10
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 claims description 9
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims description 8
- 229920000747 poly(lactic acid) Polymers 0.000 claims description 8
- 229940041260 vanadyl sulfate Drugs 0.000 claims description 7
- 229910000352 vanadyl sulfate Inorganic materials 0.000 claims description 7
- 229920001577 copolymer Polymers 0.000 claims description 6
- 238000010096 film blowing Methods 0.000 claims description 6
- UQSQSQZYBQSBJZ-UHFFFAOYSA-N fluorosulfonic acid Chemical group OS(F)(=O)=O UQSQSQZYBQSBJZ-UHFFFAOYSA-N 0.000 claims description 6
- 239000004014 plasticizer Substances 0.000 claims description 6
- 239000004631 polybutylene succinate Substances 0.000 claims description 6
- 229920002961 polybutylene succinate Polymers 0.000 claims description 6
- 239000004215 Carbon black (E152) Substances 0.000 claims description 5
- 229930195733 hydrocarbon Natural products 0.000 claims description 5
- 239000000463 material Substances 0.000 claims description 5
- VLOPEOIIELCUML-UHFFFAOYSA-L vanadium(2+);sulfate Chemical compound [V+2].[O-]S([O-])(=O)=O VLOPEOIIELCUML-UHFFFAOYSA-L 0.000 claims description 5
- 229920000954 Polyglycolide Polymers 0.000 claims description 4
- 239000003011 anion exchange membrane Substances 0.000 claims description 4
- VOZRXNHHFUQHIL-UHFFFAOYSA-N glycidyl methacrylate Chemical compound CC(=C)C(=O)OCC1CO1 VOZRXNHHFUQHIL-UHFFFAOYSA-N 0.000 claims description 4
- 150000002430 hydrocarbons Chemical class 0.000 claims description 4
- 239000002245 particle Substances 0.000 claims description 4
- 229920001707 polybutylene terephthalate Polymers 0.000 claims description 4
- 229920001610 polycaprolactone Polymers 0.000 claims description 4
- 239000004632 polycaprolactone Substances 0.000 claims description 4
- 239000004633 polyglycolic acid Substances 0.000 claims description 4
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 claims description 3
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 claims description 3
- RSWGJHLUYNHPMX-UHFFFAOYSA-N Abietic-Saeure Natural products C12CCC(C(C)C)=CC2=CCC2C1(C)CCCC2(C)C(O)=O RSWGJHLUYNHPMX-UHFFFAOYSA-N 0.000 claims description 3
- 229920000881 Modified starch Polymers 0.000 claims description 3
- 239000004368 Modified starch Substances 0.000 claims description 3
- 229920000491 Polyphenylsulfone Polymers 0.000 claims description 3
- 239000004372 Polyvinyl alcohol Substances 0.000 claims description 3
- KHPCPRHQVVSZAH-HUOMCSJISA-N Rosin Natural products O(C/C=C/c1ccccc1)[C@H]1[C@H](O)[C@@H](O)[C@@H](O)[C@@H](CO)O1 KHPCPRHQVVSZAH-HUOMCSJISA-N 0.000 claims description 3
- 239000002131 composite material Substances 0.000 claims description 3
- 235000019426 modified starch Nutrition 0.000 claims description 3
- 229920002689 polyvinyl acetate Polymers 0.000 claims description 3
- 239000011118 polyvinyl acetate Substances 0.000 claims description 3
- 229920002451 polyvinyl alcohol Polymers 0.000 claims description 3
- 239000003549 soybean oil Substances 0.000 claims description 3
- 235000012424 soybean oil Nutrition 0.000 claims description 3
- KHPCPRHQVVSZAH-UHFFFAOYSA-N trans-cinnamyl beta-D-glucopyranoside Natural products OC1C(O)C(O)C(CO)OC1OCC=CC1=CC=CC=C1 KHPCPRHQVVSZAH-UHFFFAOYSA-N 0.000 claims description 3
- LSNNMFCWUKXFEE-UHFFFAOYSA-M Bisulfite Chemical compound OS([O-])=O LSNNMFCWUKXFEE-UHFFFAOYSA-M 0.000 claims description 2
- NLZUEZXRPGMBCV-UHFFFAOYSA-N Butylhydroxytoluene Chemical compound CC1=CC(C(C)(C)C)=C(O)C(C(C)(C)C)=C1 NLZUEZXRPGMBCV-UHFFFAOYSA-N 0.000 claims description 2
- FBPFZTCFMRRESA-FSIIMWSLSA-N D-Glucitol Natural products OC[C@H](O)[C@H](O)[C@@H](O)[C@H](O)CO FBPFZTCFMRRESA-FSIIMWSLSA-N 0.000 claims description 2
- FBPFZTCFMRRESA-JGWLITMVSA-N D-glucitol Chemical compound OC[C@H](O)[C@@H](O)[C@H](O)[C@H](O)CO FBPFZTCFMRRESA-JGWLITMVSA-N 0.000 claims description 2
- 239000004696 Poly ether ether ketone Substances 0.000 claims description 2
- 239000004693 Polybenzimidazole Substances 0.000 claims description 2
- 239000004695 Polyether sulfone Substances 0.000 claims description 2
- 239000004698 Polyethylene Substances 0.000 claims description 2
- 239000004642 Polyimide Substances 0.000 claims description 2
- XBDQKXXYIPTUBI-UHFFFAOYSA-M Propionate Chemical compound CCC([O-])=O XBDQKXXYIPTUBI-UHFFFAOYSA-M 0.000 claims description 2
- 150000008064 anhydrides Chemical class 0.000 claims description 2
- IANQTJSKSUMEQM-UHFFFAOYSA-N benzofuran Natural products C1=CC=C2OC=CC2=C1 IANQTJSKSUMEQM-UHFFFAOYSA-N 0.000 claims description 2
- 125000000499 benzofuranyl group Chemical group O1C(=CC2=C1C=CC=C2)* 0.000 claims description 2
- 235000010354 butylated hydroxytoluene Nutrition 0.000 claims description 2
- 238000009826 distribution Methods 0.000 claims description 2
- 229920006242 ethylene acrylic acid copolymer Polymers 0.000 claims description 2
- 239000005038 ethylene vinyl acetate Substances 0.000 claims description 2
- 238000000034 method Methods 0.000 claims description 2
- 239000000203 mixture Substances 0.000 claims description 2
- WXZMFSXDPGVJKK-UHFFFAOYSA-N pentaerythritol Chemical compound OCC(CO)(CO)CO WXZMFSXDPGVJKK-UHFFFAOYSA-N 0.000 claims description 2
- 229920001200 poly(ethylene-vinyl acetate) Polymers 0.000 claims description 2
- 239000005014 poly(hydroxyalkanoate) Substances 0.000 claims description 2
- 229920002480 polybenzimidazole Polymers 0.000 claims description 2
- 229920006393 polyether sulfone Polymers 0.000 claims description 2
- 229920002530 polyetherether ketone Polymers 0.000 claims description 2
- 229920000573 polyethylene Polymers 0.000 claims description 2
- 229920000903 polyhydroxyalkanoate Polymers 0.000 claims description 2
- 229920001721 polyimide Polymers 0.000 claims description 2
- 229920000642 polymer Polymers 0.000 claims description 2
- 150000003242 quaternary ammonium salts Chemical class 0.000 claims description 2
- 239000000600 sorbitol Substances 0.000 claims description 2
- 150000003457 sulfones Chemical class 0.000 claims description 2
- 239000002383 tung oil Substances 0.000 claims description 2
- UUUGYDOQQLOJQA-UHFFFAOYSA-L vanadyl sulfate Chemical compound [V+2]=O.[O-]S([O-])(=O)=O UUUGYDOQQLOJQA-UHFFFAOYSA-L 0.000 claims 2
- AEMRFAOFKBGASW-UHFFFAOYSA-N Glycolic acid Natural products OCC(O)=O AEMRFAOFKBGASW-UHFFFAOYSA-N 0.000 claims 1
- 239000004734 Polyphenylene sulfide Substances 0.000 claims 1
- NFHFRUOZVGFOOS-UHFFFAOYSA-N palladium;triphenylphosphane Chemical compound [Pd].C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1 NFHFRUOZVGFOOS-UHFFFAOYSA-N 0.000 claims 1
- 229920000069 polyphenylene sulfide Polymers 0.000 claims 1
- 229920012287 polyphenylene sulfone Polymers 0.000 claims 1
- 239000003792 electrolyte Substances 0.000 abstract description 8
- 229910052720 vanadium Inorganic materials 0.000 abstract description 6
- LEONUFNNVUYDNQ-UHFFFAOYSA-N vanadium atom Chemical compound [V] LEONUFNNVUYDNQ-UHFFFAOYSA-N 0.000 abstract description 6
- 229910001456 vanadium ion Inorganic materials 0.000 abstract description 5
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 abstract description 3
- 239000000654 additive Substances 0.000 abstract description 3
- 239000006227 byproduct Substances 0.000 abstract description 2
- 238000007254 oxidation reaction Methods 0.000 abstract description 2
- 238000004080 punching Methods 0.000 abstract description 2
- 239000013589 supplement Substances 0.000 abstract description 2
- 229910002804 graphite Inorganic materials 0.000 abstract 1
- 239000010439 graphite Substances 0.000 abstract 1
- 239000010408 film Substances 0.000 description 50
- 230000000052 comparative effect Effects 0.000 description 11
- 239000000306 component Substances 0.000 description 8
- 238000006243 chemical reaction Methods 0.000 description 6
- 238000006731 degradation reaction Methods 0.000 description 6
- 239000002994 raw material Substances 0.000 description 6
- 238000000071 blow moulding Methods 0.000 description 5
- 229910052799 carbon Inorganic materials 0.000 description 5
- 238000002156 mixing Methods 0.000 description 5
- RBFRVUKIVGOWND-UHFFFAOYSA-L oxygen(2-);vanadium(4+);sulfate Chemical compound [O-2].[V+4].[O-]S([O-])(=O)=O RBFRVUKIVGOWND-UHFFFAOYSA-L 0.000 description 5
- 238000012360 testing method Methods 0.000 description 5
- 230000015556 catabolic process Effects 0.000 description 4
- 230000006835 compression Effects 0.000 description 3
- 238000007906 compression Methods 0.000 description 3
- 238000002474 experimental method Methods 0.000 description 3
- 229920006381 polylactic acid film Polymers 0.000 description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 3
- YBYIRNPNPLQARY-UHFFFAOYSA-N 1H-indene Chemical compound C1=CC=C2CC=CC2=C1 YBYIRNPNPLQARY-UHFFFAOYSA-N 0.000 description 2
- 229920002799 BoPET Polymers 0.000 description 2
- 230000004888 barrier function Effects 0.000 description 2
- 230000007547 defect Effects 0.000 description 2
- 238000013461 design Methods 0.000 description 2
- 238000009792 diffusion process Methods 0.000 description 2
- 229920000139 polyethylene terephthalate Polymers 0.000 description 2
- 239000005020 polyethylene terephthalate Substances 0.000 description 2
- 239000010409 thin film Substances 0.000 description 2
- 230000002411 adverse Effects 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000000903 blocking effect Effects 0.000 description 1
- 239000008358 core component Substances 0.000 description 1
- 239000007857 degradation product Substances 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 238000004146 energy storage Methods 0.000 description 1
- 229920006351 engineering plastic Polymers 0.000 description 1
- BEFDCLMNVWHSGT-UHFFFAOYSA-N ethenylcyclopentane Chemical compound C=CC1CCCC1 BEFDCLMNVWHSGT-UHFFFAOYSA-N 0.000 description 1
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 description 1
- 238000011065 in-situ storage Methods 0.000 description 1
- 238000005342 ion exchange Methods 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 230000002427 irreversible effect Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 231100000989 no adverse effect Toxicity 0.000 description 1
- 230000035699 permeability Effects 0.000 description 1
- 229920001432 poly(L-lactide) Polymers 0.000 description 1
- 229920001606 poly(lactic acid-co-glycolic acid) Polymers 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- 230000001681 protective effect Effects 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 230000004044 response Effects 0.000 description 1
- 238000007789 sealing Methods 0.000 description 1
- 235000010199 sorbic acid Nutrition 0.000 description 1
- 239000004334 sorbic acid Substances 0.000 description 1
- 229940075582 sorbic acid Drugs 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 238000006467 substitution reaction Methods 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
- H01M8/10—Fuel cells with solid electrolytes
- H01M8/1016—Fuel cells with solid electrolytes characterised by the electrolyte material
- H01M8/1018—Polymeric electrolyte materials
-
- 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
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M8/00—Fuel cells; Manufacture thereof
- H01M8/18—Regenerative fuel cells, e.g. redox flow batteries or secondary fuel cells
- H01M8/184—Regeneration by electrochemical means
- H01M8/188—Regeneration by electrochemical means by recharging of redox couples containing fluids; Redox flow type batteries
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/30—Hydrogen technology
- Y02E60/50—Fuel cells
Landscapes
- Life Sciences & Earth Sciences (AREA)
- Engineering & Computer Science (AREA)
- Manufacturing & Machinery (AREA)
- Sustainable Development (AREA)
- Sustainable Energy (AREA)
- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Manufacture Of Macromolecular Shaped Articles (AREA)
- Cell Separators (AREA)
Abstract
The invention provides a high-utilization low-cost flow battery ion exchange membrane, a preparation method thereof and a flow battery, wherein the structure of the ion exchange membrane comprises a degradable film layer and a diaphragm layer, wherein the degradable film layer has high tensile property and is positioned on one side or two sides of the diaphragm layer, so that the punching positioning requirement can be met; the size of the degradable film layer is consistent with the size of the electrode frame, the area of the diaphragm layer is slightly larger than the area of the graphite felt electrode and smaller than the area of the electrode frame, the size of the diaphragm layer in the length direction and the width direction is larger than the size of the electrode, and the size of the diaphragm layer in one dimension of the length and the width is the same as the size of the electrode frame or smaller than the size of the electrode frame in the two dimensions of the length and the width, so that the problems of low utilization rate of the ion exchange membrane and extra leakage current generation in the existing flow battery technology can be effectively solved; the degradable film layer contains an antioxidant and/or vanadium ion replenisher, and can prevent the additives on the high-voltage side of the vanadium redox flow battery from generating oxidation reaction byproducts through slow release action, and supplement vanadium ions in the electrolyte, so that the energy efficiency, the coulombic efficiency and the voltage efficiency of the battery are improved.
Description
Technical Field
The invention relates to the technical field of flow batteries, in particular to an ion exchange membrane, a preparation method thereof and a flow battery.
Background
The flow battery has the advantages of intrinsic safety, flexible design, high response speed, no pollution and the like, and is very suitable for the application of a large-scale energy storage system. The ion exchange membrane is a core component of the flow battery, plays an important role in blocking positive and negative electrolyte and providing a proton exchange place. The most widely used perfluorosulfonic acid (PFSA) structure ion exchange membrane at present has high cost, and the non-reaction area in the galvanic pile structure occupies a certain area, so that the utilization rate can only reach 70-80%, and the cost is high.
In addition, the stack design structure of the vanadium cell needs to consider avoiding vanadium diffusion and aprotic ion permeation of the electrolyte membrane in the non-reaction area so as to avoid seriously affecting the coulomb efficiency and the energy efficiency of the cell, and the conventional thinking is to protect the non-reaction area of the ion exchange membrane, but the ion exchange membrane with a perfluorinated structure has poor compatibility with the conventional engineering plastics, and can cause irreversible deformation after being cooled in the hot working process, so that the sealing requirement cannot be met. How to meet the positioning and assembling requirements of non-reaction areas, and at the same time, improve the film utilization rate of the ion exchange membrane, reduce or eliminate leakage current as much as possible, is a problem to be solved in the field.
CN218918969U discloses an ion exchange membrane structure and a flow battery suitable for the same, wherein polylactic acid films are attached to two sides of the ion exchange membrane, so that a protective barrier can be provided, the use requirement of a carbon felt electrode for high compression ratio is met, but the problem of positioning and assembling a non-reaction area is not solved, the size of the ion exchange membrane is not changed, and the problems of film utilization rate and leakage current are still not solved.
In addition, considering that the consistency of the film needs to be ensured, the size of the degradable film cannot be increased at will, and the existing degradable resin material polylactic acid (PLA) has poor film forming property, hard and brittle texture and poor impact resistance; polyglycolic acid (PGA) is expensive as a raw material and has high cost; polybutylene terephthalate (PBAT) has the defects of poor water vapor barrier property and the like, and the application of a plurality of degradable materials as a single component has the defects that the compatibility is poor due to the structural difference in multi-component blending, so that the practicality and the stability of the film material are problematic; in addition, the use of additives can easily adversely affect the flow battery system before and after degradation of the degradable film, resulting in reduced performance or even failure of the flow battery.
Disclosure of Invention
The invention aims at the technical problems and provides an ion exchange membrane, a preparation method thereof and a flow battery, wherein the structure of the ion exchange membrane comprises a membrane layer and a degradable membrane layer with high tensile property, so that the utilization rate of the membrane layer in the ion exchange membrane can be greatly improved, and the leakage current of the flow battery can be effectively reduced.
In order to achieve the above purpose, the invention provides an ion exchange membrane, which comprises a membrane layer and a high-tensile-property degradable film layer positioned on one side or two sides of the surface of the membrane layer, wherein the degradable film layer comprises the following components:
85-98 parts of degradable resin;
0.5-2 parts of plasticizer;
0.5-5 parts of compatibilizer;
0.5-10 parts of tackifier;
0.5-2 parts of antioxidant.
Further, the antioxidant is one or more of 2, 6-di-tert-butyl-p-cresol, pentaerythritol tetra [ beta- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionate ] and n-stearyl beta- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionate.
Further, the degradable film layer also comprises vanadium sulfate and/or vanadyl sulfate;
the mass portion of the vanadium sulfate is 1-10;
and/or the mass portion of the vanadyl sulfate is 1-10.
Further, the degradable resin is one or more of polylactic acid, polyglycolic acid, polybutylene terephthalate, polybutylene adipate succinate, polyhydroxyalkanoate polymer, polycaprolactone, polylactic acid-glycolic acid copolymer and polybutylene succinate;
and/or the plasticizer is one or more of glycerol, ethylene glycol, tung oil anhydride, sorbitol and polyvinyl alcohol;
and/or the compatibilizer is one or more than one of acrylic acid, maleic anhydride, epoxidized soybean oil, ethylene-acrylic acid copolymer, ethylene-vinyl acetate copolymer, ethylene-acrylic ester-maleic anhydride copolymer, maleic anhydride grafted ethylene-octene copolymer, maleic anhydride grafted polylactic acid, glycidyl methacrylate grafted polylactic acid, maleic anhydride grafted polybutylene succinate, glycidyl methacrylate anhydride grafted polybutylene succinate, maleic anhydride grafted polybutylene terephthalate adipate, and glycidyl methacrylate grafted polybutylene terephthalate adipate;
and/or the tackifier is a coumarone resin, polyvinyl acetate, modified starch or rosin resin.
Further, the weight average molecular weight of the degradable resin is 50000-100000, and the molecular weight distribution index is less than 4;
and/or the thickness of the degradable film layer is 5-500 μm.
Further, the membrane layer is a perfluorosulfonic acid membrane, a hydrocarbon sulfonic acid ion exchange membrane, a sulfonated polyphenylsulfone membrane, a sulfonated polyethersulfone membrane, a sulfonated polyphenylsulfide sulfone membrane, a sulfonated polyphenylsulfone membrane, a sulfonated polyetheretherketone membrane, a polybenzimidazole membrane, a polyethylene porous membrane, a polyimide membrane, a quaternary ammonium salt anion exchange membrane, a hydrocarbon anion exchange membrane, a multicomponent blend membrane or a composite membrane.
The invention further provides a preparation method of the ion exchange membrane, which comprises the steps of uniformly mixing degradable resin, plasticizer, compatibilizer, tackifier and antioxidant according to a proportion, granulating the mixed material through a double-screw extruder to obtain blended particles, and blow molding the blended particles at 120-200 ℃ through a film blowing machine to obtain the degradable film;
and attaching or bonding the degradable film to one side or two sides of the surface of the membrane layer.
It is yet another object of the present invention to provide a flow battery comprising an ion exchange membrane as described above. Further, the flow battery also comprises an electrode and a polar frame, and the degradable film layer is positioned between the electrode and the diaphragm layer.
Further, the size of the degradable film layer is consistent with the size of the polar frame, and the size of the diaphragm layer in the length direction and the width direction is larger than the size of the electrode and smaller than the size of the polar frame;
or the size of the degradable film layer is consistent with the size of the electrode frame, the size of the diaphragm layer in the length direction and the width direction is larger than the size of the electrode, the size of the diaphragm layer in one direction of the length direction and the width direction is consistent with the size of the electrode frame, and the size in the other direction is smaller than the size of the electrode frame and larger than the size of the electrode.
The beneficial effects of the invention are as follows:
(1) The degradable film layer raw materials of the ion exchange membrane are hydrocarbon oxygen compounds, and the degradable film layer raw materials are environment-friendly and pollution-free after degradation, and have no adverse effect on a flow battery electrolyte system.
(2) The antioxidant selected by the invention enables the components in the degradable film layer to be suitable for the working environment of the flow battery system, and avoids the degradation or failure of the performance of the flow battery caused by the fact that the components in the film layer are oxidized at a high voltage side before and after degradation and byproducts of the oxidation reaction are attached to the surfaces of the electrode and the diaphragm layer.
(3) The ion exchange membrane is applied to a flow battery, the degradable film layer is degraded through the circulating flow of the aqueous electrolyte, water is generated in the degradation process, vanadium sulfate and/or vanadyl sulfate is added into the degradable film layer, vanadium ions can be slowly released and supplemented to the electrolyte in situ in the degradation process of the film layer, the concentration of the vanadium ions is prevented from being reduced due to the generated water, and therefore the performances of the battery such as energy density, voltage efficiency, current efficiency and the like are improved.
(4) The degradable film layer has good permeability, and can be attached to one side or two sides of the surface of the diaphragm layer due to excellent mechanical properties, so that the assembly requirement can be met by punching and positioning, and meanwhile, the porous carbon felt electrode can be prevented from being in direct contact with the diaphragm, so that the requirement of higher compression ratio of the electrode can be met.
(5) The ion exchange membrane provided by the invention has the degradable film layer with excellent tensile property, so that the non-reaction area of the membrane layer in a pole frame area can be greatly reduced, the utilization rate of the membrane layer can be improved from 60% -75% to 85% -95%, the utilization rate of the membrane layer is greatly improved, the generation of extra leakage current can be effectively reduced, and the ion exchange membrane has great significance in cost reduction and synergy of galvanic piles and systems.
Drawings
Fig. 1 is a schematic view of the structure of a polar frame, an electrode and an ion exchange membrane of a flow battery of the present invention.
FIG. 2 is a schematic diagram of a dimensional relationship structure of a polar frame and a degradable film layer of a flow battery of the present invention.
FIG. 3 is a schematic illustration of another dimensional relationship structure of a polar frame and degradable film layer of a flow battery of the present invention.
Fig. 4 is the energy efficiency of the flow batteries of inventive examples 5-6 and comparative examples 1-2 at different current densities.
Fig. 5 is the coulombic efficiency of the flow batteries of inventive examples 5-6 and comparative examples 1-2 at different current densities.
Fig. 6 is voltage efficiencies at different current densities for the flow batteries of inventive examples 5-6 and comparative examples 1-2.
Reference numerals:
1-a degradable film layer; 2-a separator layer; 3-electrode.
Description of the embodiments
The present invention is further illustrated by the following examples and comparative examples.
Examples
Preparation of degradable film with high tensile property
95 parts of polylactic acid (PLA) resin, 0.5 part of glycerol, 0.5 part of acrylic acid, 3 parts of rosin resin and 1 part of antioxidant (264) are selected; uniformly mixing the raw material components, granulating by using a double-screw extruder, and at 160 o And C, carrying out blow molding by a film blowing machine to obtain a degradable film with the thickness of 25 mu m, which is denoted as Sample 1.
Examples
Preparation of degradable film with high tensile property
Selecting 85 parts of polylactic-co-glycolic acid (PLGA, wherein LA: GA=80:20) resin, 2 parts of polyvinyl alcohol, 4 parts of epoxidized soybean oil, 8.5 parts of modified starch and 0.5 part of antioxidant (1010); uniformly mixing the raw material components, granulating by using a double-screw extruder, and at 120 o And C, carrying out blow molding by a film blowing machine to obtain a degradable film with the thickness of 25 mu m, which is marked as Sample 2.
Examples
98 parts of Polycaprolactone (PCL) resin, 0.5 part of sorbic acid, 0.5 part of maleic anhydride, 0.5 part of indene resin and 0.5 part of antioxidant (1076) are selected; uniformly mixing the raw material components, granulating by using a double-screw extruder, and granulating at 200 o And C, carrying out blow molding by a film blowing machine to obtain a degradable film with the thickness of 25 mu m, which is marked as Sample 3.
Examples
90 parts of polylactic resin, 1 part of glycol, 4 parts of maleic anhydride grafted polylactic acid, 4.5 parts of polyvinyl acetate and 0.5 part of antioxidant (264) are selected, uniformly mixed, granulated by a double screw extruder, and processed at 160 parts by weight o Blow molding by a film blowing machine under the condition C to obtain the degradable film with the thickness controlled to be 25 mu mThe film layer was released and designated Sample 4.
Tensile property test: the tensile properties were tested using a universal tester.
Polyethylene terephthalate (PET) film and pure polylactic acid film, both having a thickness of 25 μm, were selected as comparative examples, and tensile properties were measured using a universal tester, respectively, with samples 1 to 4 described above. The test results are shown in the following table:
| sample of | Tensile Strength (Mpa) | Elongation at break (%) |
| Sample 1 | 132 | 115 |
| Sample 2 | 146 | 109 |
| Sample 3 | 113 | 147 |
| Sample 4 | 125 | 102 |
| PET film | 121 | 83 |
| Poly L-lactic acid | 127 | 20 |
As can be seen from the data in the table, the degradable film of Sample1-4 of the invention has excellent tensile strength compared with PET film and pure polylactic acid film, and meanwhile, the extensibility and extensibility of the film are obviously improved, so that the degradable film of the invention has excellent processability.
Examples
Composite ion exchange membrane with perfluorosulfonic acid film as membrane layer and Sample 4 as degradable film layer: the thickness is selected to be 4.2mm and the area is selected to be 48cm 2 The area size of the degradable film layer Sample 4 is the same as the size of the polar frame, and the area size of the degradable film layer Sample 4 is 80cm 2 The membrane layer was a perfluorosulfonic acid film having a thickness of 52 μm (10 cm. Times.8 cm), a length and a width of 8.5cm and 6.5cm, respectively, and the above-mentioned 25 μm thick degradable film layers were attached to both sides of the membrane layer, with a compression ratio of 20%.
And (3) battery testing: 70mL of vanadium electrolyte with total vanadium concentration of 1.60mol/L is added into each of the positive and negative electrode storage tanks of the battery, and the electrolyte is circulated for 48 hours by a magnetic pump and then 80mA/cm is carried out 2 、100mA/cm 2 、150mA/cm 2 And 200mA/cm 2 And (3) constant-current charge-discharge cycle test under current density, wherein the charge-discharge voltage range is 0.9-1.60V, and the coulomb efficiency, the voltage efficiency and the energy efficiency of the battery are respectively recorded.
Examples
The steps, parameters and experimental conditions of the rest of the experimental procedure were the same as those of example 5, except that the degradable thin film layer of this example, in which the separator layer was oriented to the positive electrode side, further contained 5 parts of vanadyl sulfate, and the degradable thin film layer of the separator layer was oriented to the negative electrode side, further contained 5 parts of vanadyl sulfate.
Comparative example 1
The steps, parameters and experimental conditions of the rest of the experimental procedure were the same as in example 5, except that the ion exchange membrane had no degradable membrane layer.
Comparative example 2
The steps, parameters and experimental conditions of the rest of the experimental procedure were the same as in example 5, except that the degradable film layers on both sides of the ion exchange membrane did not contain an antioxidant.
Analysis of experimental results:
example 5 compared with comparative example 1, since the ion exchange membrane uses the degradable film layer with the same area as the electrode frame, the use ratio of the membrane layer of the flow battery in example 5 is improved from 60% to 87% compared with comparative example 1 while reducing the vanadium diffusion and aprotic ion exchange of the ion exchange membrane and reducing the leakage current.
Furthermore, as can be seen from the energy efficiency, coulombic efficiency and voltage efficiency test results, referring to fig. 4 to 6 of the specification, example 5 and example 6 have better energy efficiency, coulombic efficiency and voltage efficiency than comparative example 2, because the degradable film layer contains the antioxidant (example 5), compared to the solution (comparative example 2) in which other additives are introduced into the degradable film layer without the antioxidant; in addition, the technical scheme (example 6) that the degradable film layer contains the antioxidant and the vanadium ion supplement has the best battery performance, and the energy efficiency, the coulombic efficiency and the voltage efficiency of the flow battery are all effectively improved.
While the present application has been described with reference to the present specific embodiments, those skilled in the art will recognize that the above embodiments are for illustrative purposes only, and that various equivalent changes or substitutions can be made without departing from the spirit of the present application, and therefore, all changes and modifications that come within the spirit of the present application are desired to be protected.
Claims (10)
1. An ion exchange membrane comprising a membrane layer and a high tensile property degradable film layer positioned on one side or both sides of the surface of the membrane layer, wherein the degradable film layer comprises the following components:
85-98 parts of degradable resin;
0.5-2 parts of plasticizer;
0.5-5 parts of compatibilizer;
0.5-10 parts of tackifier;
0.5-2 parts of antioxidant.
2. The ion exchange membrane of claim 1, wherein the antioxidant is one or more of 2, 6-di-tert-butyl-p-cresol, pentaerythritol tetrakis [ beta- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionate ], and n-stearyl beta- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionate.
3. The ion exchange membrane of claim 1, wherein the degradable film layer further comprises vanadium sulfate and/or vanadyl sulfate;
the mass portion of the vanadium sulfate is 1-10;
and/or the mass portion of the vanadyl sulfate is 1-10.
4. The ion exchange membrane of claim 1, wherein the degradable resin is one or more of polylactic acid, polyglycolic acid, polybutylene terephthalate, polybutylene adipate succinate, polyhydroxyalkanoate-based polymer, polycaprolactone, polylactic acid glycolic acid copolymer, and polybutylene succinate;
and/or the plasticizer is one or more of glycerol, ethylene glycol, tung oil anhydride, sorbitol and polyvinyl alcohol;
and/or the compatibilizer is one or more than one of acrylic acid, maleic anhydride, epoxidized soybean oil, ethylene-acrylic acid copolymer, ethylene-vinyl acetate copolymer, ethylene-acrylic ester-maleic anhydride copolymer, maleic anhydride grafted ethylene-octene copolymer, maleic anhydride grafted polylactic acid, glycidyl methacrylate grafted polylactic acid, maleic anhydride grafted polybutylene succinate, glycidyl methacrylate anhydride grafted polybutylene succinate, maleic anhydride grafted polybutylene terephthalate adipate, and glycidyl methacrylate grafted polybutylene terephthalate adipate;
and/or the tackifier is a coumarone resin, polyvinyl acetate, modified starch or rosin resin.
5. The ion exchange membrane of any one of claims 1-4, wherein the degradable resin has a weight average molecular weight of 50000-100000 and a molecular weight distribution index of less than 4;
and/or the thickness of the degradable film layer is 5-500 μm.
6. The ion exchange membrane of any one of claims 1-4, wherein the membrane layer is a perfluorosulfonic acid membrane, a hydrocarbon sulfonic acid ion exchange membrane, a sulfonated polyphenylsulfone membrane, a sulfonated polyethersulfone membrane, a sulfonated polyphenylenesulfide sulfone membrane, a sulfonated polyphenylenesulfone membrane, a sulfonated polyetheretherketone membrane, a polybenzimidazole membrane, a polyethylene porous membrane, a polyimide membrane, a quaternary ammonium salt anion exchange membrane, a hydrocarbon anion exchange membrane, a multicomponent blend membrane therein, or a composite membrane.
7. A method for preparing an ion exchange membrane according to any one of claims 1 to 6, wherein degradable resin, plasticizer, compatibilizer, tackifier and antioxidant are uniformly mixed in proportion, the mixed materials are granulated by a twin-screw extruder to obtain blended particles, and the blended particles are blow molded by a film blowing machine at 120-200 ℃ to obtain the degradable film;
and attaching or bonding the degradable film to one side or two sides of the surface of the membrane layer.
8. A flow battery comprising the ion exchange membrane of any one of claims 1-6.
9. The flow battery of claim 8, further comprising an electrode and a polar frame, wherein the degradable film layer is located between the electrode and the separator layer.
10. The flow battery of claim 9, wherein the degradable film layer has a size consistent with the size of the electrode frame, and the separator layer has a size in both the length direction and the width direction that is greater than the electrode size and less than the electrode frame size;
or the size of the degradable film layer is consistent with the size of the electrode frame, the size of the diaphragm layer in the length direction and the width direction is larger than the size of the electrode, the size of the diaphragm layer in one direction of the length direction and the width direction is consistent with the size of the electrode frame, and the size in the other direction is smaller than the size of the electrode frame and larger than the size of the electrode.
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| CN101764233A (en) * | 2009-11-13 | 2010-06-30 | 山东东岳高分子材料有限公司 | Cross-linking perfluorinated sulfonic acid ion exchange membrane and preparation method thereof |
| CN104716353A (en) * | 2013-12-15 | 2015-06-17 | 中国科学院大连化学物理研究所 | Porous membrane used for liquid flow cell and preparation and application thereof |
| CN105161738A (en) * | 2015-10-08 | 2015-12-16 | 四川理工学院 | Composite membrane for vanadium batteries, continuous production method and application of composite membrane |
| US20200091536A1 (en) * | 2018-09-14 | 2020-03-19 | University Of South Carolina | Polybenzimidazole (PBI) Membranes for Redox Flow Batteries |
| CN218918969U (en) * | 2022-12-07 | 2023-04-25 | 寰泰储能科技股份有限公司 | Ion exchange membrane structure and flow battery applicable to same |
| CN116387752A (en) * | 2023-04-24 | 2023-07-04 | 西北工业大学 | An easy-to-degrade battery film processing technology |
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| CN101764233A (en) * | 2009-11-13 | 2010-06-30 | 山东东岳高分子材料有限公司 | Cross-linking perfluorinated sulfonic acid ion exchange membrane and preparation method thereof |
| CN104716353A (en) * | 2013-12-15 | 2015-06-17 | 中国科学院大连化学物理研究所 | Porous membrane used for liquid flow cell and preparation and application thereof |
| CN105161738A (en) * | 2015-10-08 | 2015-12-16 | 四川理工学院 | Composite membrane for vanadium batteries, continuous production method and application of composite membrane |
| US20200091536A1 (en) * | 2018-09-14 | 2020-03-19 | University Of South Carolina | Polybenzimidazole (PBI) Membranes for Redox Flow Batteries |
| CN218918969U (en) * | 2022-12-07 | 2023-04-25 | 寰泰储能科技股份有限公司 | Ion exchange membrane structure and flow battery applicable to same |
| CN116387752A (en) * | 2023-04-24 | 2023-07-04 | 西北工业大学 | An easy-to-degrade battery film processing technology |
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