CN111403667B - 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 PDF

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CN111403667B
CN111403667B CN202010276628.XA CN202010276628A CN111403667B CN 111403667 B CN111403667 B CN 111403667B CN 202010276628 A CN202010276628 A CN 202010276628A CN 111403667 B CN111403667 B CN 111403667B
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诸轶强
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    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
    • H01M50/40—Separators; Membranes; Diaphragms; Spacing elements inside cells
    • H01M50/463—Separators, membranes or diaphragms characterised by their shape
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
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    • C08G73/06—Polycondensates having nitrogen-containing heterocyclic rings in the main chain of the macromolecule
    • C08G73/10—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
    • C08G73/1039—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors comprising halogen-containing substituents
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
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    • C08G73/1071—Wholly aromatic polyimides containing oxygen in the form of ether bonds in the main chain
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    • H01M50/40—Separators; Membranes; Diaphragms; Spacing elements inside cells
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    • Y02E60/10—Energy storage using batteries

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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

Composition of high-temperature-resistant lithium battery diaphragm and preparation method thereof
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 also 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, needs too long period and is difficult to produce in mass; for another example: the pore-forming steps described in patent CN 20141033970.9 and patent CN201720442163.4 are also quite cumbersome. 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 property 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:
Figure 634126DEST_PATH_IMAGE001
wherein Ar 1 Can be as follows:
Figure 886116DEST_PATH_IMAGE002
，
Figure 120961DEST_PATH_IMAGE003
,
Figure 687071DEST_PATH_IMAGE004
,
Figure 51057DEST_PATH_IMAGE005
，
Figure 411631DEST_PATH_IMAGE006
；
wherein R is 1 Can be as follows:
Figure 611799DEST_PATH_IMAGE007
，
Figure 981601DEST_PATH_IMAGE008
，
Figure 934513DEST_PATH_IMAGE009
，
Figure 731568DEST_PATH_IMAGE010
，
Figure 651988DEST_PATH_IMAGE011
，
Figure 825480DEST_PATH_IMAGE012
,
Figure 898479DEST_PATH_IMAGE013
;
wherein R is 1 Can be as follows:
Figure 866435DEST_PATH_IMAGE014
，
Figure 775616DEST_PATH_IMAGE015
，
Figure 487220DEST_PATH_IMAGE016
；
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:
Figure 414725DEST_PATH_IMAGE017
wherein Ar is 2 Can be as follows:
Figure 553582DEST_PATH_IMAGE018
，
Figure 448595DEST_PATH_IMAGE019
,
Figure 698310DEST_PATH_IMAGE020
,
Figure 745901DEST_PATH_IMAGE021
，
Figure 55659DEST_PATH_IMAGE022
；
wherein R is 2 Can be as follows: ,
Figure 939433DEST_PATH_IMAGE023
,
Figure 992840DEST_PATH_IMAGE024
(ii) a The values of h and g are integers from 2 to 12, respectively.
Wherein R is 2 And R 1 May be the same or different, and may be:
Figure 894937DEST_PATH_IMAGE025
，
Figure 375596DEST_PATH_IMAGE026
，
Figure 979622DEST_PATH_IMAGE027
；
wherein x is a decimal between 0 and 0.98 and Z is an integer between 5 and 50.
The polyimide chain segment 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:
Figure 836720DEST_PATH_IMAGE028
，
Figure 593323DEST_PATH_IMAGE029
,
Figure 244884DEST_PATH_IMAGE030
，
Figure 103250DEST_PATH_IMAGE031
，
wherein K, P, Q, G, J and W can be equal or unequal and are integers from 2 to 16 respectively.
Wherein contains Ar 1 And Ar 2 The dianhydrides of the structure may be the same or different and are each: pyromellitic dianhydride (PMDA), biphenyl dianhydride (PMDA), 3', 4' -diphenyl ether tetracarboxylic dianhydride (ODPA), 3', 4' -Benzophenone Tetracarboxylic Dianhydride (BTDA), and 4,4' - (hexafluoroisopropylidene) diphthalic anhydride (6 FDA). Containing R 1 Diamines 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 R 2 Diamines 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, 1,3Bis (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: under the protection of nitrogen, sequentially adding R into a dry three-neck bottle 1 Diamine monomer having an intermediate structure, and an intermediate structure having a lower number of moles than the diamine monomer and Ar 1 Stirring 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 repeatedly 1 Diamine monomer with intermediate structure, and intermediate structure with more moles of Ar than diamine monomer 1 The 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 total of amino and hydroxyl groups to the anhydride groups in the flask needs to be in equal ratio. 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 nitrogen 2 Diamine monomer with intermediate structure, and intermediate structure with Ar in less mole number than the diamine monomer 2 Stirring 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 obtain the final productAnd removing benzene and water azeotropically. After the reaction is finished, after cooling to room temperature, R is added repeatedly 2 Diamine monomer with intermediate structure, and intermediate structure with more moles of Ar than diamine monomer 2 And a certain amount of grafting monomers such as hydroxyethyl acrylate or hydroxyethyl methacrylate or 2-methyl-4-hydroxybutene, and the like, and continuously stirring 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 a wholly aromatic polyimide chain segment and a semi-aliphatic polyimide chain segment: adding R into a dry three-neck bottle in sequence under the protection of nitrogen 1 Or R 2 Or R 1 And R 2 Two diamine monomers with intermediate structure, and the intermediate structure with the mole number less than that of the diamine monomers is Ar 1 Or Ar 2 Stirring 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 ℃ for continuously reacting for 4-8 hours, and removing the toluene and water by azeotropy. After the reaction is finished, cooling to room temperature, and repeatedly adding a certain amount of R 1 Or R 2 Or R 1 And R 2 Two diamine monomers with intermediate structure, and the intermediate structure with more moles of Ar than the diamine monomers 1 Or Ar 2 The 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 total of amino and hydroxyl groups to the anhydride groups in the flask needs to be in equal ratio. 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
Adding a cross-linking agent which accounts for 2 to 50wt percent of the weight of the polyimide chain segment into a copolymer solution of a formal mixed or wholly aromatic polyimide chain segment and a semi-aliphatic polyimide chain segment, wherein the structure of the cross-linking agent is as follows:
Figure 498459DEST_PATH_IMAGE032
，
Figure 109569DEST_PATH_IMAGE033
,
Figure 197611DEST_PATH_IMAGE034
，
Figure 776228DEST_PATH_IMAGE035
wherein K, P, Q, G, J and W can be equal or unequal and are integers from 2 to 16 respectively.
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 subjected to film forming 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 a mixed solvent of methanol/ethanol and water for 2 to 5 hours, the ratio of the alcohol to the water is 5 to 5-9, then a 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 degrees. 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 each example 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 measured 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 5mm/min.
Testing of coefficient of thermal expansion CTE: the Mettler-toledo TMA1 is measured under the conditions that the test range is 20-180 ℃ and the temperature rise 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 performance: according to the film in electrolyte (LiCF) 3 SO 3 Diethyl carbonate solution) 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 GBL solvent were added successively to a dry three-necked flask under a nitrogen atmosphere, stirred at room temperature for 2-12 hours, and then toluene was continuously and slowly added dropwise to the flask, and the temperature was raised to 160 ℃ to continue the reaction at 160 ℃ for 4-8 hours, thereby azeotropically removing toluene and water. After the reaction was completed and cooled to room temperature, 2g (10 mmol) of diaminodiphenyl ether, 5.772g (13 mmol) of 4,4' - (hexafluoroisopropylene) diphthalic anhydride, 10ml of solvent GBL and 0.52g (4 mmol) of hydroxyethyl methacrylate were repeatedly added, 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.
0.72g (5 mmol) of 1, 8-diaminooctane, 1.776g (4 mmol) of 4,4' - (hexafluoroisopropylene) diphthalic anhydride and 15ml of solvent GBL are sequentially added to a dry three-necked flask under the protection of nitrogen, stirred at room temperature for 2-12 hours, and then toluene is continuously and slowly added dropwise to the reaction flask, and the temperature is raised to 160 ℃, and the reaction is continued for 4-8 hours while maintaining 160 ℃, so that toluene and water are azeotropically removed. After completion of the reaction and cooling to room temperature, 1.44g (10 mmol) of 1, 8-diaminooctane, 4.116g (14 mmol) of biphenyl dianhydride, 22ml of solvent GBL and 0.78g (6 mmol) of hydroxyethyl methacrylate were repeated, 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.
Mixing the two polyimide solutions, adding 6g of PEG cross-linking agent with 16 methacrylate end-capped repeating units and 0.4g of 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 30min in a blowing 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. 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' - (hexafluoroisopropylidene) diphthalic anhydride and 20ml of NMP as a solvent were sequentially charged into a dry three-necked flask under a nitrogen atmosphere, stirred at room temperature for 2 to 12 hours, and then toluene was continuously and slowly added dropwise into the flask, and the reaction was continued for 4 to 8 hours while the temperature was raised to 160 ℃ to azeotropically remove 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 an air-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. 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-neck 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 continued for 4-8 hours under the temperature of 160 ℃, and the toluene and water are removed azeotropically. After completion of the reaction, the reaction mixture was cooled to room temperature, and 3.28g (10 mmol) of 1, 8-bis (4-aminophenoxy) octane, 7.548g (17 mmol) of 4,4' - (hexafluoroisopropylene) diphthalic anhydride, 43ml of solvent GBL and 1.42g (12 mmol) of hydroxyethyl acrylate 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.
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 peeled and weighed. Completely immersing the film into a mixed solvent of ethanol and water (the mass ratio is 9. 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' -benzophenone tetracarboxylic dianhydride and 20ml of solvent GBL are added into a dry three-neck flask in sequence under the protection of nitrogen, stirred for 2-12 hours at room temperature, and then toluene is continuously and slowly dropped into the reaction flask and heated to 160 ℃, and the reaction is continued for 4-8 hours under the condition of keeping 160 ℃ to ensure that the toluene and the water are removed azeotropically. After the reaction was completed and cooled to room temperature, 2.32g (20 mmol) of 1, 6-diaminohexane, 5.668g (26 mmol) of pyromellitic anhydride, 10ml of solvent GBL and 1.3g (10 mmol) of hydroxyethyl methacrylate were repeatedly added, 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.
Then 8g of a polytetramethylene glycol cross-linking agent with a repeating unit of 12 and terminated by methacrylate and 0.3g of a 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 peeled off the film and weighed. Completely immersing the film into a mixed solvent of ethanol and water (the mass ratio is 8. 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' -diphenyl ether tetracarboxylic dianhydride and 26ml of NMP solvent are sequentially added into a dry three-necked flask, stirred at room temperature for 2-12 hours, then toluene is continuously and slowly added into the reaction flask, the temperature is raised to 160 ℃, the reaction is continuously carried out for 4-8 hours under the condition of keeping 160 ℃, and the toluene and water are removed azeotropically. 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' - (hexafluoroisopropylidene) 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 methacrylate end-capped repeating unit of 12 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 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 8. 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 GBL are sequentially added into a dry three-neck bottle, stirred at room temperature for 2-12 hours, and then toluene is continuously and slowly dropped 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 the reaction was completed and cooled to room temperature, 2g (10 mmol) of diaminodiphenyl ether, 5.772g (13 mmol) of 4,4' - (hexafluoroisopropylene) diphthalic anhydride, 10ml of solvent GBL and 0.52g (4 mmol) of hydroxyethyl methacrylate were repeatedly added, and stirring was continued at room temperature for 5 to 8 hours. After the second addition, the molar total of amino and hydroxyl groups to the anhydride groups in the flask needs to be in equal ratio. The resulting highly viscous polymer solution was obtained.
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 GBL 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, and 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 160 ℃, so that toluene and water are azeotropically removed. After the reaction was completed and cooled to room temperature, 3.84g (10 mmol) of 1, 12-bis (4-aminophenoxy) dodecane, 4.116g (14 mmol) of biphenyl dianhydride, 31ml of solvent GBL and 0.696g (6 mmol) of hydroxyethyl acrylate were repeated, and stirring was continued at room temperature for 5 to 8 hours. After the second addition, the molar total of amino and hydroxyl groups to the anhydride groups in the flask needs to be in equal ratio. The resulting highly viscous polymer solution was obtained.
Mixing the two polyimide solutions prepared above, adding 6g of a polybutylene glycol cross-linking agent with a methacrylate end-capped repeating unit of 12 and 0.4g of a thermal initiator AIBNP into the solutions, fully dissolving and mixing, casting the mixture on a clean glass plate to form a film, drying the film for 20min in an air-blowing 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 9. 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' - (hexafluoroisopropylene) diphthalic anhydride and 50ml of solvent GBL 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 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 completion of the reaction, the mixture was cooled to room temperature, and then 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 GBL and 0.7g (6 mmol) of hydroxyethyl acrylate were 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 adding 8g of PEG/PPO copolymer cross-linking agent with a methacrylate end-capped repeating unit of 16 and 0.4g of thermal initiator AIBN 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 an air-blast oven at the temperature of 90 ℃, taking out the film, carefully peeling the film and weighing the film. Completely immersing the film into a mixed solvent of ethanol and water (the mass ratio is 7. 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' - (hexafluoroisopropylidene) diphthalic anhydride and 40ml of NMP solvent are sequentially added 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 dropped into the reaction flask, the temperature is raised to 160 ℃, the reaction is continued for 4-8 hours under the condition of keeping 160 ℃, and the 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 solvent NMP and 0.7g (6 mmol) of hydroxyethyl acrylate were further added, 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 repeating unit of 16 and terminated by methacrylate and 0.4g of a thermal initiator AIBNP 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 an air-blast oven at the temperature of 90 ℃, taking out the film, carefully peeling the film and weighing the film. Completely immersing the film into a mixed solvent of ethanol and water (the mass ratio is 8. This film was sample eight, ready for use.
TABLE one comparison of film Properties of examples 1-8
Figure 37446DEST_PATH_IMAGE036

Claims (1)

1. A method of preparing a high temperature resistant separator for a lithium battery, the method comprising the steps of:
(1) Under the protection of nitrogen, 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 GBL are sequentially added into a dry three-necked bottle, stirred at room temperature for 2-12 hours, then toluene is continuously and slowly dropped 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 azeotropically removed;
(2) 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 16.872g (38 mmol) of 4,4' - (hexafluoroisopropylene) diphthalic anhydride, 90ml of solvent GBL and 0.7g (6 mmol) of hydroxyethyl acrylate were further added, and stirring was continued at room temperature for 5 to 8 hours to obtain a highly viscous polymer solution;
(3) 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 AIBNP 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;
(4) Completely immersing the film into the solution with the mass ratio of 7:3, soaking for 2-3 hours in a mixed solvent of ethanol and water, clamping the film by a clamp, and drying for 10 hours in a vacuum oven at 60 ℃ to obtain the high-temperature-resistant diaphragm for the lithium battery.
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