CN111403667A - Composition of high-temperature-resistant lithium battery diaphragm and preparation method thereof - Google Patents
Composition of high-temperature-resistant lithium battery diaphragm and preparation method thereof Download PDFInfo
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- C08G73/10—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
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Abstract
The invention designs and prepares the cross-linked polyimide film with higher heat-resistant grade aiming at the potential safety hazard problems that the heat-resistant grade of the diaphragm of the existing lithium battery is limited and the diaphragm of the lithium battery equipment is damaged by heating to cause short circuit. The polyimide film for the lithium battery prepared by the invention is modified by crosslinking of the flexible chain segment, has a micro-split-phase structure while preparing micropores, ensures the conduction of lithium ions so as to keep the efficiency of the battery, and has the high-temperature resistance of the polyimide material. The safety of the lithium battery equipment can be improved.
Description
Technical Field
The invention belongs to the field of lithium battery materials, and particularly relates to a composition and a preparation method of a high-temperature-resistant battery diaphragm, which achieve the purpose of improving the safety and stability of a lithium battery.
Background
Energy is an important substance on which people live and develop, the development of energy technology is determined as an important strategic development direction by various countries, and one of the biggest challenges of modern society is to ensure that energy supply can meet the increasing energy demand. The lithium ion battery has the advantages of high energy density, long cycle life, small pollution, no memory effect, quick charge and discharge and the like, is widely applied to electrical equipment such as mobile communication, notebook computers, small cameras and the like, and shows good application prospect and economic benefit in the fields of electric automobiles, aerospace, energy storage, military and the like in recent years. However, the occurrence of frequent lithium battery ignition events has attracted a great deal of attention to the safety of lithium batteries.
Among the components of lithium batteries, the separator is one of the key materials, and has the main function of absorbing electrolyte to conduct lithium ions, and at the same time, separating the positive electrode from the negative electrode of the battery to prevent short circuit caused by contact between the two electrodes. The performance of the diaphragm determines the interface structure and the internal resistance of the battery, and the diaphragm prevents the battery from being invalid due to excessive heating caused by overlarge resistance, thereby influencing the discharge capacity, the cycle performance, the rate performance, the safety performance and the like of the battery, and the diaphragm with excellent performance plays an important role in improving the comprehensive performance of the battery.
Polyimide has high heat resistance, high strength, excellent insulativity and high dimensional stability at high temperature, and a microporous membrane taking polyimide as a main material is adopted to replace the existing porous polyethylene PE and polypropylene PP battery diaphragm, so that the microporous membrane is more and more concerned by the lithium battery industry, and the core technology of the microporous membrane is a pore-forming technology of a polyimide film. The polyimide static spinning technology reported in various documents has low production efficiency, long required period and difficult mass production; for another example: the pore-forming steps described in patent CN201410339770.9 and patent CN201720442163.4 are also quite complicated. And the surface energy of the pure polyimide material is lower, and the wetting performance of the electrolyte is limited to a certain extent. In comparison, the polyolefin lithium battery diaphragm has the great advantage of cost and the advantage of high-temperature closed pores, but the polyolefin lithium battery diaphragm has poor high-temperature resistance, and the melting point of PE is lower than 120 ℃; the melting point of PP is lower than 160 ℃, short circuit is easy to occur at high temperature, and the wettability of the PP to electrolyte is poor, so that the temperature resistance, the dimensional stability and the wettability of the electrolyte of the diaphragm are improved, and the PP contributes to the improvement of the safety and the electrochemical performance of the lithium battery.
Aiming at the defects of the polyolefin diaphragm, the invention prepares the polyimide film with a cross-linking structure, and the film has a microphase separation structure. The structure of the cross-linking agent has good wetting performance with electrolyte, and the cross-linking agent can be complexed with lithium ions after being soaked in the electrolyte, so that the lithium ions can be conducted in the film, and the excellent electrochemical performance of the lithium battery is ensured. And the main chain structure of the polyimide ensures the heat resistance of the film and the dimensional stability at high temperature.
Disclosure of Invention
The invention relates to a high-temperature-resistant diaphragm for a lithium battery, which is characterized by comprising three parts: the structure can form a good phase separation structure after being solidified into a film, and can be used as a high-temperature-resistant lithium ion battery diaphragm after being soaked in electrolyte and absorbing lithium ions.
The structural formula of the wholly aromatic polyimide chain segment is as follows:
wherein Ar is1Can be as follows:
，
,
,
，
；
wherein R is1Can be as follows:
，
，
，
，
，
,
;
wherein R is1Can be as follows:
，
，
；
wherein x is a decimal between 0.5 and 1.0 and L is an integer between 5 and 50.
The structural formula of the semi-aliphatic polyimide chain segment is as follows:
wherein Ar is2Can be as follows:
，
,
,
，
；
wherein R is2Can be as follows: ,
,
(ii) a The values of h and g are integers of 2 to 12, respectively.
Wherein R is2And R1May be the same or different, and may be:
，
，
；
wherein x is a decimal between 0 and 0.98 and Z is an integer between 5 and 50.
The polyimide chain segment in the invention can exist in a form of copolymerization on a molecular chain or in a form of blending.
The structural formula of the cross-linking chain segment is as follows:
k, P, Q, G, J, W may be equal or unequal, and are integers of 2-16.
Wherein contains Ar1And Ar2The dianhydride of the structure may beThe same or different, respectively: pyromellitic dianhydride (PMDA), biphenyl dianhydride (PMDA), 3 ', 4,4' -diphenyl ether tetracarboxylic dianhydride (ODPA), 3 ', 4,4' -Benzophenone Tetracarboxylic Dianhydride (BTDA), and 4,4' - (hexafluoroisopropylene) diphthalic anhydride (6 FDA). Containing R1Diamines of the structure are: 4,4 '-diaminodiphenyl ether (ODA), 4' -bis (4-aminophenoxy) biphenyl (BAPB), 2 '-dimethyl-4, 4' -benzidine (THFB), 1, 3-bis (4-aminophenoxy) benzene, 2-bis [4- (4-aminophenoxy) phenylphenyl]Propane, 2-bis [4- (4-aminophenoxy) phenyl]Hexafluoropropane and 2, 2-bis (4-aminophenyl) propane. Containing R2Diamines of the structure are: 1, 2-diaminoethane, 1, 3-diaminopropane, 1, 4-diaminobutane, 1, 5-diaminopentane, 1, 6-diaminohexane, 1, 7-diaminoheptane, 1, 8-diaminooctane, 1, 9-diaminononane, 1, 10-diaminodecane, undecane-1, 11-diamine, dodecane-1, 12-diamine, and the like; and 1, 2-bis (4-aminophenoxy) ethane, 1, 3-bis (4-aminophenoxy) propane, 1, 4-bis (4-aminophenoxy) butane, 1, 5-bis (4-aminophenoxy) pentane, 1, 6-bis (4-aminophenoxy) hexane, 1, 7-bis (4-aminophenoxy) heptane, 1, 8-bis (4-aminophenoxy) octane, 1, 9-bis (4-aminophenoxy) nonane, 1, 10-bis (4-aminophenoxy) decane, 1, 11-bis (4-aminophenoxy) undecane, 1, 12-bis (4-aminophenoxy) dodecane. The crosslinking agent is mainly methacrylate-terminated polyethylene oxide, polymethyl ethylene oxide, a copolymer of ethylene oxide and methyl ethylene oxide, polybutylene glycol, and the like.
The experimental process of the polymerization reaction of the wholly aromatic polyimide chain segment and the semi-aliphatic polyimide chain segment related to the invention is as follows:
1. wholly aromatic polyimide segment: adding R into a dry three-neck bottle in sequence under the protection of nitrogen1Diamine monomer having an intermediate structure, and an intermediate structure having a lower number of moles than the diamine monomer and Ar1Stirring the dianhydride monomer and the organic solvent for 2 to 12 hours at room temperature, then continuously and slowly dripping toluene into a reaction bottle, heating to 160 ℃, keeping the temperature at 160 ℃, continuously reacting for 4 to 8 hours,toluene and water were removed azeotropically. After the reaction is finished, after cooling to room temperature, R is added repeatedly1Diamine monomer with intermediate structure, and intermediate structure with more moles of Ar than diamine monomer1The dianhydride monomer and a certain amount of grafting monomers such as hydroxyethyl acrylate, hydroxyethyl methacrylate or 2-methyl-4-hydroxy butylene, and the like, and the mixture is continuously stirred for 5 to 8 hours at room temperature. After the second addition, the molar sum of the amino and hydroxyl groups in the reaction flask needs to be in equal ratio to the molar sum of the anhydride groups. The resulting highly viscous polymer solution was obtained.
2. Semi-aliphatic polyimide segment: adding R into a dry three-neck bottle in sequence under the protection of nitrogen2Diamine monomer having an intermediate structure, and an intermediate structure having a lower number of moles than the diamine monomer and Ar2Stirring the dianhydride monomer and the organic solvent for 2-12 hours at room temperature, then continuously and slowly dripping toluene into a reaction bottle, heating to 160 ℃, keeping the temperature at 160 ℃ and continuously reacting for 4-8 hours to ensure that the toluene and the water are removed by azeotropy. After the reaction is finished, after cooling to room temperature, R is added repeatedly2Diamine monomer with intermediate structure, and intermediate structure with more moles of Ar than diamine monomer2The dianhydride monomer and a certain amount of grafting monomers such as hydroxyethyl acrylate, hydroxyethyl methacrylate or 2-methyl-4-hydroxy butylene, and the like, and the mixture is continuously stirred for 5 to 8 hours at room temperature. After the second addition, the molar sum of the amino and hydroxyl groups in the reaction flask needs to be in equal ratio to the molar sum of the anhydride groups. The resulting highly viscous polymer solution was obtained.
3. Copolymerization of wholly aromatic polyimide chain segment and semi-aliphatic polyimide chain segment: adding R into a dry three-neck bottle in sequence under the protection of nitrogen1Or R2Or R1And R2Two diamine monomers with intermediate structure, and the intermediate structure with the mole number less than that of the diamine monomer is Ar1Or Ar2Stirring the dianhydride monomer and the organic solvent for 2-12 hours at room temperature, then continuously and slowly dripping toluene into a reaction bottle, heating to 160 ℃, keeping the temperature at 160 ℃ and continuously reacting for 4-8 hours to ensure that the toluene and the water are removed by azeotropy. After the reaction is finished, cooling to room temperature, and repeatedly adding a certain amount of R1Or R2Or R1And R2Two diamine monomers with intermediate structure, and the intermediate structure with more moles of Ar than the diamine monomers1Or Ar2The dianhydride monomer and a certain amount of grafting monomers such as hydroxyethyl acrylate, hydroxyethyl methacrylate or 2-methyl-4-hydroxy butylene, and the like, and the mixture is continuously stirred for 5 to 8 hours at room temperature. After the second addition, the molar sum of the amino and hydroxyl groups in the reaction flask needs to be in equal ratio to the molar sum of the anhydride groups. The resulting highly viscous polymer solution was obtained.
The wholly aromatic polyimide chain segment and the semi-aliphatic polyimide chain segment which are prepared are dissolved
The copolymer solution of a wholly aromatic polyimide chain segment and a semi-aliphatic polyimide chain segment is mixed in a form, a cross-linking agent accounting for 2-50 wt% of the weight of the polyimide chain segment is added into the solution, and the cross-linking agent has the following structure:
Then adding 0.5-3wt% of thermal cross-linking initiator(s) in the total polymer mass into the solution, wherein the thermal initiator(s) may be
Are conventional peroxide-based compounds or azo-based compounds, such as: azobisisobutyronitrile (AIBN), dibenzoyl peroxide (BPO), Azobisisoheptonitrile (ABVN), and tert-Butyl Peroxybenzoate (BPB), and the like, and mixtures thereof may also be used in combination.
The mixed solution obtained by the method is formed into a film by adopting a mixed solution pouring mode, a tape casting mode or a spin coating mode, 25-75% of solvent is removed at a certain program temperature (between 80 and 175 ℃) to be baked into a film and initiate thermal crosslinking, then the film is cooled to room temperature, the film is taken down from a base material and is immersed into the mixed solvent of methanol/ethanol and water for 2-5 hours, the ratio of the alcohol to the water is 5:5-9:1, then the porous and phase-separated film is obtained, the film is clamped by a four-frame clamp, and the film is dried in a vacuum oven at 60 ℃. The thickness of the film is controlled to be 10-200 microns.
The conception, the specific structure and the technical effects of the present invention will be further described with reference to the accompanying drawings to fully understand the objects, the features and the effects of the present invention. The test results of the examples are compared in table one.
Drawings
FIG. 1 is a schematic diagram of the complexation of lithium ions with oxygen atoms in a segment of a crosslinker;
FIG. 2 is a phase-separated SEM photograph of a lithium battery separator according to a preferred embodiment of the invention;
FIG. 3 is an IR spectrum of a lithium battery separator according to a preferred embodiment of the invention;
figure 4 is an electrical diagram of a separator in a preferred embodiment of the invention.
Test method
Infrared spectrum (FT-IR): Perkin-Elmer Paragon 1000 Fourier transform infrared spectrophotometer, KBr pellet or film method.
Measurement of 5% thermal decomposition temperature: the thermal stability of the film sample was determined by a Mettler-Toliduo TGA1 thermogravimetric analyzer under nitrogen protection at a temperature rise rate of 20 ℃/min.
Determination of glass transition (Tg): the thermal stability of the film sample was measured by a Mettler-Torledo DSC 1 differential scanning calorimeter in static air at a temperature rise rate of 10 ℃/min.
Measurement of mechanical properties: the film was cut into a strip having a width of 10mm and a length of 80mm, and the tensile strength of the film was measured at room temperature (23 ℃ C.) and a relative humidity of 60% by an Instron-4465 tensile tester at a rate of 5 mm/min.
Testing of coefficient of thermal expansion CTE: the Mettler-Toriluo TMA1 is measured under the conditions that the test range is 20-180 ℃ and the heating rate is 10 ℃/min.
And (3) phase morphology observation: spraying gold on the cross section of the film, and observing the appearance of the sample by adopting a SIRION-100 field emission scanning electron microscope of Phillips, Netherlands.
Electrolyte adsorption Property according to the film in the electrolyte (L iCF)3SO3Diethyl carbonate solution) was measured and characterized by the percentage of weight gain.
The battery test system comprises: arbin company battery test system, constant current-constant voltage charging/constant current discharging module
And (3) performing cycle performance and rate performance tests between 2.0 and 4.2V.
Detailed Description
The technical contents of the preferred embodiments of the present invention will be more clearly and easily understood by referring to the drawings attached to the specification. The present invention may be embodied in many different forms of embodiments and the scope of the invention is not limited to the embodiments set forth herein.
The first embodiment is as follows:
3.18g (15 mmol) of 2,2 '-dimethyl-4, 4' -benzidine, 6.216g (14 mmol) of 4,4'- (hexafluoroisopropylene) diphthalic anhydride and 38ml of solvent GB L are added in succession to a dry three-necked flask under the protection of nitrogen, stirred at room temperature for 2 to 12 hours, then toluene is added slowly and continuously to the reaction flask and the temperature is raised to 160 ℃ and the reaction is continued for 4 to 8 hours at 160 ℃ to azeotropically remove toluene and water, after the reaction has ended, 2g (10 mmol) of diaminodiphenyl ether, 5.772g (13 mmol) of 4,4' - (hexafluoroisopropylene) diphthalic anhydride, 10ml of solvent GB L and 0.52g (4 mmol) of hydroxyethyl methacrylate are added repeatedly after cooling to room temperature, and stirring is continued at room temperature for 5 to 8 hours, after the second addition, the sum of moles of amino and hydroxyl groups and the sum of moles of anhydride groups in the reaction flask is required to achieve an equal ratio to the viscous, highly viscous polymer solution finally obtained.
0.72g (5 mmol) of 1, 8-diaminooctane, 1.776g (4 mmol) of 4,4' - (hexafluoroisopropylene) diphthalic anhydride and 15ml of solvent GB L are added in sequence to a dry three-necked flask under the protection of nitrogen, stirred at room temperature for 2-12 hours, then toluene is continuously and slowly added to the reaction flask, the temperature is raised to 160 ℃, the reaction is kept at 160 ℃ for 4-8 hours, the toluene and water are azeotropically removed, after the reaction is finished and cooled to room temperature, 1.44g (10 mmol) of 1, 8-diaminooctane, 4.116g (14 mmol) of biphenyl dianhydride, 22ml of solvent GB L and 0.78g (6 mmol) of hydroxyethyl methacrylate are repeated, and stirring is continued at room temperature for 5-8 hours.
Mixing the two polyimide solutions, adding 6g of PEG cross-linking agent with methacrylate end-capped repeating unit of 16 and 0.4g of thermal initiator AIBNB into the solution, fully dissolving and mixing, casting on a clean glass plate to form a film, drying for 30min in a forced air oven at the temperature of 90 ℃, taking out, carefully peeling off the film and weighing. Completely immersing the film into a mixed solvent of ethanol and water (the mass ratio is 7: 3), soaking for 2-3 hours, clamping the film by a clamp, drying for 10 hours in a vacuum oven at 60 ℃, taking out and quickly weighing. This film was sample one for use.
Example two:
2.052g (5 mmol) of 2, 2-bis [4- (4-aminophenoxy) phenyl ] hexafluoropropane, 1.776g (4 mmol) of 4,4' - (hexafluoroisopropylene) diphthalic anhydride and 20ml of NMP solvent were sequentially added to a dry three-necked flask under the protection of nitrogen, stirred at room temperature for 2 to 12 hours, and then toluene was continuously and slowly added dropwise to the flask, and the temperature was raised to 160 ℃ and kept at 160 ℃ for further reaction for 4 to 8 hours, thereby azeotropically removing toluene and water. After completion of the reaction, the reaction mixture was cooled to room temperature, and 1.44g (10 mmol) of 1, 8-diaminooctane, 4.116g (14 mmol) of biphenyl dianhydride, 22ml of NMP as a solvent and 0.78g (6 mmol) of hydroxyethyl methacrylate were repeatedly added thereto, followed by stirring at room temperature for 5 to 8 hours. After the second addition, the molar sum of the amino and hydroxyl groups in the reaction flask needs to be in equal ratio to the molar sum of the anhydride groups. The resulting highly viscous polymer solution was obtained.
And then 5g of PEG cross-linking agent with 16 methacrylate end-capped repeating units and 0.2g of thermal initiator AIBNP are added into the solution, fully dissolved and mixed, poured on a clean glass plate to form a film, dried for 20min in a blast oven with the temperature of 85 ℃, taken out, carefully stripped off the film and weighed. Completely immersing the film into a mixed solvent of ethanol and water (the mass ratio is 7: 3), soaking for 2-3 hours, clamping the film by a clamp, drying for 10 hours in a vacuum oven at 60 ℃, taking out and quickly weighing. This film was sample two, ready for use.
Example three:
under the protection of nitrogen, 3.39g (15 mmol) of 2, 2-bis (4-aminophenyl) propane, 3.052g (14 mmol) of pyromellitic dianhydride and 26ml of solvent DMAc are added into a dry three-necked bottle in sequence, stirred at room temperature for 2-12 hours, then toluene is continuously and slowly added into the reaction bottle, the temperature is raised to 160 ℃, the reaction is kept at 160 ℃ for 4-8 hours, the toluene and water are azeotropically removed, after the reaction is finished and cooled to room temperature, 3.28g (10 mmol) of 1, 8-bis (4-aminophenoxy) octane, 7.548g (17 mmol) of 4,4' - (hexafluoroisopropylidene) diphthalic anhydride, 43ml of solvent GB L and 1.42g (12 mmol) of hydroxyethyl acrylate are repeatedly added, and stirring is continued at room temperature for 5-8 hours, after the second addition, the total number of moles of amino and hydroxyl groups and the total number of moles of anhydride groups in the reaction bottle need to reach an equal ratio, and finally the highly viscous polymer solution is obtained.
6g of PEG/PPG block crosslinking agent with 15 methacrylate end-capped repeating units and 0.3g of thermal initiator AIBNP are added into the solution, fully dissolved and mixed, poured on a clean glass plate to form a film, dried for 20min in a blast oven with the temperature of 90 ℃, taken out, carefully stripped and weighed. Completely immersing the film into a mixed solvent of ethanol and water (the mass ratio is 9: 1), soaking for 2-3 hours, clamping the film by a clamp, drying for 10 hours in a vacuum oven at 60 ℃, taking out and quickly weighing. This film was sample three, ready for use.
Example four:
2.12g (10 mmol) of 2,2 '-dimethyl-4, 4' -benzidine, 2.898g (9 mmol) of 3,3 ', 4,4' -benzophenonetetracarboxylic dianhydride and 20ml of solvent GB L were added in succession to a dry three-necked flask under the protection of nitrogen, stirred at room temperature for 2-12 hours, then toluene was added slowly and continuously to the flask and the temperature was raised to 160 ℃ and the reaction was continued at 160 ℃ for 4-8 hours, allowing the azeotropic removal of toluene and water, after the reaction was complete, 2.32g (20 mmol) of 1, 6-diaminohexane, 5.668g (26 mmol) of pyromellitic anhydride, 10ml of solvent GB L and 1.3g (10 mmol) of hydroxyethyl methacrylate were added repeatedly after cooling to room temperature, and stirring at room temperature was continued for 5-8 hours after the second addition, the total number of moles of amino and hydroxyl groups and the total number of moles of anhydride groups in the flask needed to achieve an equal ratio.
And then 8g of a polybutanediol cross-linking agent with a methacrylate end-capped repeating unit of 12 and 0.3g of a thermal initiator AIBNB are added into the solution, fully dissolved and mixed, poured on a clean glass plate to form a film, dried for 15min in a forced air oven at the temperature of 90 ℃, taken out, carefully stripped off the film and weighed. Completely immersing the film into a mixed solvent of ethanol and water (the mass ratio is 8: 2), soaking for 2-3 hours, clamping the film by a clamp, drying for 10 hours in a vacuum oven at 60 ℃, taking out and quickly weighing. This film was sample four, ready for use.
Example five:
under the protection of nitrogen, 3.68g (10 mmol) of 4,4' -bis (4-aminophenoxy) biphenyl, 2.79g (9 mmol) of 3,3 ', 4,4' -diphenyl ether tetracarboxylic dianhydride and 26ml of NMP solvent are sequentially added into a dry three-necked bottle, stirred at room temperature for 2-12 hours, then toluene is continuously and slowly added into the reaction bottle, the temperature is raised to 160 ℃, the reaction is continued for 4-8 hours under the temperature of 160 ℃, and the toluene and water are removed by azeotropy. After completion of the reaction, the reaction mixture was cooled to room temperature, and then 2.58g (15 mmol) of 1, 10-diaminodecane, 8.88g (20 mmol) of 4,4' - (hexafluoroisopropylene) diphthalic anhydride, 40ml of solvent NMP and 1.04g (8 mmol) of hydroxyethyl methacrylate were repeatedly added thereto, followed by stirring at room temperature for 5 to 8 hours. After the second addition, the molar sum of the amino and hydroxyl groups in the reaction flask needs to be in equal ratio to the molar sum of the anhydride groups. The resulting highly viscous polymer solution was obtained.
4g of polytetramethylene glycol cross-linking agent with a repeating unit of 12 and terminated by methacrylate and 0.2g of thermal initiator AIBNP are added into the solution, fully dissolved and mixed, poured on a clean glass plate to form a film, dried for 15min in a forced air oven with the temperature of 90 ℃, taken out, carefully stripped and weighed. Completely immersing the film into a mixed solvent of ethanol and water (the mass ratio is 8: 2), soaking for 2-3 hours, clamping the film by a clamp, drying for 10 hours in a vacuum oven at 60 ℃, taking out and quickly weighing. This film was sample five, ready for use.
Example six:
under the protection of nitrogen, 3.39g (15 mmol) of 2, 2-bis (4-aminophenyl) propane, 3.052g (14 mmol) of pyromellitic anhydride and 25ml of solvent GB L are added into a dry three-necked bottle in sequence, stirred at room temperature for 2-12 hours, then toluene is continuously and slowly added into the reaction bottle, the temperature is raised to 160 ℃, the reaction is kept at 160 ℃ for 4-8 hours, the toluene and water are azeotropically removed, after the reaction is finished, 2g (10 mmol) of diaminodiphenyl ether, 5.772g (13 mmol) of 4,4' - (hexafluoroisopropylene) diphthalic anhydride, 10ml of solvent GB L and 0.52g (4 mmol) of hydroxyethyl methacrylate are repeatedly added after cooling to room temperature, stirring is continued at room temperature for 5-8 hours, after the second addition, the total number of moles of amino and hydroxyl groups and the total number of anhydride groups in the reaction bottle need to be in equal ratio.
1.92g (5 mmol) of 1, 12-bis (4-aminophenoxy) dodecane, 1.776g (4 mmol) of 4,4' - (hexafluoroisopropylene) diphthalic anhydride and 15ml of solvent GB L are added in succession to a dry three-necked flask under the protection of nitrogen, stirred at room temperature for 2 to 12 hours, then toluene is continuously and slowly added dropwise to the reaction flask, the temperature is raised to 160 ℃ and the reaction is continued for 4 to 8 hours at 160 ℃ to azeotropically remove toluene and water, after the reaction is complete, 3.84g (10 mmol) of 1, 12-bis (4-aminophenoxy) dodecane, 4.116g (14 mmol) of biphenyl dianhydride, 31ml of solvent GB L and 0.696g (6 mmol) of hydroxyethyl acrylate are repeated after cooling to room temperature, and stirring at room temperature is continued for 5 to 8 hours, after the second addition, the sum of moles of amino and hydroxyl groups and the sum of moles of anhydride groups in the reaction flask is required to reach an equal ratio to the highly viscous polymer solution finally obtained.
Mixing the two polyimide solutions prepared above, adding 6g of a polytetramethylene glycol cross-linking agent with a methacrylate end-capped repeating unit of 12 and 0.4g of a thermal initiator AIBNB into the solutions, fully dissolving and mixing, casting on a clean glass plate to form a film, drying for 20min in a forced air oven at the temperature of 90 ℃, taking out, carefully peeling off the film and weighing. Completely immersing the film into a mixed solvent of ethanol and water (the mass ratio is 9: 1), soaking for 2-3 hours, clamping the film by a clamp, drying for 10 hours in a vacuum oven at 60 ℃, taking out and quickly weighing. This film was sample six, ready for use.
Example seven:
2.12g (10 mmol) of 2,2 ' -dimethyl-4, 4' -benzidine, 3.84g (10 mmol) of 1, 12-bis (4-aminophenoxy) dodecane, 6.66g (15 mmol) of 4,4' - (hexafluoroisopropylidene) diphthalic anhydride and 50ml of solvent GB L are added in succession to a dry three-necked flask under nitrogen, stirring is carried out for 2 to 12 hours at room temperature, then toluene is continuously added dropwise slowly to the reaction flask and the temperature is raised to 160 ℃ and the reaction is continued for 4 to 8 hours at 160 ℃ to azeotropically remove toluene and water, after cooling to room temperature, 3.39g (15 mmol) of 2, 2-bis (4-aminophenyl) propane, 2.58g (15 mmol) of 1, 10-diaminodecane and 16.872g (38 mmol) of 4,4' - (hexafluoroisopropylidene) diphthalic anhydride, 90ml of solvent GB L and 0.7g (6 mmol) of hydroxyethyl acrylate are added, the total molar ratio of the total of the viscous 4,4' - (hexafluoroisopropylidene) diphthalic anhydride, 90ml of solvent GB L and the final addition of the resulting solution after the final addition of the molar ratio of the hydroxy groups to the total of the desired hydroxyl groups of the polymer.
And adding 8g of a PEG/PPO copolymer cross-linking agent with a methacrylate end-capped repeating unit of 16 and 0.4g of a thermal initiator AIBNB into the solution, fully dissolving and mixing, casting the mixture on a clean glass plate to form a film, drying the film for 10min in a forced air oven at the temperature of 90 ℃, taking out the film, carefully peeling and weighing the film. Completely immersing the film into a mixed solvent of ethanol and water (the mass ratio is 7: 3), soaking for 2-3 hours, clamping the film by a clamp, drying for 10 hours in a vacuum oven at 60 ℃, taking out and quickly weighing. This film was sample seven, ready for use.
Example eight:
2g (10 mmol) of diaminodiphenyl ether, 1.44g (10 mmol) of 1, 8-diaminooctane, 6.66g (15 mmol) of 4,4' - (hexafluoroisopropylene) diphthalic anhydride and 40ml of NMP solvent are added in this order to a dry three-necked flask under the protection of nitrogen, stirred at room temperature for 2 to 12 hours, then toluene is continuously and slowly added dropwise to the reaction flask, the temperature is raised to 160 ℃, and the reaction is continued for 4 to 8 hours while maintaining the temperature at 160 ℃, so that toluene and water are azeotropically removed. After the reaction was completed and cooled to room temperature, 3.39g (15 mmol) of 2, 2-bis (4-aminophenyl) propane, 2.58g (15 mmol) of 1, 10-diaminodecane and 8.284g (38 mmol) of pyromellitic dianhydride, 70ml of NMP as a solvent and 0.7g (6 mmol) of hydroxyethyl acrylate were added thereto, and stirring was continued at room temperature for 5 to 8 hours. After the second addition, the molar sum of the amino and hydroxyl groups in the reaction flask needs to be in equal ratio to the molar sum of the anhydride groups. The resulting highly viscous polymer solution was obtained.
And adding 8g of a polybutylene glycol cross-linking agent with a methacrylate end-capped repeating unit of 16 and 0.4g of a thermal initiator AIBNB into the solution, fully dissolving and mixing, pouring the mixture on a clean glass plate to form a film, drying the film for 10min in a forced air oven at the temperature of 90 ℃, taking out the film, carefully peeling and weighing the film. Completely immersing the film into a mixed solvent of ethanol and water (the mass ratio is 8: 2), soaking for 2-3 hours, clamping the film by a clamp, drying for 10 hours in a vacuum oven at 60 ℃, taking out and quickly weighing. This film was sample eight, ready for use.
TABLE one comparison of film Properties of examples 1-8
Claims (8)
1. A high temperature resistant diaphragm for lithium battery is characterized in that the structure of the diaphragm is composed of three parts: the film of the structure has good infiltration performance with lithium ion battery electrolyte, and after the film is formed, the microporous structure is obtained by turning over a solvent, and the film can be used as a high-temperature-resistant lithium ion battery diaphragm.
2. The wholly aromatic polyimide segment as set forth in claim 1 has a structural formula of:
wherein Ar is1Can be as follows:
wherein R is1Can be as follows:
wherein R is1Can be as follows: -CCH2OOCCH＝CH2，
Wherein x is a decimal between 0.5 and 1.0 and L is an integer between 5 and 50.
3. The semi-aliphatic polyimide segment as set forth in claim 1 having the formula:
wherein Ar is2Can be as follows:
wherein R is2Can be as follows:
the values of h and g are integers of 2 to 12, respectively.
Wherein R is2And R1May be the same or different, and may be: -CCH2OOCCH＝CH2，
Wherein the value of y is a decimal between 0 and 0.98 and the value of Z is an integer between 5 and 50.
4. The polyimide segments in claims 2 and 3 can be copolymerized in a molecular chain or blended.
5. The crosslinked segment of claim 1 having the formula:
k, P, Q, G, J, W may be equal or unequal, and are integers of 2-16.
6. The crosslinking agent according to claim 5 is added in an amount of 2 to 50wt% based on the mass of the polyimide segment.
7. The lithium battery diaphragm related by the invention adopts a mixed liquid pouring mode, a casting mode or a spin coating mode to form a film, and the thickness of the film is controlled to be 10-200 microns.
8. The solvent of the mixed solution may be: n, N-dimethylacetamide, N-methyl pyrrolidone, propylene glycol monomethyl ether acetate, gamma-butyrolactone and butyl lactate.
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