CN115101349B - Flexible self-supporting covalent organic framework fiber film and preparation method and application thereof - Google Patents
Flexible self-supporting covalent organic framework fiber film and preparation method and application thereof Download PDFInfo
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- 239000000835 fiber Substances 0.000 title claims abstract description 81
- 239000013310 covalent-organic framework Substances 0.000 title claims abstract description 74
- 238000002360 preparation method Methods 0.000 title abstract description 29
- 229920002239 polyacrylonitrile Polymers 0.000 claims abstract description 72
- 239000002131 composite material Substances 0.000 claims abstract description 59
- 239000000178 monomer Substances 0.000 claims abstract description 47
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 claims abstract description 37
- 238000000944 Soxhlet extraction Methods 0.000 claims abstract description 15
- 238000010041 electrostatic spinning Methods 0.000 claims abstract description 15
- 238000011065 in-situ storage Methods 0.000 claims abstract description 10
- 238000000034 method Methods 0.000 claims abstract description 8
- 239000012528 membrane Substances 0.000 claims description 62
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical group CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 42
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 claims description 38
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims description 21
- 150000001299 aldehydes Chemical class 0.000 claims description 16
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 14
- UHOVQNZJYSORNB-UHFFFAOYSA-N benzene Substances C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 claims description 14
- 239000000243 solution Substances 0.000 claims description 12
- 238000001035 drying Methods 0.000 claims description 7
- 238000000605 extraction Methods 0.000 claims description 7
- 238000002347 injection Methods 0.000 claims description 7
- 239000007924 injection Substances 0.000 claims description 7
- 239000002904 solvent Substances 0.000 claims description 7
- VZXTWGWHSMCWGA-UHFFFAOYSA-N 1,3,5-triazine-2,4-diamine Chemical compound NC1=NC=NC(N)=N1 VZXTWGWHSMCWGA-UHFFFAOYSA-N 0.000 claims description 6
- IJUKXLYWNIOUOH-UHFFFAOYSA-N 4-(4-carbamoylphenyl)benzamide Chemical compound C1=CC(C(=O)N)=CC=C1C1=CC=C(C(N)=O)C=C1 IJUKXLYWNIOUOH-UHFFFAOYSA-N 0.000 claims description 6
- 239000003960 organic solvent Substances 0.000 claims description 6
- WQOWBWVMZPPPGX-UHFFFAOYSA-N 2,6-diaminoanthracene-9,10-dione Chemical compound NC1=CC=C2C(=O)C3=CC(N)=CC=C3C(=O)C2=C1 WQOWBWVMZPPPGX-UHFFFAOYSA-N 0.000 claims description 4
- GJAJJEGWMDUKFM-UHFFFAOYSA-N 5-[3,5-bis(6-formylpyridin-3-yl)phenyl]pyridine-2-carbaldehyde Chemical compound O=Cc1ccc(cn1)-c1cc(cc(c1)-c1ccc(C=O)nc1)-c1ccc(C=O)nc1 GJAJJEGWMDUKFM-UHFFFAOYSA-N 0.000 claims description 4
- 238000005406 washing Methods 0.000 claims description 2
- 238000004519 manufacturing process Methods 0.000 claims 4
- 239000002994 raw material Substances 0.000 abstract 1
- 239000000203 mixture Substances 0.000 description 15
- 238000009987 spinning Methods 0.000 description 15
- 230000002194 synthesizing effect Effects 0.000 description 10
- 239000003990 capacitor Substances 0.000 description 8
- 239000007772 electrode material Substances 0.000 description 8
- 238000001291 vacuum drying Methods 0.000 description 5
- MKHDOBRSMHTMOK-UHFFFAOYSA-N 5-amino-2-(4-amino-2-carboxyphenyl)benzoic acid Chemical group OC(=O)C1=CC(N)=CC=C1C1=CC=C(N)C=C1C(O)=O MKHDOBRSMHTMOK-UHFFFAOYSA-N 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- 239000000463 material Substances 0.000 description 4
- JPYHHZQJCSQRJY-UHFFFAOYSA-N Phloroglucinol Natural products CCC=CCC=CCC=CCC=CCCCCC(=O)C1=C(O)C=C(O)C=C1O JPYHHZQJCSQRJY-UHFFFAOYSA-N 0.000 description 3
- 238000013461 design Methods 0.000 description 3
- 238000011161 development Methods 0.000 description 3
- QCDYQQDYXPDABM-UHFFFAOYSA-N phloroglucinol Chemical compound OC1=CC(O)=CC(O)=C1 QCDYQQDYXPDABM-UHFFFAOYSA-N 0.000 description 3
- 229960001553 phloroglucinol Drugs 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- 239000007983 Tris buffer Substances 0.000 description 2
- 239000011230 binding agent Substances 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- 238000004146 energy storage Methods 0.000 description 2
- 238000009776 industrial production Methods 0.000 description 2
- 239000000843 powder Substances 0.000 description 2
- CEPNDKRJQPJVNM-UHFFFAOYSA-N 2,4-dihydroxybenzene-1,3,5-tricarbaldehyde Chemical compound OC1=C(C=O)C=C(C=O)C(O)=C1C=O CEPNDKRJQPJVNM-UHFFFAOYSA-N 0.000 description 1
- 239000011149 active material Substances 0.000 description 1
- 239000013543 active substance Substances 0.000 description 1
- 238000010923 batch production Methods 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 238000012512 characterization method Methods 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 238000006482 condensation reaction Methods 0.000 description 1
- 239000006258 conductive agent Substances 0.000 description 1
- 238000005336 cracking Methods 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
- 238000003487 electrochemical reaction Methods 0.000 description 1
- 239000003792 electrolyte Substances 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 125000000524 functional group Chemical group 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 239000002052 molecular layer Substances 0.000 description 1
- 239000002121 nanofiber Substances 0.000 description 1
- 239000013384 organic framework Substances 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- 230000002441 reversible effect Effects 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 239000002002 slurry Substances 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-SENSITIVE DEVICES OF THE ELECTROLYTIC TYPE
- H01G11/00—Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
- H01G11/22—Electrodes
- H01G11/24—Electrodes characterised by structural features of the materials making up or comprised in the electrodes, e.g. form, surface area or porosity; characterised by the structural features of powders or particles used therefor
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-SENSITIVE DEVICES OF THE ELECTROLYTIC TYPE
- H01G11/00—Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
- H01G11/22—Electrodes
- H01G11/30—Electrodes characterised by their material
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-SENSITIVE DEVICES OF THE ELECTROLYTIC TYPE
- H01G11/00—Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
- H01G11/84—Processes for the manufacture of hybrid or EDL capacitors, or components thereof
- H01G11/86—Processes for the manufacture of hybrid or EDL capacitors, or components thereof specially adapted for electrodes
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- 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
- Y02E60/13—Energy storage using capacitors
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Abstract
The invention relates to a flexible self-supporting covalent organic framework fiber film, a preparation method and application thereof, wherein an amino monomer and polyacrylonitrile are prepared into a composite fiber film through electrostatic spinning, then the composite fiber film is prepared into a covalent organic framework/polyacrylonitrile composite fiber film through in-situ growth, and finally a polyacrylonitrile template is removed through Soxhlet extraction. The invention has simple process and good feasibility and can realize large-scale preparation; the raw materials are various in variety, the morphology and the structure are controllable, the preparation of the flexible self-supporting film of the pure covalent organic framework is realized, and the preparation method has a good application prospect in the field of flexible supercapacitors.
Description
Technical Field
The invention belongs to the field of supercapacitors, and particularly relates to a flexible self-supporting covalent organic framework fiber film, and a preparation method and application thereof.
Background
As a result of the push of the growing demand for portable electronic products, flexible, high-performance, wearable energy storage devices have become a mainstream trend in the development of electronic products. Among them, supercapacitors having high energy density, high power density and long cycle life have attracted considerable attention from researchers. Compared with the traditional super capacitor, the flexible solid super capacitor not only has higher mass/volume ratio capacitance, but also has the following advantages: small in size, highly reliable, lightweight, environmentally friendly, easy to handle, and easy to fold or attach to any surface. Based on the development progress of the current all-solid-state super capacitor, the development of a flexible electrode with high capacitance and high flexibility is a key for realizing a high electrochemical performance device. Among them, organic electrode materials have received extensive attention due to the characteristics of diversity of molecular layer structure design, environmental friendliness, low cost and the like. Organic electrode materials store energy primarily through reversible and rapid electrochemical reactions occurring at the electrode surface or in bulk phase. Therefore, the structure of the organic electrode material can be regulated through structural design, so that more organic functional groups with redox activity are obtained, and the energy storage of the organic electrode material is further improved. However, organic electrodes also have some obvious drawbacks, such as easy dissolution, etc., which seriously affect their further widespread use. And the functional organic unit framework of the covalent organic framework can greatly prevent the covalent organic framework from being dissolved in electrolyte, so that the covalent organic framework has better electrochemical performance compared with the common organic framework.
The covalent organic framework is a two-dimensional or three-dimensional porous crystalline polymer formed by covalent bond connection of light elements such as C, N, B through condensation reaction. Since the first report of covalent organic frameworks by the group of professor Yaghi in 2005, many covalent organic framework materials with tunable structures have been successfully synthesized and applied in various fields such as gas storage/separation, photoelectric conversion, catalysis, etc. However, the processability is limited due to its insoluble and infusible cross-linked structure, greatly limiting its practical application. Therefore, most of the covalent organic frame-based electrode materials applied to the super capacitor are in powder form, and the electrode is required to be coated on the current collector by adding a binder and the like to prepare the electrode for test characterization, so that the preparation process of the electrode is strict, and the phenomena of cracking, falling of active substances and the like of an electrode plate are extremely easy to occur, and the requirements of flexible devices on bendable and self-supporting electrode materials cannot be met. For example, patent CN110483799A, CN110790932A, CN105348303a synthesizes covalent organic frame electrode materials for various supercapacitors, but in the application process, the electrode is prepared by adding conductive agent and binder, the electrode preparation process is relatively lengthy, and the electrode sheet is easy to crack, active material fall off, etc.
Disclosure of Invention
The invention aims to solve the technical problem of providing a flexible self-supporting covalent organic framework fiber film, a preparation method and application thereof, and overcomes the current situation that COFs materials are powder materials in the prior art.
The invention provides a flexible self-supporting covalent organic framework fiber film, which is prepared by preparing an amino monomer and polyacrylonitrile into a composite fiber film through electrostatic spinning, then preparing the covalent organic framework/polyacrylonitrile composite fiber film through in-situ growth, and finally removing a polyacrylonitrile template through Soxhlet extraction.
The invention also provides a preparation method of the flexible self-supporting covalent organic framework fiber film, which comprises the following steps:
(1) Dissolving amino monomers and polyacrylonitrile in an organic solvent according to the mass ratio of (0.5-4) to obtain an electrostatic spinning solution, and preparing the flexible self-supporting amino monomer/polyacrylonitrile composite fiber membrane through electrostatic spinning;
(2) Preparing the amino monomer/polyacrylonitrile composite fiber membrane into a covalent organic framework/polyacrylonitrile composite fiber membrane through in-situ growth;
(3) And Soxhlet extraction is adopted, and the flexible self-supporting covalent organic framework fiber membrane is obtained by removing the polyacrylonitrile template.
The amino monomer in the step (1) is one or more of 2, 6-diaminoanthraquinone, 4 '-diaminobiphenyl-2, 2' -dicarboxylic acid, 2, 4-diamino-1, 3, 5-triazine and [1, 1-biphenyl ] -4, 4-dicarboxamide. The chemical formula is as follows;
The organic solvent in the step (1) is N, N-dimethylformamide; the mass ratio of the polyacrylonitrile to the organic solvent is 1: (6-12).
The electrostatic spinning process parameters in the step (1) are as follows: the distance is 10-30cm, the voltage is 10-30kV, and the sample injection rate is 0.6-2mL h -1.
The aldehyde monomer used in the step (2) for in-situ growth is one or more of 4-hydroxy m-benzene tricaldehyde, 2, 4-dihydroxy-1, 3, 5-trimesic aldehyde, trialdehyde m-benzene, 1,3, 5-tri (2-formylpyridine-5-yl) benzene and 3,4', 5-trialdehyde-1, 1-biphenyl. The chemical formula is as follows;
The in-situ growth in the step (2) is specifically as follows: the preparation method comprises the steps of placing an amino monomer/polyacrylonitrile composite fiber membrane, an aldehyde monomer, 2mL of 6mol L -1 acetic acid and 30mL of methylene dichloride in a hydrothermal kettle, oscillating for 5min, placing in an oven at 120-160 ℃ for 24-72h, collecting the composite fiber membrane, respectively washing three times with methylene dichloride and acetone, and drying to obtain the covalent organic framework/polyacrylonitrile composite fiber membrane.
The Soxhlet extraction step in the step (3) comprises the following steps: placing the covalent organic framework/polyacrylonitrile composite fiber membrane in a Soxhlet extractor for Soxhlet extraction to remove polyacrylonitrile, wherein the solvent is N, N-dimethylformamide, the temperature is 150-190 ℃, and the extraction time is 24-48h.
The invention also provides application of the flexible self-supporting covalent organic framework fiber film in a super capacitor.
The invention prepares the flexible self-supporting covalent organic framework fiber film which can be directly applied to the electrode material of the super capacitor and has controllable chemical structure, compact arrangement, mechanical property and electrochemical property by utilizing electrostatic spinning, in-situ growth and Soxhlet extraction; the preparation method has mild conditions, simple operation and wide sources of instruments and equipment, can realize industrial production, lays theoretical and technical foundation for implementing high-efficiency new energy industrial production, and has important demonstration effect and application value.
Advantageous effects
(1) The preparation method has the advantages of high feasibility, simple process and wide equipment sources, and can realize batch production.
(2) The covalent organic framework has large structural design space, and has rich open pore structure and electrochemical activity and can store charges.
(3) The covalent organic framework fiber film prepared by adopting the electrostatic spinning and in-situ growth process can realize a structure that covalent organic frameworks are closely arranged instead of stacked and agglomerated, and realize the high tensile property of the flexible self-supporting covalent organic framework fiber film.
(4) According to the invention, the pure covalent organic framework fiber film is prepared by removing the polyacrylonitrile template through Soxhlet extraction, so that the nanofiber morphology of the covalent organic framework film is completely reserved, and monomers and oligomers which do not participate in covalent organic framework reaction can be effectively removed.
(5) The material prepared by the method has good flexibility, can be directly used for preparing the super capacitor, omits electrode pretreatment steps such as slurry configuration and coating, and the like, has excellent electrochemical performance, and has great application potential in the field of super capacitors.
Detailed Description
The application will be further illustrated with reference to specific examples. It is to be understood that these examples are illustrative of the present application and are not intended to limit the scope of the present application. Furthermore, it should be understood that various changes and modifications can be made by one skilled in the art after reading the teachings of the present application, and such equivalents are intended to fall within the scope of the application as defined in the appended claims.
Example 1
Preparation of amino monomer/polyacrylonitrile composite fiber membrane: the amino monomer selected for synthesizing the covalent organic framework is 4,4 '-diaminobiphenyl-2, 2' -dicarboxylic acid. 3.16g (11.61 mmol) of 4,4 '-diaminobiphenyl-2, 2' -dicarboxylic acid and 1.58g of polyacrylonitrile were placed in 10mL of N, N-dimethylformamide, and the mixture was vigorously stirred for 24 hours until the mixture became clear, to obtain an amino monomer/polyacrylonitrile spinning solution. And carrying out electrostatic spinning on the obtained spinning solution in a set parameter with a spinning voltage of 10kV and a sample injection flow rate of 0.6mL/h and a receiving distance of 10 cm. A composite fiber membrane with a diameter of about 500nm was obtained on a receiving device. And then vacuum drying the mixture at room temperature for 12 hours to obtain the amino monomer/polyacrylonitrile composite fiber membrane.
Preparation of covalent organic framework/polyacrylonitrile composite fiber film: the aldehyde monomer selected for synthesizing the covalent organic framework is 1,3, 5-tri (2-formylpyridine-5-yl) benzene. The amino monomer/polyacrylonitrile composite fiber membrane obtained above, 3.04g (7.74 mmol) of 1,3, 5-tris (2-formylpyridin-5 yl) benzene, 2mL of 6mol L -1 acetic acid and 30mL of methylene chloride are placed in a hydrothermal kettle, vibrated for 5min, placed in an oven at 120 ℃ for 72h, the composite fiber membrane is collected, washed three times with methylene chloride and acetone respectively, and then dried at 60 ℃ for 12h to obtain the covalent organic framework/polyacrylonitrile composite fiber membrane.
Preparation of a flexible self-supporting covalent organic framework fibrous membrane: placing the prepared covalent organic framework/polyacrylonitrile composite fiber membrane in a Soxhlet extractor for Soxhlet extraction to remove polyacrylonitrile, wherein the selected solvent is N, N-dimethylformamide, the temperature is 150 ℃, the extraction time is 48 hours, and then the flexible self-supporting covalent organic framework fiber membrane is obtained by drying at 60 ℃ for 24 hours, wherein the mechanical strength can reach 12MPa, and the mass specific capacitance can reach 450F g -1.
Example 2
Preparation of amino monomer/polyacrylonitrile composite fiber membrane: amino monomers selected for synthesizing the covalent organic framework are 2, 6-diaminoanthraquinone and 2, 4-diamino-1, 3, 5-triazine. 0.81g (3.41 mmol) of 2, 6-diaminoanthraquinone, 0.38g (3.41 mmol) of 2, 4-diamino-1, 3, 5-triazine and 1.19g of polyacrylonitrile are placed in 10mL of N, N-dimethylformamide, and the mixture is stirred vigorously for 24 hours until the mixture is clear, so that an amino monomer/polyacrylonitrile spinning solution is obtained. And carrying out electrostatic spinning on the obtained spinning solution in a set parameter with a spinning voltage of 30kV and a sample injection flow rate of 2mL/h and a receiving distance of 30 cm. A composite fiber membrane with a diameter of about 600nm was obtained on a receiving device. And then vacuum drying the mixture at room temperature for 12 hours to obtain the amino monomer/polyacrylonitrile composite fiber membrane.
Preparation of covalent organic framework/polyacrylonitrile composite fiber film: the aldehyde monomer selected for synthesizing the covalent organic framework is 4-hydroxy-m-benzene trimethyl aldehyde. The amino monomer/polyacrylonitrile composite fiber membrane obtained above, 0.81g (4.55 mmol) of 4-hydroxy trimellitic aldehyde, 2mL of 6mol L -1 acetic acid and 30mL of dichloromethane are placed in a hydrothermal kettle, vibrated for 5min, placed in a baking oven at 140 ℃ for 36h, the composite fiber membrane is collected, washed three times with dichloromethane and acetone respectively, and then dried at 60 ℃ for 12h to obtain the covalent organic framework/polyacrylonitrile composite fiber membrane.
Preparation of a flexible self-supporting covalent organic framework fibrous membrane: placing the prepared covalent organic framework/polyacrylonitrile composite fiber membrane in a Soxhlet extractor for Soxhlet extraction to remove polyacrylonitrile, wherein the selected solvent is N, N-dimethylformamide, the temperature is 190 ℃, the extraction time is 24 hours, and then drying is carried out at 60 ℃ for 24 hours to obtain the flexible self-supporting covalent organic framework fiber membrane, the mechanical strength of the flexible self-supporting covalent organic framework fiber membrane can reach 25MPa, and the mass specific capacitance can reach 523F g -1.
Example 3
Preparation of amino monomer/polyacrylonitrile composite fiber membrane: amino monomers selected for synthesizing the covalent organic framework are 2, 4-diamino-1, 3, 5-triazine and [1, 1-biphenyl ] -4, 4-dicarboxamide. 0.062g (0.56 mmol) of 2, 4-diamino-1, 3, 5-triazine, 0.13g (0.56 mmol) of [1, 1-biphenyl ] -4, 4-dicarboxamide and 0.79g of polyacrylonitrile are placed in 10mL of N, N-dimethylformamide, and the mixture is stirred vigorously for 24 hours until the mixture is clear, so as to obtain amino monomer/polyacrylonitrile spinning solution. And carrying out electrostatic spinning on the obtained spinning solution in a set parameter with a spinning voltage of 20kV and a sample injection flow rate of 1mL/h and a receiving distance of 15 cm. A composite fiber membrane with a diameter of about 450nm was obtained on a receiving device. And then vacuum drying the mixture at room temperature for 12 hours to obtain the amino monomer/polyacrylonitrile composite fiber membrane.
Preparation of covalent organic framework/polyacrylonitrile composite fiber film: the aldehyde monomers selected for synthesizing the covalent organic framework are 2, 4-dihydroxy-1, 3, 5-trimesic aldehyde and trialdehyde phloroglucinol. The amino monomer/polyacrylonitrile composite fiber membrane obtained above, 0.097g (0.50 mmol) of 2, 4-dihydroxyl-1, 3, 5-trimellitic aldehyde, 0.052g (0.25 mmol) of trialdehyde phloroglucinol, 2mL of 6mol L -1 acetic acid and 30mL of dichloromethane are placed in a hydrothermal kettle, vibrated for 5min, placed in an oven at 160 ℃ for 24h, the composite fiber membrane is collected, washed three times with dichloromethane and acetone respectively, and then dried for 12h at 60 ℃ to obtain the covalent organic framework/polyacrylonitrile composite fiber membrane.
Preparation of a flexible self-supporting covalent organic framework fibrous membrane: placing the prepared covalent organic framework/polyacrylonitrile composite fiber membrane in a Soxhlet extractor for Soxhlet extraction to remove polyacrylonitrile, wherein the selected solvent is N, N-dimethylformamide, the temperature is 170 ℃, the extraction time is 36h, and then the flexible self-supporting covalent organic framework fiber membrane is obtained by drying at 60 ℃ for 24h, wherein the mechanical strength can reach 15MPa, and the mass specific capacitance can reach 478F g -1.
Example 4
Preparation of amino monomer/polyacrylonitrile composite fiber membrane: the amino monomer selected for synthesizing the covalent organic framework is [1, 1-biphenyl ] -4, 4-dicarboxamide. 0.47g (1.96 mmol) of [1, 1-biphenyl ] -4, 4-dicarboxamide and 0.95g of polyacrylonitrile are placed in 10mL of N, N-dimethylformamide, and the mixture is stirred vigorously for 24 hours until the mixture is clear, so as to obtain an amino monomer/polyacrylonitrile spinning solution. And carrying out electrostatic spinning on the obtained spinning solution in a set parameter with a spinning voltage of 12kV and a sample injection flow rate of 1.5mL/h and a receiving distance of 20 cm. A composite fiber film having a diameter of about 550nm was obtained on a receiving device. And then vacuum drying the mixture at room temperature for 12 hours to obtain the amino monomer/polyacrylonitrile composite fiber membrane.
Preparation of covalent organic framework/polyacrylonitrile composite fiber film: the aldehyde monomers selected for synthesizing the covalent organic framework are 1,3, 5-tri (2-formylpyridinium-5-yl) benzene and 3,4', 5-trialdehyde-1, 1-biphenyl. The amino monomer/polyacrylonitrile composite fiber membrane obtained above, 0.21g (0.65 mmol) of 1,3, 5-tris (2-formylpyridin-5 yl) benzene, 0.15g (0.65 mmol) of 3,4', 5-trialdehyde-1, 1-biphenyl, 2mL of 6mol L -1 acetic acid and 30mL of methylene chloride were placed in a hydrothermal kettle, vibrated for 5min, placed in an oven at 150 ℃ for 30h, the composite fiber membrane was collected, washed three times with methylene chloride and acetone respectively, and then dried at 60 ℃ for 12h to obtain the covalent organic framework/polyacrylonitrile composite fiber membrane.
Preparation of a flexible self-supporting covalent organic framework fibrous membrane: placing the prepared covalent organic framework/polyacrylonitrile composite fiber membrane in a Soxhlet extractor for Soxhlet extraction to remove polyacrylonitrile, wherein the selected solvent is N, N-dimethylformamide, the temperature is 150 ℃, the extraction time is 24 hours, and then the flexible self-supporting covalent organic framework fiber membrane is obtained by drying at 60 ℃ for 24 hours, the mechanical strength can reach 17MPa, and the mass specific capacitance can reach 365F g -1.
Example 5
Preparation of amino monomer/polyacrylonitrile composite fiber membrane: the amino monomer selected for synthesizing the covalent organic framework is 4,4 '-diaminobiphenyl-2, 2' -dicarboxylic acid. 0.45g (1.65 mmol) of 4,4 '-diaminobiphenyl-2, 2' -dicarboxylic acid and 1.35g of polyacrylonitrile are placed in 10mL of N, N-dimethylformamide, and the mixture is stirred vigorously for 24 hours until the mixture is clarified, so that an amino monomer/polyacrylonitrile spinning solution is obtained. And carrying out electrostatic spinning on the obtained spinning solution in a set parameter with a spinning voltage of 25kV and a sample injection flow rate of 1.8mL/h and a receiving distance of 18 cm. A composite fiber film having a diameter of about 480nm was obtained on a receiving device. And then vacuum drying the mixture at room temperature for 12 hours to obtain the amino monomer/polyacrylonitrile composite fiber membrane.
Preparation of covalent organic framework/polyacrylonitrile composite fiber film: the aldehyde monomers selected for synthesizing the covalent organic framework are 4-hydroxy m-benzene tricaldehyde, 2, 4-dihydroxy-1, 3, 5-trimesic aldehyde and trialdehyde phloroglucinol. The amino monomer/polyacrylonitrile composite fiber membrane obtained above, 0.053g (0.30 mmol) of 4-hydroxy-m-benzene tricarboxaldehyde, 0.058g (0.30 mmol) of 2, 4-dihydroxy-1, 3, 5-benzene tricarboxaldehyde, 0.11g (0.50 mmol) of trialdehyde-m-benzene tricarboxyl, 2mL of 6mol L -1 acetic acid and 30mL of dichloromethane were placed in a hydrothermal kettle, shaken for 5min, placed in an oven at 140 ℃ for 24h, and the composite fiber membrane was collected, washed three times with dichloromethane and acetone respectively, and then dried at 60 ℃ for 12h to obtain the covalent organic framework/polyacrylonitrile composite fiber membrane.
Preparation of a flexible self-supporting covalent organic framework fibrous membrane: placing the prepared covalent organic framework/polyacrylonitrile composite fiber membrane in a Soxhlet extractor for Soxhlet extraction to remove polyacrylonitrile, wherein the selected solvent is N, N-dimethylformamide, the temperature is 190 ℃, the extraction time is 48 hours, and then drying is carried out at 60 ℃ for 24 hours to obtain the flexible self-supporting covalent organic framework fiber membrane, the mechanical strength of the flexible self-supporting covalent organic framework fiber membrane can reach 21MPa, and the mass specific capacitance can reach 613F g -1.
Claims (6)
1. A method of preparing a flexible self-supporting covalent organic framework fibrous membrane comprising:
(1) Dissolving amino monomers and polyacrylonitrile in an organic solvent according to the mass ratio of (0.5-4) to obtain an electrostatic spinning solution, and preparing the flexible self-supporting amino monomer/polyacrylonitrile composite fiber membrane through electrostatic spinning; wherein, the electrostatic spinning technological parameters are as follows: distance is 10-30 cm, voltage is 10-30 kV, sample injection rate is 0.6-2 mL h -1;
(2) Preparing the amino monomer/polyacrylonitrile composite fiber membrane into a covalent organic framework/polyacrylonitrile composite fiber membrane through in-situ growth; wherein, the in situ growth specifically comprises: placing an amino monomer/polyacrylonitrile composite fiber membrane, an aldehyde monomer, 2 mL of 6 mol L -1 acetic acid and 30 mL methylene dichloride in a hydrothermal kettle, oscillating 5min, placing into a baking oven at 120-160 ℃ for 24-72 h, collecting the composite fiber membrane, respectively washing three times with methylene dichloride and acetone, and drying to obtain a covalent organic framework/polyacrylonitrile composite fiber membrane;
(3) Soxhlet extraction is adopted, and a flexible self-supporting covalent organic framework fiber film is obtained by removing a polyacrylonitrile template; wherein, the Soxhlet extraction step comprises: placing the covalent organic framework/polyacrylonitrile composite fiber membrane in a Soxhlet extractor for Soxhlet extraction to remove polyacrylonitrile, wherein the solvent is N, N-dimethylformamide, the temperature is 150-190 ℃, and the extraction time is 24-48 h.
2. The method of manufacturing according to claim 1, characterized in that: the amino monomer in the step (1) is one or more of 2, 6-diaminoanthraquinone, 4 '-diaminobiphenyl-2, 2' -dicarboxylic acid, 2, 4-diamino-1, 3, 5-triazine and [1, 1-biphenyl ] -4, 4-dicarboxamide.
3. The method of manufacturing according to claim 1, characterized in that: the organic solvent in the step (1) is N, N-dimethylformamide; the mass ratio of the polyacrylonitrile to the organic solvent is 1: (6-12).
4. The method of manufacturing according to claim 1, characterized in that: the aldehyde monomer used in the step (2) for in-situ growth is one or more of 4-hydroxy m-benzene tricaldehyde, 2, 4-dihydroxy-1, 3, 5-trimesic aldehyde, trialdehyde m-benzene, 1,3, 5-tri (2-formylpyridine-5-yl) benzene and 3,4', 5-trialdehyde-1, 1-biphenyl.
5. A flexible self-supporting covalent organic framework fibrous membrane obtained by the method of manufacture of claim 1.
6. Use of the flexible self-supporting covalent organic framework fiber film of claim 5 in a supercapacitor.
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