CN114940759A - Fluorine-containing polyimide film, preparation method thereof and supercapacitor - Google Patents
Fluorine-containing polyimide film, preparation method thereof and supercapacitor Download PDFInfo
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- CN114940759A CN114940759A CN202210757565.9A CN202210757565A CN114940759A CN 114940759 A CN114940759 A CN 114940759A CN 202210757565 A CN202210757565 A CN 202210757565A CN 114940759 A CN114940759 A CN 114940759A
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- 229920001721 polyimide Polymers 0.000 title claims abstract description 40
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 title claims abstract description 37
- 229910052731 fluorine Inorganic materials 0.000 title claims abstract description 37
- 239000011737 fluorine Substances 0.000 title claims abstract description 37
- 238000002360 preparation method Methods 0.000 title claims abstract description 12
- 238000006243 chemical reaction Methods 0.000 claims abstract description 26
- 239000002904 solvent Substances 0.000 claims abstract description 18
- 238000001035 drying Methods 0.000 claims abstract description 15
- 239000003792 electrolyte Substances 0.000 claims abstract description 13
- 239000007787 solid Substances 0.000 claims abstract description 13
- GTDPSWPPOUPBNX-UHFFFAOYSA-N ac1mqpva Chemical compound CC12C(=O)OC(=O)C1(C)C1(C)C2(C)C(=O)OC1=O GTDPSWPPOUPBNX-UHFFFAOYSA-N 0.000 claims abstract description 11
- 239000003990 capacitor Substances 0.000 claims abstract description 10
- 150000004985 diamines Chemical class 0.000 claims abstract description 9
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims abstract description 8
- 239000003054 catalyst Substances 0.000 claims abstract description 7
- 238000000967 suction filtration Methods 0.000 claims abstract description 7
- 238000005266 casting Methods 0.000 claims abstract description 6
- 239000011248 coating agent Substances 0.000 claims abstract description 6
- 238000000576 coating method Methods 0.000 claims abstract description 6
- 238000003756 stirring Methods 0.000 claims abstract description 6
- 238000010438 heat treatment Methods 0.000 claims abstract description 5
- 238000005406 washing Methods 0.000 claims abstract description 5
- 229910052757 nitrogen Inorganic materials 0.000 claims abstract description 4
- RLSSMJSEOOYNOY-UHFFFAOYSA-N m-cresol Chemical compound CC1=CC=CC(O)=C1 RLSSMJSEOOYNOY-UHFFFAOYSA-N 0.000 claims description 14
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical group CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 12
- 238000004519 manufacturing process Methods 0.000 claims description 11
- AWJUIBRHMBBTKR-UHFFFAOYSA-N isoquinoline Chemical compound C1=NC=CC2=CC=CC=C21 AWJUIBRHMBBTKR-UHFFFAOYSA-N 0.000 claims description 10
- 238000005530 etching Methods 0.000 claims description 7
- PBKONEOXTCPAFI-UHFFFAOYSA-N 1,2,4-trichlorobenzene Chemical compound ClC1=CC=C(Cl)C(Cl)=C1 PBKONEOXTCPAFI-UHFFFAOYSA-N 0.000 claims description 6
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 claims description 6
- RFFLAFLAYFXFSW-UHFFFAOYSA-N 1,2-dichlorobenzene Chemical compound ClC1=CC=CC=C1Cl RFFLAFLAYFXFSW-UHFFFAOYSA-N 0.000 claims description 4
- FXHOOIRPVKKKFG-UHFFFAOYSA-N N,N-Dimethylacetamide Chemical group CN(C)C(C)=O FXHOOIRPVKKKFG-UHFFFAOYSA-N 0.000 claims description 4
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 claims description 4
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 claims description 4
- QTWJRLJHJPIABL-UHFFFAOYSA-N 2-methylphenol;3-methylphenol;4-methylphenol Chemical compound CC1=CC=C(O)C=C1.CC1=CC=CC(O)=C1.CC1=CC=CC=C1O QTWJRLJHJPIABL-UHFFFAOYSA-N 0.000 claims description 2
- FJVIHKKXPLPDSV-UHFFFAOYSA-N 4-phenoxybenzene-1,2-diamine Chemical group C1=C(N)C(N)=CC=C1OC1=CC=CC=C1 FJVIHKKXPLPDSV-UHFFFAOYSA-N 0.000 claims description 2
- 239000000010 aprotic solvent Substances 0.000 claims description 2
- 238000009835 boiling Methods 0.000 claims description 2
- 229930003836 cresol Natural products 0.000 claims description 2
- 125000002183 isoquinolinyl group Chemical group C1(=NC=CC2=CC=CC=C12)* 0.000 claims description 2
- 125000003717 m-cresyl group Chemical group [H]C1=C([H])C(O*)=C([H])C(=C1[H])C([H])([H])[H] 0.000 claims description 2
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 claims description 2
- 238000010329 laser etching Methods 0.000 abstract description 3
- 239000012716 precipitator Substances 0.000 abstract description 3
- 238000005470 impregnation Methods 0.000 abstract description 2
- 238000007790 scraping Methods 0.000 abstract description 2
- 239000012528 membrane Substances 0.000 abstract 2
- 239000007788 liquid Substances 0.000 abstract 1
- 239000000243 solution Substances 0.000 description 14
- 239000002244 precipitate Substances 0.000 description 8
- 239000011521 glass Substances 0.000 description 4
- 238000000034 method Methods 0.000 description 3
- 238000001000 micrograph Methods 0.000 description 3
- 238000012360 testing method Methods 0.000 description 3
- 239000003153 chemical reaction reagent Substances 0.000 description 2
- 238000010790 dilution Methods 0.000 description 2
- 239000012895 dilution Substances 0.000 description 2
- 238000000635 electron micrograph Methods 0.000 description 2
- 230000002349 favourable effect Effects 0.000 description 2
- 238000001914 filtration Methods 0.000 description 2
- 238000007654 immersion Methods 0.000 description 2
- 239000011259 mixed solution Substances 0.000 description 2
- 238000000643 oven drying Methods 0.000 description 2
- 238000011056 performance test Methods 0.000 description 2
- 239000011148 porous material Substances 0.000 description 2
- 230000008569 process Effects 0.000 description 2
- 238000003892 spreading Methods 0.000 description 2
- 230000007480 spreading Effects 0.000 description 2
- 125000002023 trifluoromethyl group Chemical group FC(F)(F)* 0.000 description 2
- 239000004642 Polyimide Substances 0.000 description 1
- 239000007833 carbon precursor Substances 0.000 description 1
- 239000003575 carbonaceous material Substances 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 239000008367 deionised water Substances 0.000 description 1
- 229910021641 deionized water Inorganic materials 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 238000004146 energy storage Methods 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 239000012299 nitrogen atmosphere Substances 0.000 description 1
- 239000011368 organic material Substances 0.000 description 1
- 230000035515 penetration Effects 0.000 description 1
- 238000000197 pyrolysis Methods 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
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- 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
- C08G73/00—Macromolecular compounds obtained by reactions forming a linkage containing nitrogen with or without oxygen or carbon in the main chain of the macromolecule, not provided for in groups C08G12/00 - C08G71/00
- C08G73/06—Polycondensates having nitrogen-containing heterocyclic rings in the main chain of the macromolecule
- C08G73/10—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
- C08G73/1067—Wholly aromatic polyimides, i.e. having both tetracarboxylic and diamino moieties aromatically bound
- C08G73/1071—Wholly aromatic polyimides containing oxygen in the form of ether bonds in the main chain
-
- 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
- C08G73/00—Macromolecular compounds obtained by reactions forming a linkage containing nitrogen with or without oxygen or carbon in the main chain of the macromolecule, not provided for in groups C08G12/00 - C08G71/00
- C08G73/06—Polycondensates having nitrogen-containing heterocyclic rings in the main chain of the macromolecule
- C08G73/10—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
- C08G73/1003—Preparatory processes
- C08G73/1007—Preparatory processes from tetracarboxylic acids or derivatives and diamines
-
- 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
- C08G73/00—Macromolecular compounds obtained by reactions forming a linkage containing nitrogen with or without oxygen or carbon in the main chain of the macromolecule, not provided for in groups C08G12/00 - C08G71/00
- C08G73/06—Polycondensates having nitrogen-containing heterocyclic rings in the main chain of the macromolecule
- C08G73/10—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
- C08G73/1039—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors comprising halogen-containing substituents
-
- 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
- C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
- C08J5/18—Manufacture of films or sheets
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES OR LIGHT-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
- H01G11/04—Hybrid capacitors
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES OR LIGHT-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
- H01G11/48—Conductive polymers
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES OR LIGHT-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
-
- 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
- C08J2379/00—Characterised by the use of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing nitrogen with or without oxygen, or carbon only, not provided for in groups C08J2361/00 - C08J2377/00
- C08J2379/04—Polycondensates having nitrogen-containing heterocyclic rings in the main chain; Polyhydrazides; Polyamide acids or similar polyimide precursors
- C08J2379/08—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
-
- 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
Abstract
The invention provides a fluorine-containing polyimide film, a preparation method thereof and a super capacitor, wherein the preparation method of the fluorine-containing polyimide film comprises the following steps: uniformly stirring diamine and a first solvent under the protection of nitrogen, adding dianhydride and a catalyst, and heating until the reaction is complete to obtain a viscous solution; uniformly stirring the viscous solution and a precipitator, washing for multiple times, performing suction filtration, drying the solid obtained by suction filtration, dissolving the solid in a second solvent to obtain a casting membrane solution, and performing membrane castingAnd (4) coating the liquid on a template in a scraping manner, drying and stripping to obtain the required fluorine-containing polyimide film. The fluorine-containing polyimide film of the invention uses-CF in the preparation process 3 The dianhydride of (1) is CHF in laser etching 2 、CH 2 F and COF 2 The gaseous state is released, so that more microporous structures are generated in the fluorine-containing polyimide film, the impregnation of electrolyte is facilitated, and the performance of the prepared super capacitor is improved.
Description
Technical Field
The invention belongs to the field of chemical synthesis, and particularly relates to a fluorine-containing polyimide film, a preparation method thereof and a supercapacitor.
Background
Recently, the demand for miniature electronic devices has rapidly increased. In particular, transparent devices in wearable device applications have received great attention. This trend has therefore led to active research into small, flexible and transparent energy storage devices.
Supercapacitors have long cycle life and high power density, and are one of the strongest candidates for replacing traditional batteries, which are typically opaque and inflexible miniature energy devices; recently, various organic materials, such as human hair and polyimide, from which a porous carbon material is derived by pyrolysis, can be used as a carbon precursor. However, the commercial polyimide film has small and few pores after laser etching, which is not favorable for the sufficient penetration of electrolyte, so that the electrochemical performance of the supercapacitor is poor.
Disclosure of Invention
In view of this, the present invention is directed to a fluorine-containing polyimide film, a method for preparing the same, and a super capacitor, so as to prepare a polyimide film suitable for a super capacitor, so as to facilitate the immersion of an electrolyte and improve the performance of the super capacitor.
In order to achieve the purpose, the technical scheme of the invention is realized as follows:
a preparation method of a fluorine-containing polyimide film comprises the following steps:
s1: putting diamine and a first solvent into a container, stirring uniformly at normal temperature for a certain time under the protection of nitrogen, adding a certain mass of dianhydride and a catalyst to prepare a mixed solution, and heating until the reaction is complete to obtain a viscous solution; preferably, the solid content of the mixed solution is 15-20%;
s2: uniformly stirring the viscous solution and a precipitator to generate solid precipitate, washing the solid precipitate for multiple times by using the precipitator, then carrying out suction filtration, drying the solid obtained by suction filtration in a vacuum oven to obtain dried solid, dissolving the dried solid in a second solvent to obtain a casting solution, scraping the casting solution on a template, drying in the vacuum oven, cooling to room temperature, putting in deionized water, peeling and drying to obtain the required fluorine-containing polyimide film; preferably, the drying temperature of the solid obtained by suction filtration in a vacuum oven is 100 ℃, the drying time is 12 hours, the drying temperature of the casting solution in the vacuum oven is 180 ℃, and the drying time is 12 hours.
Further, the diamine is 3, 4-diaminodiphenyl ether, and the dianhydride is hexafluorodianhydride.
Further, the molar ratio of the diamine to the dianhydride is 1: 1.
Further, the first solvent is a high boiling point solvent; preferably, the first solvent comprises one of phenol, cresol, m-cresol, o-dichlorobenzene, 1,2, 4-trichlorobenzene; further preferably, the first solvent is m-cresol.
Further, one of pyridine, isoquinoline and triethylamine is used as the catalyst; preferably, the catalyst is isoquinoline.
Further, the reaction conditions in step S1 are reaction at a temperature of 40 ℃ for 1h, reaction at a temperature of 80 ℃ for 1h, reaction at a temperature of 120 ℃ for 2h, reaction at a temperature of 140 ℃ for 2h, reaction at a temperature of 160 ℃ for 2h, and reaction at a temperature of 180 ℃ for 1h, in this order.
Further, the second solvent is an aprotic solvent; preferably, the second solvent is N, N-dimethylacetamide.
Further, the precipitant is ethanol.
The fluorine-containing polyimide film produced according to the above production method.
A super capacitor is prepared by the preparation method or the fluorine-containing polyimide film, and the preparation method of the super capacitor comprises the following steps:
etching the fluorine-containing polyimide film to form an interdigital electrode by laser, and coating an electrolyte on the electrode to obtain a super capacitor; preferably, the laser power is 100%, and the etching depth is 10-15; preferably, the electrolyte is PVA/H 2 SO 4 An electrolyte.
Compared with the prior art, the fluorine-containing polyimide film, the preparation method thereof and the supercapacitor have the following advantages:
the fluorine-containing polyimide film of the invention uses-CF in the preparation process 3 The dianhydride of (1) is CHF in laser etching 2 、CH 2 F and COF 2 The gaseous state is released, so that more microporous structures are generated in the fluorine-containing polyimide film, the impregnation of electrolyte is facilitated, and the performance of the prepared super capacitor is improved.
Drawings
The accompanying drawings, which are incorporated in and constitute a part of this specification, illustrate an embodiment of the invention and, together with the description, serve to explain the invention and not to limit the invention. In the drawings:
FIG. 1 is a schematic view showing a sample of a fluorine-containing polyimide film obtained in example 1 of the present invention;
FIG. 2 is a schematic diagram of a sample of a supercapacitor made according to example 1 of the present invention;
FIG. 3 is an electron micrograph of a fluorine-containing polyimide film obtained in example 1 of the present invention;
FIG. 4 is an electron micrograph of a prior art commercial film.
Detailed Description
Unless defined otherwise, technical terms used in the following examples have the same meanings as commonly understood by one of ordinary skill in the art to which the present invention belongs. The test reagents used in the following examples, unless otherwise specified, are all conventional biochemical reagents; the experimental methods are conventional methods unless otherwise specified.
The present invention will be described in detail with reference to the following examples and accompanying drawings.
Example 1
(1) Diamine 3,4-ODA, 1.20142g, 15mL m-cresol was added to a three-neck flask and stirred at room temperature for 1h under nitrogen.
(2) 6FDA dianhydride, 2.66542g, 2 drops of isoquinoline was added.
(3) Then heating to 40 ℃ for reaction for 1h, 80 ℃ for reaction for 1h, 120 ℃ for reaction for 2h, 140 ℃ for reaction for 2h, 160 ℃ for reaction for 2h, and 180 ℃ for reaction for 1h, and stopping the reaction to obtain a viscous solution. 5mL of m-cresol was added for dilution during the process.
(4) The viscous solution was poured into ethanol to obtain a solid precipitate. Washing with ethanol for several times, vacuum filtering, placing the precipitate in an oven, and oven drying at 100 deg.C.
(5) Preparing 20% solution from 1g of precipitate and 4ml of DMAc, spreading the solution on a clean glass plate, placing the glass plate in an oven, drying for 12 hours at 180 ℃, and stripping to obtain the fluorine-containing polyimide film, wherein the solution is shown in figure 1.
(6) Etching the appearance of an interdigital electrode with the depth of 10 on a commercial film and a dried fluorine-containing polyimide film by using laser, and coating PVA/H on the electrode 2 SO 4 Electrolyte, and after drying for several hours, performance tests were performed.
Example 2
(1) Diamine 3,4-ODA, 1.20142g, 15mL m-cresol was added to a three-necked flask, and stirred at room temperature for 1h under a nitrogen atmosphere.
(2) 6FDA dianhydride, 2.66542g, 2 drops of isoquinoline was added.
(3) Then respectively heating to 40 ℃ for reaction for 1h, reacting at 80 ℃ for 1h, reacting at 120 ℃ for 2h, reacting at 140 ℃ for 2h, reacting at 160 ℃ for 2h, and reacting at 180 ℃ for 1h, and stopping the reaction to obtain a viscous solution. 5mL of m-cresol was added for dilution during the process.
(4) The viscous solution was poured into ethanol to obtain a solid precipitate. Washing with ethanol for several times, vacuum filtering, placing the precipitate in an oven, and oven drying at 100 deg.C.
(5) Preparing 20% solution from 1g of precipitate and 4ml of DMAc, spreading the solution on a clean glass plate, putting the glass plate in a drying oven, drying for 12 hours at 180 ℃, and stripping to obtain the fluorine-containing polyimide film.
(6) Etching the dried film with laser to form an interdigital electrode with a depth of 15, and coating PVA/H on the electrode 2 SO 4 Electrolyte, and dried for several hours, after which performance tests were performed.
The test results of examples 1-2 are shown in Table 1.
TABLE 1 area-specific capacitance calculation results of fluorine-containing polyimide film produced in examples 1-2 and commercial film
Fig. 3 is an electron microscope image of the fluorine-containing polyimide film prepared in example 1, fig. 4 is an electron microscope image of a commercial film, and it can be seen from the electron microscope image that the self-made film containing trifluoromethyl has more pores after etching than the commercial film containing no trifluoromethyl, which is more favorable for the immersion of electrolyte and improves the electrochemical performance, and it can be known from the area specific capacitance data calculated after the test in table 1 that the area specific capacitance of the fluorine-containing polyimide film prepared by the present invention is about 4 times higher than that of the commercial film, and has good electrical properties.
The above description is only for the purpose of illustrating the preferred embodiments of the present invention and should not be taken as limiting the scope of the present invention, which is intended to cover any modifications, equivalents, improvements, etc. within the spirit and scope of the present invention.
Claims (10)
1. The preparation method of the fluorine-containing polyimide film is characterized by comprising the following steps:
s1: uniformly stirring diamine and a first solvent under the protection of nitrogen, adding dianhydride and a catalyst, and heating until the reaction is complete to obtain a viscous solution;
s2: and uniformly stirring the viscous solution and the precipitant, washing for multiple times, carrying out suction filtration, drying the solid obtained by suction filtration, dissolving the solid in a second solvent to obtain a casting solution, carrying out blade coating on the casting solution on a template, drying and stripping to obtain the required fluorine-containing polyimide film.
2. The method for producing a fluorine-containing polyimide film according to claim 1, characterized in that: the diamine is 3, 4-diaminodiphenyl ether, and the dianhydride is hexafluorodianhydride.
3. The method for producing a fluorine-containing polyimide film according to claim 1, characterized in that: the molar ratio of diamine to dianhydride is 1: 1.
4. The method for producing a fluorine-containing polyimide film according to claim 1, characterized in that: the first solvent is a high boiling point solvent; preferably, the first solvent comprises one of phenol, cresol, m-cresol, o-dichlorobenzene, 1,2, 4-trichlorobenzene; further preferably, the first solvent is m-cresol.
5. The method for producing a fluorine-containing polyimide film according to claim 1, characterized in that: one of pyridine, isoquinoline and triethylamine serving as the catalyst; preferably, the catalyst is isoquinoline.
6. The method for producing a fluorine-containing polyimide film according to claim 1, characterized in that: the reaction conditions in step S1 are reaction at 40 ℃ for 1h, reaction at 80 ℃ for 1h, reaction at 120 ℃ for 2h, reaction at 140 ℃ for 2h, reaction at 160 ℃ for 2h, and reaction at 180 ℃ for 1 h.
7. The method for producing a fluorine-containing polyimide film according to claim 1, characterized in that: the second solvent is an aprotic solvent; preferably, the second solvent is N, N-dimethylacetamide.
8. The method for producing a fluorine-containing polyimide film according to claim 1, characterized in that: the precipitant is ethanol.
9. A fluorine-containing polyimide film produced by the production method according to any one of claims 1 to 8.
10. A supercapacitor to which the method of manufacturing according to any one of claims 1 to 9 or the fluorine-containing polyimide film according to claim 9 is applied, the method of manufacturing the supercapacitor comprising the steps of:
etching the fluorine-containing polyimide film by laser to form interdigital electrodes, and coating electrolyte on the electrodesObtaining a super capacitor; preferably, the laser power is 100%, and the etching depth is 10-15; preferably, the electrolyte is PVA/H 2 SO 4 An electrolyte.
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN116462967A (en) * | 2023-04-26 | 2023-07-21 | 昶力管业(常州)有限公司 | Transparent flame-retardant Gao Wenlei-carving-resistant identification product and preparation method thereof |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105348551A (en) * | 2015-12-11 | 2016-02-24 | 桂林电器科学研究院有限公司 | Polyimide porous membrane and preparation method thereof |
| CN111019129A (en) * | 2019-11-22 | 2020-04-17 | 桂林电器科学研究院有限公司 | Low-thermal expansion coefficient soluble polyimide resin powder and preparation method thereof |
| CN112086290A (en) * | 2020-09-11 | 2020-12-15 | 闽江学院 | Flexible extensible supercapacitor array based on mechanical buckling principle and preparation method thereof |
| WO2022079454A1 (en) * | 2020-10-16 | 2022-04-21 | Rd Groupco Limited | Flexible supercapacitor with graphene electrodes embedded in hydrogel electrolyte |
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| CN105348551A (en) * | 2015-12-11 | 2016-02-24 | 桂林电器科学研究院有限公司 | Polyimide porous membrane and preparation method thereof |
| CN111019129A (en) * | 2019-11-22 | 2020-04-17 | 桂林电器科学研究院有限公司 | Low-thermal expansion coefficient soluble polyimide resin powder and preparation method thereof |
| CN112086290A (en) * | 2020-09-11 | 2020-12-15 | 闽江学院 | Flexible extensible supercapacitor array based on mechanical buckling principle and preparation method thereof |
| WO2022079454A1 (en) * | 2020-10-16 | 2022-04-21 | Rd Groupco Limited | Flexible supercapacitor with graphene electrodes embedded in hydrogel electrolyte |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN116462967A (en) * | 2023-04-26 | 2023-07-21 | 昶力管业(常州)有限公司 | Transparent flame-retardant Gao Wenlei-carving-resistant identification product and preparation method thereof |
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