CN115678065B - Preparation method and application of polyimide film - Google Patents
Preparation method and application of polyimide film Download PDFInfo
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- CN115678065B CN115678065B CN202211387252.5A CN202211387252A CN115678065B CN 115678065 B CN115678065 B CN 115678065B CN 202211387252 A CN202211387252 A CN 202211387252A CN 115678065 B CN115678065 B CN 115678065B
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- 229920001721 polyimide Polymers 0.000 title claims abstract description 57
- 238000002360 preparation method Methods 0.000 title claims abstract description 15
- 238000010438 heat treatment Methods 0.000 claims abstract description 42
- 239000002994 raw material Substances 0.000 claims abstract description 37
- 239000011521 glass Substances 0.000 claims abstract description 28
- 238000003756 stirring Methods 0.000 claims abstract description 28
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims abstract description 24
- 238000000034 method Methods 0.000 claims abstract description 19
- 239000002253 acid Substances 0.000 claims abstract description 17
- USIUVYZYUHIAEV-UHFFFAOYSA-N diphenyl ether Chemical compound C=1C=CC=CC=1OC1=CC=CC=C1 USIUVYZYUHIAEV-UHFFFAOYSA-N 0.000 claims abstract description 16
- 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
- 230000001112 coagulating effect Effects 0.000 claims abstract description 11
- 239000011248 coating agent Substances 0.000 claims abstract description 11
- 238000000576 coating method Methods 0.000 claims abstract description 11
- 238000001291 vacuum drying Methods 0.000 claims abstract description 10
- FXHOOIRPVKKKFG-UHFFFAOYSA-N N,N-Dimethylacetamide Chemical compound CN(C)C(C)=O FXHOOIRPVKKKFG-UHFFFAOYSA-N 0.000 claims abstract description 5
- 238000004090 dissolution Methods 0.000 claims abstract description 3
- 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
- 239000002904 solvent Substances 0.000 claims description 17
- 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 11
- 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
- 239000004952 Polyamide Substances 0.000 claims description 9
- 229920002647 polyamide Polymers 0.000 claims description 9
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 8
- 239000000463 material Substances 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
- RWCCWEUUXYIKHB-UHFFFAOYSA-N benzophenone Chemical compound C=1C=CC=CC=1C(=O)C1=CC=CC=C1 RWCCWEUUXYIKHB-UHFFFAOYSA-N 0.000 claims description 4
- 125000006158 tetracarboxylic acid group Chemical group 0.000 claims description 3
- 239000007788 liquid Substances 0.000 abstract description 17
- 238000010521 absorption reaction Methods 0.000 abstract description 16
- 238000000614 phase inversion technique Methods 0.000 abstract description 12
- 238000001556 precipitation Methods 0.000 abstract description 9
- 238000007654 immersion Methods 0.000 abstract description 8
- 230000009286 beneficial effect Effects 0.000 abstract description 4
- 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
- 229920005575 poly(amic acid) Polymers 0.000 description 58
- 239000004642 Polyimide Substances 0.000 description 50
- 238000001035 drying Methods 0.000 description 15
- 229920000642 polymer Polymers 0.000 description 7
- 239000012528 membrane Substances 0.000 description 6
- 238000011161 development Methods 0.000 description 5
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 4
- 238000005516 engineering process Methods 0.000 description 4
- 229910001416 lithium ion Inorganic materials 0.000 description 4
- 238000009210 therapy by ultrasound Methods 0.000 description 4
- 239000003792 electrolyte Substances 0.000 description 3
- 230000007613 environmental effect Effects 0.000 description 3
- 239000000835 fiber Substances 0.000 description 3
- 238000005213 imbibition Methods 0.000 description 3
- 230000008018 melting Effects 0.000 description 3
- 238000002844 melting Methods 0.000 description 3
- 239000002121 nanofiber Substances 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 description 2
- 238000005266 casting Methods 0.000 description 2
- 238000002485 combustion reaction Methods 0.000 description 2
- 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
- 238000004519 manufacturing process Methods 0.000 description 2
- 229920000098 polyolefin Polymers 0.000 description 2
- 230000000630 rising effect Effects 0.000 description 2
- 238000000935 solvent evaporation Methods 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
- 230000009471 action Effects 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 230000000903 blocking effect Effects 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- 238000012512 characterization method Methods 0.000 description 1
- 230000001419 dependent effect Effects 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 238000000578 dry spinning Methods 0.000 description 1
- 238000001523 electrospinning Methods 0.000 description 1
- 230000005686 electrostatic field Effects 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 229920006351 engineering plastic Polymers 0.000 description 1
- 238000004880 explosion Methods 0.000 description 1
- 150000003949 imides Chemical class 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 230000006698 induction Effects 0.000 description 1
- 230000003993 interaction Effects 0.000 description 1
- 238000004377 microelectronic Methods 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000005191 phase separation Methods 0.000 description 1
- 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
- 238000001223 reverse osmosis Methods 0.000 description 1
- 238000007711 solidification Methods 0.000 description 1
- 230000008023 solidification Effects 0.000 description 1
- 238000004528 spin coating Methods 0.000 description 1
- 230000002269 spontaneous effect Effects 0.000 description 1
- 239000002344 surface layer Substances 0.000 description 1
- 238000010345 tape casting Methods 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 238000000108 ultra-filtration Methods 0.000 description 1
- 238000002166 wet spinning Methods 0.000 description 1
Classifications
-
- 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
Landscapes
- Manufacture Of Porous Articles, And Recovery And Treatment Of Waste Products (AREA)
- Macromolecular Compounds Obtained By Forming Nitrogen-Containing Linkages In General (AREA)
Abstract
The invention discloses a preparation method and application of a polyimide film, wherein the method comprises the steps of taking acid dianhydride and diphenyl ether as raw materials, and preparing the PI film with high porosity and high liquid absorption rate through an immersion precipitation phase inversion method and a vacuum programmed temperature method. The preparation method comprises the following steps: firstly, acid dianhydride and diphenyl ether are dissolved in one solution of N, N-dimethylformamide and N, N-dimethylacetamide, and stirred for dissolution; then inert gas is introduced into the reactor for heating and stirring; then placing the glass plate for coating and solidifying; finally, vacuum drying is carried out on the coagulating solution, and high-temperature heat treatment is carried out, thus preparing 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% at most. The invention has simple operation and low cost, does not need special professional equipment, and is beneficial to large-scale production.
Description
Technical Field
The invention relates to the field of manufacturing of polymer battery diaphragm materials, in particular to a preparation method and application of a polyimide film.
Background
New energy automobiles and electric bicycles have become indispensable transportation means due to the characteristics of convenience, low energy consumption, environmental protection and the like. According to statistics, the number of the new energy automobiles in 2021 in China is 784 ten thousand, and 291.98 ten thousand are increased compared with 2020, and the number of the new energy automobiles in 2021 in China is increased by 59.34% in a same ratio, wherein the number of the new energy automobiles in the pure electric automobiles in 2021 in China is 640 ten thousand; the society of electric bicycle keeps the volume about 3 hundred million. However, with the continuous increase of the popularity of new energy automobiles and electric bicycles, the problem of potential safety hazards is also increasingly highlighted.
According to statistics, 80% of fire accidents are caused by spontaneous combustion of the battery, and the problem of safety of the electric bicycle is mainly solved. The lithium ion battery is a power supply of an electric bicycle advocated by the state at present because of long service life, high specific energy and wide working temperature range. Lithium ion batteries are 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 a critical role in the safety of the battery. Research shows that diaphragm failure caused by high temperature when a lithium ion battery is charged and discharged with large current and overcharged and overdischarged is a main cause of battery fire. When the temperature of the battery exceeds 150 ℃, the polyolefin diaphragm at the present stage can shrink or fuse, so that the anode and the cathode are in contact short circuit, and the combustion or explosion of the battery is initiated. The development of the high-temperature safe lithium ion battery diaphragm is hopeful to fundamentally solve the battery safety problem and realize key technical breakthrough. In order to improve the safety of battery separators, researchers have been favoured for polymers with high glass transition temperatures or high melting points in view of the low melting point and limited heat resistance of conventional polyolefins.
The conventional polymer battery diaphragm materials mainly comprise polyvinylidene fluoride, polyether-ether-ketone, polyimide, polyacrylonitrile, polybenzimidazole and the like, wherein Polyimide (PI) is expected to become a new generation battery diaphragm with excellent thermal stability, chemical stability, electrolyte wettability and outstanding mechanical properties. However, foreign technology blocking and product banning policies are adopted for the PI industry in China, so that the development of PI films with excellent performance is a key problem to be solved urgently. Polyimide (PI) is a polymer with imide rings on the main chain, and because of the existence of repeated imide structural units in the main chain, the Polyimide (PI) material has excellent thermal stability and chemical stability, becomes high-performance engineering plastics with development prospect, and is applied to various fields such as microelectronics, aerospace, machinery, chemical industry and the like in various forms.
The current PI material preparation method is diversified in combination with the application requirements, for example, polyamide acid is used as a precursor, and PI fibers can be prepared through electrostatic spinning, wet spinning, dry spinning and other methods; the PI film can be prepared by a tape casting method and a spin coating method. The high melting temperature and the high glass transition temperature of the PI material increase the processing difficulty, so that the preparation process of the PI film is limited. The most commonly used PI preparation method at present is the electrospinning technique. The electrostatic spinning technology is a novel technology for stretching a high polymer solution or melt into nanofibers under the action of a strong electrostatic field. The nanofiber 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, controllable thickness, high heat resistance and the like. However, since PI fibers have weak interactions, the nanofiber membrane has poor mechanical strength, and at the same time PI fibers are easily expanded in an electrolyte, and the size after the expansion is difficult to control. Meanwhile, the problems of high preparation cost, high equipment manufacturing cost, complex process, severe requirements on external conditions such as environmental temperature, humidity and the like, difficulty in large-scale production and low efficiency exist.
The phase inversion method is currently becoming one of the most important processes for polymer film forming process, and has been used in various 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. Solvent evaporation phase inversion is the most common one, but the membrane surface has a compact surface layer, and the membrane liquid absorption rate 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 phase separation rate in the preparation process of the immersed precipitation phase inversion method and the steam-induced phase inversion method is relatively slow, the pore structure size is relatively small, and the preparation process is seriously dependent on equipment, process and environmental conditions.
Disclosure of Invention
In order to meet the development requirements of safety and high performance of the battery and solve the technical problem of preparation of the polymer battery diaphragm material, the invention prepares the PI film with high porosity and high liquid absorption rate by taking acid dianhydride and diphenyl ether as raw materials through an immersion precipitation phase inversion method and a vacuum programmed temperature rising method, and meets the development requirements of safety and high performance of the battery while ensuring high safety.
The invention aims to provide a preparation method of a polyimide film, which comprises the following steps:
(1) Acid dianhydride and diphenyl ether are taken as raw materials and dissolved in N, N-dimethylformamide or N, N-dimethylacetamide according to a certain proportion, and stirred and dissolved until a uniform solution is formed;
(2) Introducing inert atmosphere into the uniform solution obtained in the step (1), and stirring under certain conditions to obtain polyamic 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) Vacuum drying the solidified PAA solution obtained in the step (4) in a temperature programming mode to prepare a PAA film;
(6) And (3) performing high-temperature heat treatment on the PAA film 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 1:1-1:1.5, and the dissolution proportion of the raw materials is 10-20% of the mass fraction of the total mass of the raw materials in the solvent.
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 coating in the step (3) is controlled to be 75-200 μm.
Preferably, the temperature of the solidification bath in the step (4) is 25-40 ℃, and the standing time is 10-30 min.
Preferably, the program heating 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 30-12 h.
Preferably, the temperature rising rate of the high-temperature heat treatment in the step (6) is 2-5 ℃/min, the temperature is 100-300 ℃, the high-temperature heat treatment time is 1-6 h, and the heat treatment atmosphere is one of nitrogen, argon and hydrogen/argon mixed gas.
The beneficial effects of the invention are as follows:
(1) The PI film with high porosity and high liquid absorption rate is prepared by combining an immersion precipitation phase inversion method with vacuum programmed temperature rise;
(2) The method of combining the immersion precipitation phase inversion method and the vacuum temperature programming adopted by the invention can effectively control the volatilization rates of solvents with different boiling points in the casting film liquid due to the adoption of the vacuum temperature programming mode in the drying process, realizes the gradient formation mode of the pore structure and improves the porosity of the PI film;
(3) The porosity of the PI film prepared by adopting the combination of the immersion precipitation phase inversion method and the vacuum programmed temperature rise is 32-52%;
(4) The liquid absorption rate of the PI film prepared by adopting the combination of the immersion precipitation phase inversion method and the vacuum programmed temperature rise can reach 145-171%;
(5) The immersion precipitation phase inversion method and the vacuum temperature programming method adopted by the invention have simple operation and low cost, do not need special professional equipment, and are beneficial to large-scale production.
Drawings
FIG. 1 is a photograph of a PI film;
FIG. 2 is a graph of the infrared signature results of PI films;
FIG. 3 is a graph comparing contact angles of PI films with commercial diaphragms;
FIG. 4 is a graph of porosity versus PI film for commercial battery separators;
fig. 5 is a graph of the liquid absorption ratio of a commercial battery separator versus a PI film.
Detailed Description
Example 1:
(1) The pyromellitic dianhydride and the 4,4' -diaminodiphenyl ether are taken as raw materials, the raw materials are dissolved in an N, N-dimethylformamide solvent according to the molar ratio of 1:1, and the raw materials are subjected to ultrasonic treatment and stirring until a uniform solution is formed, wherein the mass fraction of the total mass of the raw materials in the solvent is 10%.
(2) And (3) introducing high-purity nitrogen into the uniform solution obtained in the step (1), and stirring for 15 hours under the condition that the temperature is 40 ℃ and the stirring speed is 400rpm under the protection of gas, so as 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 coater to 200. Mu.m.
(4) And (3) placing the coated glass plate in the step (3) in an ethanol coagulating 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 (3) rapidly placing the solidified PAA solution obtained in the step (4) in a vacuum drying oven, drying in a temperature programming mode, heating to 40 ℃ at a speed of 2 ℃/min, keeping the temperature for 10min, and drying in a temperature programming mode of heating to 70 ℃ at a speed of 2 ℃/min and keeping the temperature for 12h to obtain the PAA film.
(6) And (3) placing the PAA film 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 of 171%.
As can be seen from the photograph of the PI film (as shown in fig. 1), PI prepared in this example is yellow and has a flat surface. As can be seen from the infrared characterization result of the PI film (as shown in FIG. 2), the PI films were respectively at 1780cm -1 ,1716cm -1 Where a c=o bond in the imide group appears at 1372cm -1 The C-N stretching vibration peak appears, which shows that the PI can be successfully prepared by the invention. Fig. 3 shows the contact angle test results of PI films and commercial separators, and the hydrophilicity of the films 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 7 for PI films4.5 ° (as shown in fig. 3 b). This result shows that the PI separator prepared according to the present invention has more excellent hydrophilicity and the wettability of the solution thereof is more excellent, meaning that the PI film is more suitable for use in a battery, as compared to a commercial separator.
Fig. 4 shows the comparison of the porosities of the commercial battery separator and the PI film, wherein the porosity of the commercial battery separator measured by the n-butanol method is 37.9% and the PI film is 52%, which means that the PI film prepared by the method has higher porosity, and the high porosity can provide a channel for the transmission of battery ions, thereby being beneficial to the improvement of battery performance.
Fig. 5 is a comparison of the imbibition of a commercial battery separator with a PI film, and it can be seen from the graph that the imbibition of a commercial battery separator is 111.6%, and the imbibition of a PI film prepared according to the invention is as high as 171%, which is sufficient to demonstrate that the PI film prepared according to the invention is more suitable for use in an ion battery.
Example 2:
(1) 3,3', 4' -diphenyl ether tetracarboxylic dianhydride and 4,4' -diaminodiphenyl ether are taken as raw materials, the raw materials are dissolved in an N, N-dimethylformamide solvent according to the molar ratio of 1:1, and the raw materials are ultrasonically stirred until a uniform solution is formed, wherein the mass fraction of the total mass of the raw materials in the solvent is 10%.
(2) And (3) introducing high-purity nitrogen into the uniform solution obtained in the step (1), and stirring for 15 hours under the condition that the temperature is 40 ℃ and the stirring speed is 400rpm under the protection of gas, so as 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 coater to 200. Mu.m.
(4) And (3) placing the coated glass plate in the step (3) in an ethanol coagulating 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 (3) rapidly placing the solidified PAA solution obtained in the step (4) in a vacuum drying oven, drying in a temperature programming mode, heating to 40 ℃ at a speed of 2 ℃/min, keeping the temperature for 10min, and drying in a temperature programming mode of heating to 70 ℃ at a speed of 2 ℃/min and keeping the temperature for 12h to obtain the PAA film.
(6) And (3) placing the PAA film 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 of 145%.
Example 3:
(1) The pyromellitic dianhydride and the 4,4' -diaminodiphenyl ether are taken as raw materials, the raw materials are dissolved in an N, N-dimethylformamide solvent according to the molar ratio of 1:1.5, and the raw materials are subjected to ultrasonic treatment and stirring until a uniform solution is formed, wherein the mass fraction of the total mass of the raw materials in the solvent is 17%.
(2) And (3) introducing high-purity nitrogen into the uniform solution obtained in the step (1), and stirring for 15 hours under the condition that the temperature is 40 ℃ and the stirring speed is 400rpm under the protection of gas, so as 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 coater to 200. Mu.m.
(4) And (3) placing the coated glass plate in the step (3) in an ethanol coagulating 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 (3) rapidly placing the solidified PAA solution obtained in the step (4) in a vacuum drying oven, drying in a temperature programming mode, heating to 40 ℃ at a speed of 2 ℃/min, keeping the temperature for 10min, and drying in a temperature programming mode of heating to 70 ℃ at a speed of 2 ℃/min and keeping the temperature for 12h to obtain the PAA film.
(6) And (3) placing the PAA film 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 of 148%.
Example 4:
(1) The pyromellitic dianhydride and the 4,4' -diaminodiphenyl ether are taken as raw materials, the raw materials are dissolved in an N, N-dimethylformamide solvent according to the molar ratio of 1:1, and the raw materials are subjected to ultrasonic treatment and stirring until a uniform solution is formed, wherein the mass fraction of the total mass of the raw materials in the solvent is 10%.
(2) And (3) introducing high-purity nitrogen into the uniform solution obtained in the step (1), and stirring for 15 hours under the condition that the temperature is 40 ℃ and the stirring speed is 400rpm under the protection of gas, so as 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 coater to 200. Mu.m.
(4) And (3) placing the coated glass plate in the step (3) in an ethanol coagulating 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 (3) rapidly placing the solidified PAA solution obtained in the step (4) in a vacuum drying oven, drying in a temperature programming mode, heating to 40 ℃ at a speed of 2 ℃/min, keeping the temperature for 10min, and drying in a temperature programming mode of heating to 70 ℃ at a speed of 2 ℃/min and keeping the temperature for 12h to obtain the PAA film.
(6) And (3) placing the PAA film 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 39% of porosity and 151% of liquid absorption.
Example 5:
(1) The pyromellitic dianhydride and the 4,4' -diaminodiphenyl ether are taken as raw materials, the raw materials are dissolved in an N, N-dimethylformamide solvent according to the molar ratio of 1:1, and the raw materials are subjected to ultrasonic treatment and stirring until a uniform solution is formed, wherein the mass fraction of the total mass of the raw materials in the solvent is 10%.
(2) And (3) introducing high-purity nitrogen into the uniform solution obtained in the step (1), and stirring for 15 hours under the condition that the temperature is 40 ℃ and the stirring speed is 400rpm under the protection of gas, so as 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 coater to 200. Mu.m.
(4) And (3) placing the coated glass plate in the step (3) in an ethanol coagulating 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 (3) rapidly placing the solidified PAA solution obtained in the step (4) in a vacuum drying oven, drying in a temperature programming mode, heating to 40 ℃ at a speed of 5 ℃/min, keeping the temperature for 10min, and drying in a temperature programming mode of heating to 70 ℃ at a speed of 5 ℃/min and keeping the temperature for 12h to obtain the PAA film.
(6) And (3) placing the PAA film 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 of 158%.
Example 6:
(1) 3,3', 4' -benzophenone tetracarboxylic dianhydride and 4,4' -diaminodiphenyl ether are taken as raw materials, the raw materials are dissolved in an N, N-dimethylacetamide solvent according to a molar ratio of 1:1, and the raw materials are ultrasonically stirred until a uniform solution is formed, wherein the mass fraction of the total mass of the raw materials in the solvent is 20%.
(2) And (3) introducing high-purity argon into the uniform solution obtained in the step (1), and stirring for 10 hours under the condition that the temperature is 20 ℃ and the stirring speed is 450rpm under the protection of gas, so as 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 coater to 150. Mu.m.
(4) And (3) placing the coated glass plate in the step (3) in an acetone coagulating bath, standing for 30min at 40 ℃, and taking out the coagulated PAA solution after the PAA solution on the glass plate is solidified.
(5) And (3) rapidly placing the solidified PAA solution obtained in the step (4) in a vacuum drying oven, drying in a temperature programming mode, heating to 40 ℃ at a speed of 2 ℃/min, keeping the temperature for 20min, and drying in a temperature programming mode of heating to 70 ℃ at a speed of 5 ℃/min and keeping the temperature for 12h to obtain the PAA film.
(6) And (3) placing the PAA film in the step (5) in a tube furnace, and 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 of 163%.
Example 7:
(1) 3,3', 4' -benzophenone tetracarboxylic dianhydride and 4,4' -diaminodiphenyl ether are taken as raw materials, the raw materials are dissolved in an N, N-dimethylacetamide solvent according to a molar ratio of 1:1.5, and the raw materials are ultrasonically stirred 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 (3) introducing high-purity hydrogen/nitrogen into the uniform solution obtained in the step (1), and stirring for 24 hours under the condition that the temperature is 0 ℃ and the stirring speed is 200rpm under the protection of gas, so as 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 coater to 75. Mu.m.
(4) And (3) placing the coated glass plate in the step (3) in an acetone coagulating bath, standing for 10min at 40 ℃, and taking out the coagulated PAA solution after the PAA solution on the glass plate is solidified.
(5) And (3) rapidly placing the solidified PAA solution obtained in the step (4) in a vacuum drying oven, drying by adopting a temperature programming mode, heating to 40 ℃ at a speed of 5 ℃/min, keeping the temperature for 30min, and drying by adopting a temperature programming mode of heating to 70 ℃ at a speed of 2 ℃/min and keeping the temperature for 30min to obtain the PAA film.
(6) And (3) placing the PAA film in the step (5) in a tube furnace, and 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 of 168%.
The above embodiments are only for illustrating the technical concept and features of the present invention, and are intended to enable those skilled in the art to understand the content of the present invention and implement the same, and are not intended to limit the scope of the present invention. All equivalent changes or modifications made in accordance with the essence of the present invention are intended to be included within the scope of the present invention.
Claims (3)
1. The application of the polyimide film in the battery diaphragm material is characterized in that the preparation process of the polyimide film comprises the following steps:
(1) Acid dianhydride and diphenyl ether are taken as raw materials, the raw materials are dissolved in N, N-dimethylformamide or N, N-dimethylacetamide according to the mol ratio of 1:1-1:1.5, stirring is carried out until a uniform solution is formed, the acid dianhydride is one of 3,3', 4' -diphenyl ether tetracarboxylic dianhydride, pyromellitic dianhydride and 3,3', 4' -benzophenone tetracarboxylic dianhydride, the diphenyl ether is 4,4' -diaminodiphenyl ether, and the dissolution proportion of the raw materials is that the mass fraction of the total mass of the raw materials in the solvent is 10-20%;
(2) Introducing inert atmosphere into the uniform solution in the step (1), and stirring under certain conditions until 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, wherein the thickness of the coated film is controlled to be 75-200 mu m;
(4) Placing the coated glass plate in the step (3) in an ethanol or acetone coagulating bath, standing, taking out the coagulated PAA solution after the PAA solution on the glass plate is solidified, wherein the coagulating bath temperature is 25-40 ℃, and the standing time is 10-30 min;
(5) And (3) vacuum drying the solidified PAA solution in the step (4) in a temperature programming mode to prepare the PAA film, wherein the temperature programming process 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 30-12 h;
(6) And (3) performing high-temperature heat treatment on the PAA film in the step (5) to prepare the PI film.
2. The method according to claim 1, wherein the inert atmosphere in the step (2) is one of high-purity nitrogen, argon and a 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.
3. The use 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 high-temperature heat treatment time is 1-6 h, and the heat treatment atmosphere is one of nitrogen, argon and hydrogen/argon mixed gas.
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| 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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| Publication number | Priority date | Publication date | Assignee | Title |
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| 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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