CN114614197B - Modified PVDF/nano MOFs low-crosslinking-density composite film and preparation method thereof - Google Patents
Modified PVDF/nano MOFs low-crosslinking-density composite film and preparation method thereof Download PDFInfo
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- 239000002033 PVDF binder Substances 0.000 title claims abstract description 47
- 229920002981 polyvinylidene fluoride Polymers 0.000 title claims abstract description 47
- 239000013105 nano metal-organic framework Substances 0.000 title claims abstract description 29
- 239000002131 composite material Substances 0.000 title claims abstract description 25
- 238000004132 cross linking Methods 0.000 title claims abstract description 19
- 238000002360 preparation method Methods 0.000 title claims abstract description 9
- 239000003446 ligand Substances 0.000 claims abstract description 35
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 claims abstract description 35
- 239000012621 metal-organic framework Substances 0.000 claims abstract description 14
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 24
- 238000003756 stirring Methods 0.000 claims description 19
- VOZRXNHHFUQHIL-UHFFFAOYSA-N glycidyl methacrylate Chemical compound CC(=C)C(=O)OCC1CO1 VOZRXNHHFUQHIL-UHFFFAOYSA-N 0.000 claims description 16
- 239000000178 monomer Substances 0.000 claims description 16
- ONDPHDOFVYQSGI-UHFFFAOYSA-N zinc nitrate Chemical compound [Zn+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O ONDPHDOFVYQSGI-UHFFFAOYSA-N 0.000 claims description 12
- BQCIDUSAKPWEOX-UHFFFAOYSA-N 1,1-Difluoroethene Chemical compound FC(F)=C BQCIDUSAKPWEOX-UHFFFAOYSA-N 0.000 claims description 11
- 238000001035 drying Methods 0.000 claims description 11
- 238000006243 chemical reaction Methods 0.000 claims description 8
- 239000002904 solvent Substances 0.000 claims description 7
- 238000009210 therapy by ultrasound Methods 0.000 claims description 7
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 6
- DBMJMQXJHONAFJ-UHFFFAOYSA-M Sodium laurylsulphate Chemical compound [Na+].CCCCCCCCCCCCOS([O-])(=O)=O DBMJMQXJHONAFJ-UHFFFAOYSA-M 0.000 claims description 5
- USHAGKDGDHPEEY-UHFFFAOYSA-L potassium persulfate Chemical compound [K+].[K+].[O-]S(=O)(=O)OOS([O-])(=O)=O USHAGKDGDHPEEY-UHFFFAOYSA-L 0.000 claims description 5
- 229920001577 copolymer Polymers 0.000 claims description 4
- 239000000203 mixture Substances 0.000 claims description 4
- DWAQJAXMDSEUJJ-UHFFFAOYSA-M Sodium bisulfite Chemical compound [Na+].OS([O-])=O DWAQJAXMDSEUJJ-UHFFFAOYSA-M 0.000 claims description 3
- 239000008367 deionised water Substances 0.000 claims description 3
- 229910021641 deionized water Inorganic materials 0.000 claims description 3
- 230000001804 emulsifying effect Effects 0.000 claims description 3
- RPQRDASANLAFCM-UHFFFAOYSA-N oxiran-2-ylmethyl prop-2-enoate Chemical compound C=CC(=O)OCC1CO1 RPQRDASANLAFCM-UHFFFAOYSA-N 0.000 claims description 3
- 239000002245 particle Substances 0.000 claims description 3
- 235000010267 sodium hydrogen sulphite Nutrition 0.000 claims description 3
- 238000004945 emulsification Methods 0.000 claims description 2
- 238000001027 hydrothermal synthesis Methods 0.000 claims description 2
- 238000002156 mixing Methods 0.000 claims description 2
- 239000004289 sodium hydrogen sulphite Substances 0.000 claims description 2
- 238000003892 spreading Methods 0.000 claims description 2
- 238000004519 manufacturing process Methods 0.000 claims 1
- IHYNKGRWCDKNEG-UHFFFAOYSA-N n-(4-bromophenyl)-2,6-dihydroxybenzamide Chemical compound OC1=CC=CC(O)=C1C(=O)NC1=CC=C(Br)C=C1 IHYNKGRWCDKNEG-UHFFFAOYSA-N 0.000 claims 1
- 238000010521 absorption reaction Methods 0.000 abstract description 11
- 239000007788 liquid Substances 0.000 abstract description 11
- 229910001416 lithium ion Inorganic materials 0.000 abstract description 10
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 abstract description 8
- 239000003431 cross linking reagent Substances 0.000 abstract description 3
- 230000000694 effects Effects 0.000 abstract description 3
- 238000011049 filling Methods 0.000 abstract description 3
- 239000003463 adsorbent Substances 0.000 abstract description 2
- 239000012767 functional filler Substances 0.000 abstract description 2
- 239000003792 electrolyte Substances 0.000 description 9
- 230000000052 comparative effect Effects 0.000 description 6
- 239000012528 membrane Substances 0.000 description 6
- 229920000642 polymer Polymers 0.000 description 5
- 238000000034 method Methods 0.000 description 4
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 4
- 229920002313 fluoropolymer Polymers 0.000 description 3
- 239000004811 fluoropolymer Substances 0.000 description 3
- 235000019333 sodium laurylsulphate Nutrition 0.000 description 3
- -1 Polyethylene Polymers 0.000 description 2
- 239000004698 Polyethylene Substances 0.000 description 2
- 229910004298 SiO 2 Inorganic materials 0.000 description 2
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 2
- 238000010041 electrostatic spinning Methods 0.000 description 2
- 238000011065 in-situ storage Methods 0.000 description 2
- 229910010272 inorganic material Inorganic materials 0.000 description 2
- 239000011147 inorganic material Substances 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 239000011368 organic material Substances 0.000 description 2
- 229920000573 polyethylene Polymers 0.000 description 2
- 239000011148 porous material Substances 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 238000005303 weighing Methods 0.000 description 2
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 1
- 229910010413 TiO 2 Inorganic materials 0.000 description 1
- 150000001450 anions Chemical class 0.000 description 1
- FPCJKVGGYOAWIZ-UHFFFAOYSA-N butan-1-ol;titanium Chemical compound [Ti].CCCCO.CCCCO.CCCCO.CCCCO FPCJKVGGYOAWIZ-UHFFFAOYSA-N 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 150000001768 cations Chemical class 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 238000003618 dip coating Methods 0.000 description 1
- 238000001523 electrospinning Methods 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 125000000524 functional group Chemical group 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 229910052744 lithium Inorganic materials 0.000 description 1
- PQXKHYXIUOZZFA-UHFFFAOYSA-M lithium fluoride Chemical compound [Li+].[F-] PQXKHYXIUOZZFA-UHFFFAOYSA-M 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 239000002086 nanomaterial Substances 0.000 description 1
- 239000002105 nanoparticle Substances 0.000 description 1
- 239000013110 organic ligand Substances 0.000 description 1
- 229920005569 poly(vinylidene fluoride-co-hexafluoropropylene) Polymers 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- 238000001878 scanning electron micrograph Methods 0.000 description 1
- 238000007789 sealing Methods 0.000 description 1
- WBHQBSYUUJJSRZ-UHFFFAOYSA-M sodium bisulfate Chemical compound [Na+].OS([O-])(=O)=O WBHQBSYUUJJSRZ-UHFFFAOYSA-M 0.000 description 1
- 229910000342 sodium bisulfate Inorganic materials 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
- 239000004408 titanium dioxide Substances 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
- H01M50/40—Separators; Membranes; Diaphragms; Spacing elements inside cells
- H01M50/409—Separators, membranes or diaphragms characterised by the material
- H01M50/411—Organic material
- H01M50/414—Synthetic resins, e.g. thermoplastics or thermosetting resins
- H01M50/426—Fluorocarbon polymers
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F214/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen
- C08F214/18—Monomers containing fluorine
- C08F214/22—Vinylidene fluoride
- C08F214/225—Vinylidene fluoride with non-fluorinated comonomers
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G83/00—Macromolecular compounds not provided for in groups C08G2/00 - C08G81/00
- C08G83/008—Supramolecular polymers
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- C—CHEMISTRY; METALLURGY
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- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J3/00—Processes of treating or compounding macromolecular substances
- C08J3/24—Crosslinking, e.g. vulcanising, of macromolecules
- C08J3/246—Intercrosslinking of at least two polymers
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
- H01M50/40—Separators; Membranes; Diaphragms; Spacing elements inside cells
- H01M50/409—Separators, membranes or diaphragms characterised by the material
- H01M50/411—Organic material
- H01M50/414—Synthetic resins, e.g. thermoplastics or thermosetting resins
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
- H01M50/40—Separators; Membranes; Diaphragms; Spacing elements inside cells
- H01M50/489—Separators, membranes, diaphragms or spacing elements inside the cells, characterised by their physical properties, e.g. swelling degree, hydrophilicity or shut down properties
- H01M50/491—Porosity
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
- C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
- C08F220/10—Esters
- C08F220/26—Esters containing oxygen in addition to the carboxy oxygen
- C08F220/32—Esters containing oxygen in addition to the carboxy oxygen containing epoxy radicals
- C08F220/325—Esters containing oxygen in addition to the carboxy oxygen containing epoxy radicals containing glycidyl radical, e.g. glycidyl (meth)acrylate
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- C—CHEMISTRY; METALLURGY
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- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2327/00—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Derivatives of such polymers
- C08J2327/02—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Derivatives of such polymers not modified by chemical after-treatment
- C08J2327/12—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Derivatives of such polymers not modified by chemical after-treatment containing fluorine atoms
- C08J2327/16—Homopolymers or copolymers of vinylidene fluoride
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2487/00—Characterised by the use of unspecified macromolecular compounds, obtained otherwise than by polymerisation reactions only involving unsaturated carbon-to-carbon bonds
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Abstract
The invention discloses a modified PVDF/nanometer MOFs low-crosslinking-density composite film and a preparation method thereof. The composite film is formed by compositely crosslinking MOFs containing amino ligands and modified PVDF with low GMA content, and comprises 0.5-5wt% of nano MOFs containing amino ligands and 95-99.5wt% of modified PVDF. According to the invention, nano MOFs are used as a cross-linking agent, functional filler and adsorbent, and are compounded with modified PVDF with low GMA content, so that the filling enhancement effect is achieved through low-density cross-linking, the mechanical strength and heat resistance of the film are improved, meanwhile, due to the high specific surface area and porous characteristics of the nano MOFs, lithium ions possibly generated by a system can be adsorbed, and the film has high liquid absorption rate.
Description
Technical Field
The invention belongs to the field of lithium ion battery diaphragms, and relates to a modified PVDF/nanometer MOFs low-crosslinking-density composite film and a preparation method thereof.
Background
The separator in the lithium ion battery has the function of separating the positive electrode from the negative electrode, and the pore canal in the separator enables the anions and cations in the electrolyte to pass through selectively and freely, so that the reaction in the battery is circularly carried out. Commercial lithium ion battery separators are mainly made of Polyethylene (PE) and the like, however, the separators have potential safety hazards and have weak affinity to electrolytes.
Attempts have been made to use fluoropolymers, i.e., polymeric compounds in which some or all of the C-H bonds are replaced by C-F bonds, as separators. The fluoropolymer as a battery separator should have good chemical stability, thermal stability, lyophilic properties and dielectric properties. At present, only polyvinylidene fluoride (PVDF) series fluoropolymers can meet the requirements of lithium ion battery diaphragms. However, the single-component separator does not fully meet the application requirements of high-performance lithium ion batteries.
By adding inorganic nano materials into the pure PVDF or the pure PVDF-HFP, the diaphragm has the characteristics of both organic and inorganic materials. The inorganic nano particles can improve mechanical strength and heat resistance, enhance the capacity of the diaphragm for absorbing and storing electrolyte, and prolong the cycle life of the battery. Xia et al wet-method for adding SiO with particle size of 40nm into PVDF and N, N-dimethylformamide system 2 Preparation of PVDF/SiO 2 Film containing 5% SiO 2 The membrane has uniform pore structure, the porosity is 43%, the liquid absorption rate is 340%, and the membrane is improved by 70% compared with a commercial PP membrane (A high-safety PVDF/Al) 2 O 3 composite separator for Li-ion batteries via tip-induced electrospinning and dip-coating.RSC Adv,2017,7 (39): 24410-24.416.). Korean collar hydrolyzes butyl titanate in PVDF solution to generate TiO in situ 2 Then preparing PVDF/TiO by adopting an electrostatic spinning method 2 Composite diaphragm, when TiO 2 When the content of the nano TiO is 5wt%, the comprehensive performance of the diaphragm is best, and the nano TiO is never added in the ion conductivity at room temperature 2 3.9X10 of diaphragm -3 S/cm is increased to 5.1X10 -3 S/cm (influence of in-situ generation of titanium dioxide on mechanical property and electrochemical property of electrostatic spinning polyvinylidene fluoride lithium ion battery diaphragm. Polymer journal 2012, (11): 1.319-1325).
As an emerging organic-inorganic hybrid material, metal Organic Frameworks (MOFs) have the advantages of diversity and adjustability of components and structures, porosity, high specific surface area, excellent thermal stability, chemical stability and the like compared with the traditional organic and inorganic materials, and have great application potential in the fields of gas adsorption storage, catalysis, sensing and the like.
Disclosure of Invention
Aiming at the problems of poor mechanical strength, poor capacity of absorbing and storing electrolyte, poor cycle life of a battery and the like of the conventional lithium battery diaphragm, the invention provides a modified PVDF/nano MOFs low-crosslinking-density composite film and a preparation method thereof. The method adopts modified PVDF with low glycidyl acrylate (GMA) content to be matched with nano MOFs containing amino ligands, achieves filling enhancement effect through low-degree crosslinking, and improves the mechanical strength and heat resistance of the film; meanwhile, due to the high specific surface and the porous characteristic of the nanometer MOFs, lithium ions possibly generated by the system can be adsorbed.
The modified PVDF/nano MOFs low-crosslinking-density composite film is formed by compositely crosslinking nano MOFs containing amino ligands and modified PVDF with low glycidyl acrylate (GMA) content, and the crosslinking density is 3-10%; the components are as follows according to mass fraction: the nanometer MOFs containing amino ligand accounts for 0.5-5wt% and the modified PVDF accounts for 95-99.5wt%, wherein the modified PVDF is copolymer of vinylidene fluoride (VDF) and Glycidyl Methacrylate (GMA), and the monomer content of the GMA accounts for 0.5wt% -5wt%.
Preferably, the modified PVDF/nanometer MOFs low-crosslinking-density composite film has a crosslinking density of 4-8%, and comprises the following components in percentage by mass: 1wt% of nano MOFs containing amino ligand and 99wt% of modified PVDF; the GMA monomer content in the modified PVDF was 3.5% by weight.
The modified PVDF is a copolymer of vinylidene fluoride (VDF) and Glycidyl Methacrylate (GMA), and is prepared by the following steps:
adding sodium dodecyl sulfate into deionized water, stirring and dissolving, adding monomer VDF and monomer GMA, stirring and emulsifying, then adding potassium persulfate, stirring for 3-8 minutes, adding sodium bisulfate, stirring for 5-15 minutes, reacting at 55+/-5 ℃ for 6-8 hours, removing residual monomers after the reaction is finished, demulsifying and drying to obtain the modified PVDF.
Preferably, the emulsification time is 10 to 15 minutes.
Preferably, sodium lauryl sulfate: monomer VDF: monomer GMA: potassium persulfate: the mass ratio of the sodium bisulphite is 0.1:96:3.5:0.3:0.1.
The invention is characterized in thatThe preparation method of the nano MOFs containing the amino ligand comprises the following steps: zinc nitrate and amino-containing ligand are added into water, the mixture is heated to 120+/-5 ℃ for hydrothermal reaction for 24+/-2 hours, and after the reaction is finished, the mixture is filtered, washed and dried to obtain the amino-containing ligand nano MOFs, wherein the structural formula of the amino-containing ligand is as follows:
preferably, the molar ratio of zinc nitrate to amino-containing ligand is 2:1.
Preferably, the particle size of the nano MOF containing the amino ligand is 50 to 500 nm.
The invention also provides a preparation method of the modified PVDF/nanometer MOFs low-crosslinking-density composite film, which comprises the following steps: mixing modified PVDF, nano MOFs containing amino ligand and solvent N, N-dimethylformamide according to a certain proportion, carrying out ultrasonic treatment for 0.5-1 hour, stirring for 2-3 hours, spreading a film, and drying at 75+/-5 ℃ under vacuum to obtain the composite film.
Compared with the prior art, the invention has the following advantages:
the nano MOFs containing the amino ligand is used as a cross-linking agent, a functional filler and an adsorbent. On the one hand, the nanometer MOFs containing amino ligand is used as a cross-linking agent, the organic ligand of the nanometer MOFs has better affinity with polymer chains of modified PVDF with low GMA content, and can endow the polymer with more functional groups, and the filling enhancement effect is achieved through low-degree cross-linking, so that the mechanical strength and heat resistance of the film are improved; on the other hand, due to the characteristics of high crystallinity, porosity and high specific surface area of the nano MOFs, the morphology and structure of the polymer can be regulated and controlled, and the mechanical strength of the material is further improved; on the other hand, due to the high specific surface area and the porous characteristic of the nanometer MOFs, lithium ions possibly generated by the system can be adsorbed, and the liquid absorption rate is improved.
Drawings
FIG. 1 is an SEM image of nano MOFs containing amino ligands prepared according to the present invention.
Detailed Description
The present invention will be further described with reference to examples, but the scope of the present invention is not limited thereto.
In the following examples and comparative examples, unless otherwise specified, reagents used were commercially available, and methods used were those conventionally used in the art.
In the following examples and comparative examples, the modified PVDF was prepared by the following steps: 2 kg of deionized water is added into a 10-liter reaction kettle, 2 g of sodium dodecyl sulfate is added, stirring and dissolving are carried out, 1920 g of monomer VDF and 70 g of GMA are added, stirring and emulsifying are carried out for 10 minutes, 6 g of potassium persulfate is added, stirring is carried out for 5 minutes, 2 g of sodium bisulfite is added, stirring is carried out for 10 minutes, reaction is carried out for 6 hours at 55 ℃, residual monomers are removed, and demulsification and drying are carried out, thus obtaining the modified PVDF.
In the following examples and comparative examples, nano MOFs containing amino ligands were prepared by the following steps: adding zinc nitrate, amino-containing ligand and water into a hydrothermal kettle according to the molar ratio of zinc nitrate to amino-containing ligand of 2:1, sealing the kettle, putting the kettle into an oven, heating to 120 ℃ for reaction for 24 hours, filtering, washing and drying to obtain the amino-containing ligand nano MOFs, wherein the amino-containing ligand has the following structural formula:
in the following examples and comparative examples, the test methods of the films were as follows:
(1) The film mechanical properties were determined according to ISO 527.
(2) Liquid absorption rate measurement: and weighing the film to be measured, immersing the film into electrolyte for 4 hours, and fully immersing the diaphragm by the electrolyte. After taking out the membrane, sucking the superfluous electrolyte on the surface of the membrane by using filter paper, weighing, and calculating the liquid absorption rate of the membrane by the following formula:
liquid absorption= (W-W) 0 /W 0 )*100％
In which W is 0 The mass of the diaphragm before electrolyte is absorbed, and the mass of the diaphragm after electrolyte is absorbed is W.
Comparative example 1
10 g of modified PVDF and 90 g of solvent N, N-dimethylformamide are added into a container, ultrasonic treatment is carried out for half an hour, stirring is carried out for 2 hours, then film laying is carried out, drying is carried out under vacuum at 75 ℃, and the modified PVDF film is prepared, wherein the tensile strength is 5.1Mpa, the elongation at break is 250%, and the liquid absorption is 100%.
Comparative example 2
9.0 g of modified PVDF, 1 g of nano MOFs containing amino ligand and 90 g of solvent N, N-dimethylformamide are added into a container, ultrasonic treatment is carried out for half an hour, stirring is carried out for 2 hours, then film laying is carried out, drying is carried out under vacuum at 75 ℃, and a composite film is obtained, wherein the tensile strength is 8.8Mpa, the elongation at break is 95%, and the liquid absorption is 180%.
Example 1
9.95 g of modified PVDF, 0.05 g of nano MOFs containing amino ligand and 90 g of solvent N, N-dimethylformamide are added into a container, ultrasonic treatment is carried out for half an hour, stirring is carried out for 2 hours, then a film is paved, and drying is carried out under vacuum at 75 ℃ to obtain a composite film, wherein the tensile strength is 6.3Mpa, the elongation at break is 180%, and the liquid absorption is 120%.
Example 2
9.90 g of modified PVDF, 0.10 g of nano MOFs containing amino ligand and 90 g of solvent N, N-dimethylformamide are added into a container, ultrasonic treatment is carried out for half an hour, stirring is carried out for 2 hours, then a film is paved, and drying is carried out under vacuum at 75 ℃ to obtain a composite film, wherein the tensile strength is 7.1Mpa, the elongation at break is 160%, and the liquid absorption is 150%.
Example 3
9.5 g of modified PVDF, 0.5 g of nano MOFs containing amino ligand and 90 g of solvent N, N-dimethylformamide are added into a container, ultrasonic treatment is carried out for half an hour, stirring is carried out for 2 hours, then a film is paved, drying is carried out under vacuum at 75 ℃, and a composite film with the tensile strength of 7.8Mpa, the elongation at break of 130% and the liquid absorption of 170% is obtained.
Claims (7)
1. The modified PVDF/nano MOFs low-crosslinking-density composite film is characterized by being formed by composite crosslinking of nano MOFs containing amino ligands and modified PVDF with low glycidyl acrylate content, wherein the crosslinking density is 3-10%; the components are as follows according to mass fraction: nanometer MOFs 0.5-5wt% containing amino ligand and modified PVDF 95-99.5wt%, wherein the modified PVDF is copolymer of vinylidene fluoride and glycidyl methacrylate, and the monomer content of the glycidyl methacrylate is as followsThe preparation method of the nano MOFs containing the amino ligand is as follows: zinc nitrate and amino-containing ligand are added into water, the mixture is heated to 120+/-5 ℃ for hydrothermal reaction for 24+/-2 hours, and after the reaction is finished, the mixture is filtered, washed and dried to obtain the amino-containing ligand nano MOFs, wherein the structural formula of the amino-containing ligand is as follows:the molar ratio of zinc nitrate to amino-containing ligand was 2:1.
2. The composite film according to claim 1, wherein the crosslinking density is 4-8%, and the components are as follows by mass fraction: nano MOFs 1wt% containing amino ligand and modified PVDF 99% by weight; the glycidyl methacrylate monomer content in the modified PVDF was 3.5% by weight.
3. The composite film according to claim 1 or 2, wherein the modified PVDF is a copolymer of vinylidene fluoride and glycidyl methacrylate, prepared by:
adding sodium dodecyl sulfate into deionized water, stirring and dissolving, adding monomer vinylidene fluoride and monomer glycidyl methacrylate, stirring and emulsifying, then adding potassium persulfate, stirring for 3-8 minutes, adding sodium bisulfide, stirring for 5-15 minutes, reacting for 6-8 hours at 55+/-5 ℃, removing residual monomers after the reaction is finished, and demulsifying and drying to obtain the modified PVDF.
4. The composite film according to claim 3, wherein the emulsification time is 10 to 15 minutes.
5. A composite film according to claim 3, wherein sodium dodecyl sulfate: monomer vinylidene fluoride: monomer glycidyl methacrylate: potassium persulfate: the mass ratio of the sodium bisulphite is 0.1:96:3.5:0.3:0.1.
6. The composite film according to claim 1 or 2, wherein the particle size of the amino ligand-containing nano MOFs is 50 to 500 nm.
7. The method for producing a composite film according to claim 1 or 2, comprising the steps of: mixing the modified PVDF, the nanometer MOFs containing the amino ligand and the solvent N, N-dimethylformamide according to a proportion, carrying out ultrasonic treatment for 0.5-1 hour, stirring for 2-3 hours, spreading a film, and drying at 75+/-5 ℃ under vacuum to obtain the composite film.
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