CN115678065A - Preparation method and application of polyimide film - Google Patents
Preparation method and application of polyimide film Download PDFInfo
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- CN115678065A CN115678065A CN202211387252.5A CN202211387252A CN115678065A CN 115678065 A CN115678065 A CN 115678065A CN 202211387252 A CN202211387252 A CN 202211387252A CN 115678065 A CN115678065 A CN 115678065A
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- 229920001721 polyimide Polymers 0.000 title claims abstract description 62
- 238000002360 preparation method Methods 0.000 title claims abstract description 19
- 238000010438 heat treatment Methods 0.000 claims abstract description 53
- 238000000034 method Methods 0.000 claims abstract description 35
- 239000011521 glass Substances 0.000 claims abstract description 29
- 238000003756 stirring Methods 0.000 claims abstract description 25
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims abstract description 24
- USIUVYZYUHIAEV-UHFFFAOYSA-N diphenyl ether Chemical compound C=1C=CC=CC=1OC1=CC=CC=C1 USIUVYZYUHIAEV-UHFFFAOYSA-N 0.000 claims abstract description 18
- 239000002253 acid Substances 0.000 claims abstract description 17
- 239000002994 raw material Substances 0.000 claims abstract description 15
- 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 12
- 238000001291 vacuum drying Methods 0.000 claims abstract description 10
- 239000011248 coating agent Substances 0.000 claims abstract description 6
- 238000000576 coating method Methods 0.000 claims abstract description 6
- FXHOOIRPVKKKFG-UHFFFAOYSA-N N,N-Dimethylacetamide Chemical compound CN(C)C(C)=O FXHOOIRPVKKKFG-UHFFFAOYSA-N 0.000 claims abstract description 5
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 30
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims description 22
- 229910052757 nitrogen Inorganic materials 0.000 claims description 15
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 14
- 229910052786 argon Inorganic materials 0.000 claims description 11
- 239000007789 gas Substances 0.000 claims description 10
- 239000002904 solvent Substances 0.000 claims description 10
- HLBLWEWZXPIGSM-UHFFFAOYSA-N 4-Aminophenyl ether Chemical group C1=CC(N)=CC=C1OC1=CC=C(N)C=C1 HLBLWEWZXPIGSM-UHFFFAOYSA-N 0.000 claims description 9
- 238000005345 coagulation Methods 0.000 claims description 9
- 230000015271 coagulation Effects 0.000 claims description 9
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 8
- 239000004952 Polyamide Substances 0.000 claims description 8
- 229920002647 polyamide Polymers 0.000 claims description 8
- VLDPXPPHXDGHEW-UHFFFAOYSA-N 1-chloro-2-dichlorophosphoryloxybenzene Chemical compound ClC1=CC=CC=C1OP(Cl)(Cl)=O VLDPXPPHXDGHEW-UHFFFAOYSA-N 0.000 claims description 6
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 6
- 239000001257 hydrogen Substances 0.000 claims description 6
- 229910052739 hydrogen Inorganic materials 0.000 claims description 6
- 230000008569 process Effects 0.000 claims description 5
- 125000006158 tetracarboxylic acid group Chemical group 0.000 claims description 3
- RWCCWEUUXYIKHB-UHFFFAOYSA-N benzophenone Chemical compound C=1C=CC=CC=1C(=O)C1=CC=CC=C1 RWCCWEUUXYIKHB-UHFFFAOYSA-N 0.000 claims description 2
- 230000001112 coagulating effect Effects 0.000 claims description 2
- 239000007888 film coating Substances 0.000 claims description 2
- 238000009501 film coating Methods 0.000 claims description 2
- 238000004090 dissolution Methods 0.000 claims 1
- 239000000203 mixture Substances 0.000 claims 1
- 238000010521 absorption reaction Methods 0.000 abstract description 19
- 239000007788 liquid Substances 0.000 abstract description 19
- 238000007654 immersion Methods 0.000 abstract description 9
- 238000001556 precipitation Methods 0.000 abstract description 9
- 238000006243 chemical reaction Methods 0.000 abstract description 7
- 239000011148 porous material Substances 0.000 abstract description 4
- 238000011031 large-scale manufacturing process Methods 0.000 abstract description 3
- 239000011261 inert gas Substances 0.000 abstract 1
- 239000004642 Polyimide Substances 0.000 description 49
- 239000012528 membrane Substances 0.000 description 10
- 238000001035 drying Methods 0.000 description 8
- 239000000463 material Substances 0.000 description 7
- 229920000642 polymer Polymers 0.000 description 6
- 238000011161 development Methods 0.000 description 5
- 238000000614 phase inversion technique Methods 0.000 description 5
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 4
- 229910001416 lithium ion Inorganic materials 0.000 description 4
- 239000003792 electrolyte Substances 0.000 description 3
- 238000005516 engineering process Methods 0.000 description 3
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- 238000002844 melting Methods 0.000 description 3
- 239000002121 nanofiber Substances 0.000 description 3
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 description 2
- 230000009471 action Effects 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 238000005266 casting Methods 0.000 description 2
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- 238000010041 electrostatic spinning Methods 0.000 description 2
- 230000009477 glass transition Effects 0.000 description 2
- 125000005462 imide group Chemical group 0.000 description 2
- 150000002500 ions Chemical class 0.000 description 2
- 229920005575 poly(amic acid) Polymers 0.000 description 2
- 229920000098 polyolefin Polymers 0.000 description 2
- 238000000935 solvent evaporation Methods 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 206010000369 Accident Diseases 0.000 description 1
- 239000002033 PVDF binder Substances 0.000 description 1
- 239000004696 Poly ether ether ketone Substances 0.000 description 1
- 239000004693 Polybenzimidazole Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- 238000003889 chemical engineering Methods 0.000 description 1
- 229920000891 common polymer Polymers 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 238000007599 discharging Methods 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
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- 230000005684 electric field Effects 0.000 description 1
- 238000001523 electrospinning Methods 0.000 description 1
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- 229920006351 engineering plastic Polymers 0.000 description 1
- 238000004880 explosion Methods 0.000 description 1
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- 238000012986 modification Methods 0.000 description 1
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- 229920002239 polyacrylonitrile Polymers 0.000 description 1
- 229920002480 polybenzimidazole Polymers 0.000 description 1
- 229920002530 polyetherether ketone Polymers 0.000 description 1
- 229920006254 polymer film Polymers 0.000 description 1
- 229920002981 polyvinylidene fluoride Polymers 0.000 description 1
- 239000002243 precursor Substances 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 238000011160 research Methods 0.000 description 1
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Images
Classifications
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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
- Y02E60/10—Energy storage using batteries
Abstract
The invention discloses a preparation method and application of a polyimide film, which comprises the steps of taking acid dianhydride and diphenyl ether as raw materials, and preparing a PI film with high porosity and high liquid absorption rate by an immersion precipitation phase conversion method and a vacuum programmed heating method. The preparation method comprises the following steps: firstly, dissolving acid dianhydride and diphenyl ether in one of N, N-dimethylformamide and N, N-dimethylacetamide, and stirring for dissolving; then introducing inert gas, heating and stirring; then placing the glass plate on a glass plate for coating and solidifying; and finally, carrying out vacuum drying and high-temperature heat treatment on the solidified solution to prepare the PI film. By the method, the PI film with the characteristics of high porosity and high liquid absorption rate is prepared, the pore structure can be effectively controlled in the preparation process, and the liquid absorption rate of the PI film can reach 171 percent to the maximum. The method has the advantages of simple operation, low cost, no need of special professional equipment and contribution to large-scale production.
Description
Technical Field
The invention relates to the field of polymer battery diaphragm material manufacturing, in particular to a preparation method and application of a polyimide film.
Background
New energy automobiles and electric bicycles become indispensable vehicles due to the characteristics of convenience, low energy consumption, environmental protection and the like. According to statistics, the quantity of new energy automobiles in 2021 is 784 thousands of new energy automobiles, 291.98 thousands of new energy automobiles are increased in 2020, the year-by-year growth is 59.34%, and the quantity of pure electric automobiles is 640 thousands of new energy automobiles; the social population of electric bicycles is about 3 hundred million. However, with the increasing popularity of new energy automobiles and electric bicycles, the problem of potential safety hazard is increasingly highlighted.
According to statistics, 80% of fire accidents are caused by spontaneous combustion of the battery, and the safety problem of the electric vehicle and the bicycle is mainly solved. The lithium ion battery is a power supply of the electric bicycle which is advocated vigorously by the state at present due to long service life, high specific energy and wide working temperature range. The lithium ion battery is composed of a positive electrode, a negative electrode, a separator and an electrolyte, wherein the separator, which is one of important components of the battery, plays an important role in the aspect of battery safety. Research shows that diaphragm failure caused by high temperature of the lithium ion battery during large-current charging and discharging, and overcharge and overdischarge is a main cause of battery fire. At present, when the temperature of the battery exceeds 150 ℃, the polyolefin diaphragm can shrink or fuse, so that the contact of the positive electrode and the negative electrode is short-circuited, and the combustion or explosion of the battery is caused. The development of the high-temperature safety lithium ion battery diaphragm is hopeful to fundamentally solve the safety problem of the battery and realize key technical breakthrough. In order to improve the safety of the battery separator, researchers have favored polymers with high glass transition temperatures or high melting points in view of the low melting point and limited heat resistance of conventional polyolefins.
At present, common polymer battery diaphragm materials mainly comprise polyvinylidene fluoride, polyether ether ketone, polyimide, polyacrylonitrile, polybenzimidazole and the like, wherein the Polyimide (PI) is expected to become a battery diaphragm of a new generation with excellent thermal stability, chemical stability, electrolyte wettability and outstanding mechanical properties. However, the foreign countries adopt the policies of technical blockade and product prohibition for the PI industry in China, so that the development of a PI film with excellent performance becomes a key problem which needs to be solved urgently at present. Polyimide (PI) is a polymer having an imide ring in the main chain, and due to the presence of repeated imide structural units in the main chain, the PI material is endowed with excellent thermal stability and chemical stability, thus being a high-performance engineering plastic with great development prospects and being applied to various fields, such as microelectronics, aerospace, machinery, chemical engineering and the like, in various forms.
At present, the preparation method of the PI material is diversified by combining the requirements of application and acquisition, for example, the PI fiber can be prepared by using polyamic acid as a precursor through an electrostatic spinning method, a wet spinning method, a dry spinning method and other methods; the PI film can be prepared by a tape casting method and a spin coating method. Due to the high melting temperature and high glass transition temperature of the PI material, the processing difficulty is increased, and the preparation process of the PI film is limited. The most common method for preparing PI at present is the electrospinning technique. The electrostatic spinning technology is a novel technology that a high polymer solution or melt is stretched into nano-fibers under the action of a strong electrostatic field force under the action of a high-voltage electric field. The nano-fiber prepared by the method has the characteristics of small diameter, large surface area, high porosity, uniform pore size distribution and the like. Although the diaphragm material prepared by the technology has the characteristics of high porosity, high liquid absorption rate, controllable thickness, high heat resistance and the like. However, since the interaction between PI fibers is weak, the mechanical strength of the nanofiber membrane is poor, and at the same time, PI fibers are likely to expand in an electrolyte, and the size after swelling is difficult to control. Meanwhile, the problems of high preparation cost, high equipment cost, complex process, and harsh preparation conditions, such as environmental temperature, humidity and other external conditions, difficulty in large-scale production and low efficiency exist.
Phase inversion is currently becoming one of the most important processes for polymer film formation, and the method has been used in many fields, such as ultrafiltration membrane, reverse osmosis membrane, etc., wherein the phase inversion method can be divided into: solvent evaporation phase inversion, immersion precipitation phase inversion, thermally induced phase inversion and steam induced phase inversion. The solvent evaporation phase conversion method is the most common method, but a compact surface layer exists on the surface of the membrane, so that the liquid absorption rate of the membrane is greatly limited; the thermal induction phase inversion method is a casting solution prepared at high temperature, and is more suitable for polymers with poor solubility; the immersion precipitation phase inversion method and the steam induced phase inversion method have the advantages that the phase separation rate is relatively slow, the pore structure size is relatively small, and the preparation process depends on equipment, process and environmental conditions seriously.
Disclosure of Invention
In order to meet the development requirement of high safety performance of the battery and solve the technical problem of preparation of a polymer battery diaphragm material, acid dianhydride and diphenyl ether are used as raw materials, and a PI film with high porosity and high liquid absorption rate is prepared by an immersion precipitation phase inversion method and a vacuum programmed heating method, so that the development requirement of high safety performance of the battery is met while high safety is ensured.
The invention aims to provide a preparation method of a polyimide film, which comprises the following steps:
(1) Acid dianhydride and diphenyl ether are used as raw materials, are dissolved in N, N-dimethylformamide or N, N-dimethylacetamide according to a certain proportion, and are stirred and dissolved until a uniform solution is formed;
(2) Introducing the uniform solution obtained in the step (1) into an inert atmosphere, and stirring under certain conditions to obtain a polyamide acid (PAA) solution;
(3) Placing the PAA solution obtained in the step (2) on a glass plate, and coating the PAA solution;
(4) Placing the coated glass plate in the step (3) in an ethanol or acetone coagulating bath, standing, and taking out the coagulated PAA solution after the PAA solution on the glass plate is solidified;
(5) Performing vacuum drying on the solidified PAA solution obtained in the step (4) by adopting a temperature programming mode to prepare a PAA film;
(6) And (4) carrying out high-temperature heat treatment on the PAA film obtained in the step (5) to prepare the PI film.
Preferably, the acid dianhydride in the step (1) is one of 3,3', 4' -diphenyl ether tetracarboxylic dianhydride, pyromellitic dianhydride, and 3,3', 4' -benzophenone tetracarboxylic dianhydride.
Preferably, the diphenyl ether in the step (1) is 4,4' -diaminodiphenyl ether.
Preferably, in the step (1), the molar ratio of the acid dianhydride to the diphenyl ether is 1.
Preferably, the inert atmosphere in the step (2) is one of high-purity nitrogen, argon and hydrogen/argon mixed gas, the stirring temperature is 0-40 ℃, the stirring time is 10-24 h, and the stirring speed is 200-450 rpm.
Preferably, the thickness of the film after the film coating in the step (3) is controlled to be 75-200 μm.
Preferably, the temperature of the coagulation bath in the step (4) is 25-40 ℃, and the standing time is 10-30 min.
Preferably, the temperature raising process in the step (5) is as follows: heating to 40 ℃ at the speed of 2-5 ℃/min, keeping the temperature for 10-30 min, heating to 70 ℃ at the speed of 2-5 ℃/min, and keeping the temperature for 30 min-12 h.
Preferably, the temperature rise rate of the high-temperature heat treatment in the step (6) is 2-5 ℃/min, the temperature is 100-300 ℃, the time of the high-temperature heat treatment is 1-6 h, and the heat treatment atmosphere is one of nitrogen, argon and hydrogen/argon mixed gas.
The invention has the beneficial effects that:
(1) The invention prepares the PI film with the characteristics of high porosity and high liquid absorption rate by combining the immersion precipitation phase conversion method with vacuum temperature programming;
(2) The invention adopts a mode of combining the immersion precipitation phase conversion method with vacuum programmed heating, and because the drying process adopts the vacuum programmed heating mode, the volatilization rates of solvents with different boiling points in the casting solution can be effectively controlled, the gradient formation mode of a pore structure is realized, and the porosity of the PI film is improved;
(3) The porosity of the PI film prepared by combining the immersion precipitation phase conversion method and the vacuum temperature programming method is 32-52%;
(4) The liquid absorption rate of the PI film prepared by the method combining the immersion precipitation phase conversion method and the vacuum programmed temperature rise can reach 145-171 percent;
(5) The immersion precipitation phase conversion method and the vacuum program heating method adopted by the invention have the advantages of simple operation, low cost, no need of special professional equipment and contribution to large-scale production.
Drawings
FIG. 1 is a photograph of a PI film;
FIG. 2 is a diagram of infrared characterization results of PI films;
FIG. 3 is a graph comparing the contact angle of PI films to commercial membranes;
FIG. 4 is a graph comparing porosity of commercial battery separator films to PI films;
fig. 5 is a graph comparing the liquid absorption rates of commercial battery separators and PI films.
Detailed Description
Example 1:
(1) Pyromellitic dianhydride and 4,4' -diaminodiphenyl ether are taken as raw materials, dissolved in N, N-dimethylformamide solvent according to the molar ratio of 1.
(2) And (2) introducing high-purity nitrogen into the uniform solution obtained in the step (1), and stirring for 15 hours at the temperature of 40 ℃ and the stirring speed of 400rpm under the protection of gas to form viscous yellow polyamide acid (PAA) solution.
(3) The PAA solution obtained in step (2) was placed on a glass plate, and the thickness of the PAA solution was adjusted to 200 μm by an applicator to coat the PAA solution.
(4) And (4) placing the coated glass plate in the step (3) in an ethanol coagulation bath, standing for 20min at the temperature of 25 ℃, and taking out the coagulated PAA solution after the PAA solution on the glass plate is solidified.
(5) And (5) quickly placing the solidified PAA solution in the step (4) into a vacuum drying oven to be dried by adopting a programmed heating mode, heating to 40 ℃ at the speed of 2 ℃/min, keeping the temperature for 10min, heating to 70 ℃ at the speed of 2 ℃/min, keeping the temperature for 12h, and drying to prepare the PAA film.
(6) And (4) placing the PAA film obtained in the step (5) in a tube furnace, heating to 200 ℃ at a heating rate of 2 ℃/min under the protection of nitrogen, and keeping the temperature for 2 hours to prepare the PI film with the porosity of 52% and the liquid absorption rate of 171%.
As can be seen from the photographs of the PI films (as shown in fig. 1), the PI prepared in this example appears yellow and has a flat surface. As can be seen from the infrared characterization results of the PI films (as shown in FIG. 2), the PI films are respectively 1780cm -1 ,1716cm -1 At 1372cm, where the C = O bond in the imide group appears -1 The C-N stretching vibration peak appears, which shows that the PI can be successfully prepared by the method. Fig. 3 shows the contact angle test results of the PI film and the commercial separator, and the hydrophilicity of the film can be analyzed by comparing the contact angles. By comparison, the contact angle of the commercial membrane was found to be 111.4 ° (as shown in fig. 3 a), significantly higher than 74.5 ° (as shown in fig. 3 b) for the PI film. This result indicates that the PI membrane prepared according to the present invention has more excellent hydrophilicity and more excellent solution wettability than the commercial membrane, which means that the PI membrane is more suitable for use in batteries.
Fig. 4 is a comparison of the porosity of the commercial battery separator and the porosity of the PI film, where the porosity of the commercial battery separator measured by the n-butanol method is 37.9% and the porosity of the PI film is 52%, which means that the PI film prepared by the present invention has higher porosity, and the high porosity can provide a channel for the transmission of battery ions, which is helpful for improving the battery performance.
Fig. 5 is a comparison of the liquid absorption rates of the commercial battery diaphragm and the PI film, and it can be seen from the figure that the liquid absorption rate of the commercial battery diaphragm is 111.6%, and the liquid absorption rate of the PI film prepared by the invention is up to 171%, which is enough to indicate that the PI film prepared by the invention is more suitable for the ion battery.
Example 2:
(1) Dissolving 3,3', 4' -diphenyl ether tetracarboxylic dianhydride and 4,4' -diaminodiphenyl ether serving as raw materials in an N, N-dimethylformamide solvent according to the molar ratio of 1.
(2) And (2) introducing high-purity nitrogen into the uniform solution obtained in the step (1), and stirring for 15 hours at the temperature of 40 ℃ and the stirring speed of 400rpm under the protection of gas to form viscous yellow polyamide acid (PAA) solution.
(3) The PAA solution obtained in step (2) was placed on a glass plate, and the thickness of the PAA solution was adjusted to 200 μm by an applicator to coat the PAA solution.
(4) And (4) placing the coated glass plate in the step (3) in an ethanol coagulation bath, standing for 20min at the temperature of 25 ℃, and taking out the coagulated PAA solution after the PAA solution on the glass plate is solidified.
(5) And (4) quickly placing the solidified PAA solution in the step (4) into a vacuum drying oven to be dried by adopting a programmed heating mode, heating to 40 ℃ at the speed of 2 ℃/min, keeping the temperature for 10min, heating to 70 ℃ at the speed of 2 ℃/min, keeping the temperature for 12h, and drying to prepare the PAA film.
(6) And (4) placing the PAA film obtained in the step (5) in a tube furnace, heating to 200 ℃ at a heating rate of 2 ℃/min under the protection of nitrogen, and keeping the temperature for 2 hours to prepare the PI film with the porosity of 32% and the liquid absorption rate of 145%.
Example 3:
(1) Pyromellitic dianhydride and 4,4' -diaminodiphenyl ether are used as raw materials, and are dissolved in an N, N-dimethylformamide solvent according to the molar ratio of 1.
(2) And (2) introducing high-purity nitrogen into the uniform solution obtained in the step (1), and stirring for 15 hours at the temperature of 40 ℃ and the stirring speed of 400rpm under the protection of gas to form viscous yellow polyamide acid (PAA) solution.
(3) The PAA solution obtained in step (2) was placed on a glass plate, and the thickness of the PAA solution was adjusted to 200 μm by an applicator to coat the PAA solution.
(4) And (4) placing the coated glass plate in the step (3) in an ethanol coagulation bath, standing for 20min at the temperature of 25 ℃, and taking out the coagulated PAA solution after the PAA solution on the glass plate is solidified.
(5) And (5) quickly placing the solidified PAA solution in the step (4) into a vacuum drying oven to be dried by adopting a programmed heating mode, heating to 40 ℃ at the speed of 2 ℃/min, keeping the temperature for 10min, heating to 70 ℃ at the speed of 2 ℃/min, keeping the temperature for 12h, and drying to prepare the PAA film.
(6) And (4) placing the PAA film obtained in the step (5) in a tube furnace, heating to 200 ℃ at a heating rate of 2 ℃/min under the protection of nitrogen, and keeping the temperature for 2 hours to prepare the PI film with the porosity of 35% and the liquid absorption rate of 148%.
Example 4:
(1) Pyromellitic dianhydride and 4,4' -diaminodiphenyl ether are taken as raw materials, dissolved in an N, N-dimethylformamide solvent according to the molar ratio of 1.
(2) And (2) introducing high-purity nitrogen into the uniform solution obtained in the step (1), and stirring for 15 hours at the temperature of 40 ℃ and the stirring speed of 400rpm under the protection of gas to form viscous yellow polyamide acid (PAA) solution.
(3) The PAA solution obtained in step (2) was placed on a glass plate, and the thickness of the coating film was adjusted to 200 μm by an applicator.
(4) And (4) placing the coated glass plate in the step (3) in an ethanol coagulation bath, standing for 20min at 25 ℃, and taking out the coagulated PAA solution after the PAA solution on the glass plate is solidified.
(5) And (5) quickly placing the solidified PAA solution in the step (4) into a vacuum drying oven to be dried by adopting a programmed heating mode, heating to 40 ℃ at the speed of 2 ℃/min, keeping the temperature for 10min, heating to 70 ℃ at the speed of 2 ℃/min, keeping the temperature for 12h, and drying to prepare the PAA film.
(6) And (4) placing the PAA film obtained in the step (5) in a tube furnace, heating to 200 ℃ at a heating rate of 2 ℃/min under the protection of nitrogen, and keeping the temperature for 2 hours to prepare the PI film with the porosity of 39% and the liquid absorption rate of 151%.
Example 5:
(1) Pyromellitic dianhydride and 4,4' -diaminodiphenyl ether are taken as raw materials, dissolved in an N, N-dimethylformamide solvent according to the molar ratio of 1.
(2) And (2) introducing high-purity nitrogen into the uniform solution obtained in the step (1), and stirring for 15 hours at the temperature of 40 ℃ and the stirring speed of 400rpm under the protection of gas to form viscous yellow polyamide acid (PAA) solution.
(3) The PAA solution obtained in step (2) was placed on a glass plate, and the thickness of the PAA solution was adjusted to 200 μm by an applicator to coat the PAA solution.
(4) And (4) placing the coated glass plate in the step (3) in an ethanol coagulation bath, standing for 20min at the temperature of 25 ℃, and taking out the coagulated PAA solution after the PAA solution on the glass plate is solidified.
(5) And (4) quickly placing the solidified PAA solution in the step (4) into a vacuum drying oven to be dried by adopting a programmed heating mode, heating to 40 ℃ at the speed of 5 ℃/min, keeping the temperature for 10min, heating to 70 ℃ at the speed of 5 ℃/min, keeping the temperature for 12h, and drying to prepare the PAA film.
(6) And (4) placing the PAA film obtained in the step (5) in a tube furnace, heating to 200 ℃ at a heating rate of 2 ℃/min under the protection of nitrogen, and keeping the temperature for 2 hours to prepare the PI film with the porosity of 43% and the liquid absorption rate of 158%.
Example 6:
(1) Dissolving 3,3', 4' -benzophenonetetracarboxylic dianhydride and 4,4' -diaminodiphenyl ether which are used as raw materials in an N, N-dimethylacetamide solvent according to the molar ratio of 1.
(2) And (2) introducing high-purity argon into the uniform solution obtained in the step (1), and stirring for 10 hours at the temperature of 20 ℃ and the stirring speed of 450rpm under the protection of gas to form a viscous yellow polyamide acid (PAA) solution.
(3) The PAA solution of step (2) was placed on a glass plate, and the coating was performed by adjusting the thickness of the coating film to 150 μm using an applicator.
(4) And (4) placing the coated glass plate in the step (3) in an acetone coagulation bath, standing for 30min at the temperature of 40 ℃, and taking out the coagulated PAA solution after the PAA solution on the glass plate is solidified.
(5) And (5) quickly placing the solidified PAA solution in the step (4) into a vacuum drying oven to be dried by adopting a programmed heating mode, heating to 40 ℃ at the speed of 2 ℃/min, keeping the temperature for 20min, heating to 70 ℃ at the speed of 5 ℃/min, keeping the temperature for 12h, and drying to prepare the PAA film.
(6) And (4) placing the PAA film obtained in the step (5) in a tube furnace, heating to 100 ℃ at a heating rate of 5 ℃/min under the protection of argon, and keeping the temperature for 6 hours to prepare the PI film with the porosity of 47% and the liquid absorption rate of 163%.
Example 7:
(1) Dissolving 3,3', 4' -benzophenonetetracarboxylic dianhydride and 4,4' -diaminodiphenyl ether which are used as raw materials in a molar ratio of 1.5 in an N, N-dimethylacetamide solvent, and carrying out ultrasonic stirring until a uniform solution is formed, wherein the mass fraction of the total mass of the raw materials in the solvent is 15%.
(2) And (2) introducing high-purity hydrogen/nitrogen into the uniform solution obtained in the step (1), and stirring for 24 hours at the temperature of 0 ℃ and the stirring speed of 200rpm under the protection of gas to form a viscous yellow polyamic acid (PAA) solution.
(3) The PAA solution obtained in step (2) was placed on a glass plate, and the thickness thereof was adjusted to 75 μm by an applicator to coat the PAA solution.
(4) And (4) placing the coated glass plate in the step (3) in an acetone coagulation bath, standing for 10min at the temperature of 40 ℃, and taking out the coagulated PAA solution after the PAA solution on the glass plate is solidified.
(5) And (4) quickly placing the solidified PAA solution in the step (4) into a vacuum drying oven to be dried by adopting a programmed heating mode, heating to 40 ℃ at the speed of 5 ℃/min, keeping the temperature for 30min, heating to 70 ℃ at the speed of 2 ℃/min, and drying at the constant temperature for 30min to prepare the PAA film.
(6) And (4) placing the PAA film obtained in the step (5) in a tube furnace, heating to 300 ℃ at a heating rate of 3 ℃/min under the protection of hydrogen/argon, and keeping the temperature for 1h to prepare the PI film with the porosity of 50% and the liquid absorption rate of 168%.
The above embodiments are only for illustrating the technical idea and features of the present invention, and the purpose of the present invention is to enable those skilled in the art to understand the content of the present invention and implement the present invention, and not to limit the protection scope of the present invention by this. All equivalent changes or modifications made in accordance with the spirit of the present disclosure are intended to be covered by the scope of the present disclosure.
Claims (8)
1. The preparation method and the application of the polyimide film are characterized in that the preparation process comprises the following steps:
(1) Acid dianhydride and diphenyl ether are used as raw materials, dissolved in N, N-dimethylformamide or N, N-dimethylacetamide according to a certain proportion, and stirred to dissolve until a uniform solution is formed;
(2) Introducing the uniform solution obtained in the step (1) into an inert atmosphere, and stirring under certain conditions until a polyamide acid (PAA) solution is formed;
(3) Placing the PAA solution obtained in the step (2) on a glass plate, and coating the PAA solution;
(4) Placing the coated glass plate in the step (3) in an ethanol or acetone coagulating bath, standing, and taking out the coagulated PAA solution after the PAA solution on the glass plate is solidified;
(5) Carrying out vacuum drying on the solidified PAA solution obtained in the step (4) by adopting a temperature programming mode to prepare a PAA film;
(6) And (6) carrying out high-temperature heat treatment on the PAA film obtained in the step (5) to prepare the PI film.
2. The method for preparing a polyimide film according to claim 1, wherein the acid dianhydride in step (1) is one of 3,3', 4' -diphenyl ether tetracarboxylic dianhydride, pyromellitic dianhydride, and 3,3', 4' -benzophenone tetracarboxylic dianhydride, and the diphenyl ether is 4,4' -diaminodiphenyl ether.
3. The preparation method and the application of the polyimide film according to claim 1, wherein in the step (1), the molar ratio of the acid dianhydride to the diphenyl ether in the raw materials is 1-1 to 1.5, and the dissolution ratio of the raw materials is 10-20% of the total mass of the raw materials in the solvent.
4. The method for preparing polyimide film according to claim 1, wherein the inert atmosphere in step (2) is one of high purity nitrogen, argon and hydrogen/argon mixture, the stirring temperature is 0-40 ℃, the stirring time is 10-24 h, and the stirring speed is 200-450 rpm.
5. The preparation method and the application of the polyimide film as claimed in claim 1, wherein the thickness of the film after the film coating in the step (3) is controlled to be 75-200 μm.
6. The preparation method and the application of the polyimide film as claimed in claim 1, wherein the temperature of the coagulation bath in the step (4) is 25-40 ℃, and the standing time is 10-30 min.
7. The preparation method and the application of the polyimide film according to claim 1, wherein the temperature raising process in the step (5) is as follows: heating to 40 ℃ at the speed of 2-5 ℃/min, keeping the temperature for 10-30 min, heating to 70 ℃ at the speed of 2-5 ℃/min, and keeping the temperature for 30 min-12 h.
8. The method for preparing a polyimide film according to claim 1, wherein the temperature rise rate of the high-temperature heat treatment in the step (6) is 2-5 ℃/min, the temperature is 100-300 ℃, the time of the high-temperature heat treatment is 1-6 h, and the heat treatment atmosphere is one of nitrogen, argon and a hydrogen/argon mixed gas.
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Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108365151A (en) * | 2018-01-31 | 2018-08-03 | 青岛蓝科途膜材料有限公司 | A kind of polyimide high temperature-resistant lithium battery diaphragm and preparation method thereof |
| WO2018218984A1 (en) * | 2017-06-01 | 2018-12-06 | 青岛中科华联新材料股份有限公司 | High temperature-resistant aramid lithium-ion battery composite separator and manufacturing method therefor |
| CN110256709A (en) * | 2019-07-07 | 2019-09-20 | 齐鲁工业大学 | A kind of preparation method based on the molding Kapton of coagulating bath |
| CN110256717A (en) * | 2019-07-03 | 2019-09-20 | 西安交通大学 | A kind of porous polyimide film and its preparation method and application |
| CN110828750A (en) * | 2019-10-30 | 2020-02-21 | 桑顿新能源科技有限公司 | Porous polyimide film, preparation method thereof and lithium ion battery |
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Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2018218984A1 (en) * | 2017-06-01 | 2018-12-06 | 青岛中科华联新材料股份有限公司 | High temperature-resistant aramid lithium-ion battery composite separator and manufacturing method therefor |
| CN108365151A (en) * | 2018-01-31 | 2018-08-03 | 青岛蓝科途膜材料有限公司 | A kind of polyimide high temperature-resistant lithium battery diaphragm and preparation method thereof |
| CN110256717A (en) * | 2019-07-03 | 2019-09-20 | 西安交通大学 | A kind of porous polyimide film and its preparation method and application |
| CN110256709A (en) * | 2019-07-07 | 2019-09-20 | 齐鲁工业大学 | A kind of preparation method based on the molding Kapton of coagulating bath |
| CN110828750A (en) * | 2019-10-30 | 2020-02-21 | 桑顿新能源科技有限公司 | Porous polyimide film, preparation method thereof and lithium ion battery |
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