CN111430648B - Polyimide lithium ion battery diaphragm, preparation method and lithium ion battery - Google Patents
Polyimide lithium ion battery diaphragm, preparation method and lithium ion battery Download PDFInfo
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- CN111430648B CN111430648B CN202010382382.4A CN202010382382A CN111430648B CN 111430648 B CN111430648 B CN 111430648B CN 202010382382 A CN202010382382 A CN 202010382382A CN 111430648 B CN111430648 B CN 111430648B
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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
- H01M50/409—Separators, membranes or diaphragms characterised by the material
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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
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/052—Li-accumulators
- H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
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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
- H01M50/403—Manufacturing processes of separators, membranes or diaphragms
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2379/00—Characterised by the use of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing nitrogen with or without oxygen, or carbon only, not provided for in groups C08J2361/00 - C08J2377/00
- C08J2379/04—Polycondensates having nitrogen-containing heterocyclic rings in the main chain; Polyhydrazides; Polyamide acids or similar polyimide precursors
- C08J2379/08—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2479/00—Characterised by the use of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing nitrogen with or without oxygen, or carbon only, not provided for in groups C08J2461/00 - C08J2477/00
- C08J2479/04—Polycondensates having nitrogen-containing heterocyclic rings in the main chain; Polyhydrazides; Polyamide acids or similar polyimide precursors
- C08J2479/08—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
Abstract
The invention belongs to the technical field of lithium ion batteries, and particularly relates to a polyimide lithium ion battery diaphragm, a preparation method and a lithium ion battery, wherein the diaphragm comprises the following components in parts by weight; the average grain diameter of the first ceramic powder is 1-3 mu m; the average particle diameter of the second ceramic powder is 0.01-0.06 mu m. According to the invention, the ceramic micro powder modified by the aminosilane coupling agent is used as a crosslinking point, and the similar concentrated crosslinking effect is generated by utilizing the different particle sizes of the two ceramic micro powder, so that the stress can be dispersed when the diaphragm encounters puncture, and the diaphragm has higher puncture strength.
Description
Technical Field
The invention belongs to the technical field of lithium ion batteries, and relates to a polyimide lithium ion battery diaphragm, a preparation method and a lithium ion battery.
Background
Lithium ion batteries are increasingly being used in various fields due to their environmental friendliness and convenience. The separator is one of the key components of the lithium ion battery, and the performance of the separator has a great influence on the performance of the lithium ion battery. In addition to conventional polyolefin separators such as polyethylene and polypropylene, some new separators have been developed, and Polyimide (PI) is one of them. CN109119572a discloses a polyimide lithium battery diaphragm, which comprises binary organic amine, binary organic anhydride, polyamino cross-linking agent and ceramic powder modified by the surface of the amino coupling agent, and is subjected to reaction and imidization to form polyimide, so that the mechanical strength of the diaphragm is effectively improved, but the puncture strength of the diaphragm is not high enough.
Disclosure of Invention
One object of the present invention is to overcome the defects of the prior art and provide a polyimide lithium ion battery diaphragm
The invention further aims to provide a preparation method of the polyimide lithium ion battery.
It is yet another object of the present invention to provide a lithium ion battery.
The technical scheme of the invention is as follows:
the polyimide lithium ion battery diaphragm comprises, by weight, 30-50 parts of aromatic binary organic amine, 30-50 parts of aromatic binary organic anhydride, 2-4 parts of aromatic polyamino cross-linking agent, 5-15 parts of first ceramic powder modified by an aminosilane coupling agent and 3-8 parts of second ceramic powder modified by the aminosilane coupling agent;
the average grain diameter of the first ceramic powder is 1-3 mu m;
the average particle diameter of the second ceramic powder is 0.01-0.06 mu m. Preferably, the weight of the aminosilane coupling agent modified second ceramic powder is no more than 70% but no less than 30% of the weight of the aminosilane coupling agent modified first ceramic powder.
Preferably, the aromatic binary organic amine is at least one selected from the group consisting of 4,4 '-diaminodiphenyl ether, p-phenylenediamine, m-phenylenediamine, 4' -bis (4-aminophenoxy) biphenyl and 1, 3-bis (4-aminophenoxy) benzene; the aromatic binary organic anhydride is at least one selected from pyromellitic dianhydride, biphenyl tetracarboxylic dianhydride and benzophenone tetracarboxylic dianhydride; the aromatic polyamino crosslinking agent is at least one selected from 1,3, 5-triaminobenzene and 1,3, 5-tris (4-aminophenoxy) benzene.
Preferably, the aminosilane coupling agent is selected from at least one of 3-aminopropyl trimethoxysilane, 3-aminopropyl triethoxysilane, 3-aminopropyl methyldimethoxysilane, 3-aminopropyl methyldiethoxysilane, N- (2-aminoethyl) -3-aminopropyl trimethoxysilane, N- (2-aminoethyl) -3-aminopropyl triethoxysilane, N- (2-aminoethyl) -3-aminopropyl methyldimethoxysilane, N- (2-aminoethyl) -3-aminopropyl methyldiethoxysilane, 3-diethylenetriaminopropyl trimethoxysilane, 3-diethylenetriaminopropyl triethoxysilane, 3-diethylenetriaminopropyl methyldimethoxysilane and 3-diethylenetriaminopropyl methyldiethoxysilane. The silane coupling agent is used for treating ceramic powder in a conventional treatment method, and the ceramic powder can be directly subjected to silanization treatment after water and oil removal, or can be subjected to silanization treatment after alkali liquor treatment.
Preferably, the first ceramic powder is selected from at least one of alumina, silicon carbide, aluminum carbide, boron carbide, aluminum nitride, boron nitride, and silicon dioxide. More preferably, the first ceramic powder is selected from alumina, silica or silicon carbide.
Preferably, the second ceramic powder is selected from at least one of alumina, silicon carbide, aluminum carbide, boron carbide, aluminum nitride, boron nitride, and silicon dioxide. More preferably, the second ceramic powder is selected from alumina, silica or silicon carbide.
A method for preparing a lithium ion battery separator according to any of the above embodiments, comprising the steps of,
s1, dispersing the first ceramic micro powder modified by the aminosilane coupling agent, the second ceramic micro powder modified by the aminosilane coupling agent, aromatic binary organic amine, aromatic binary organic anhydride and aromatic polyamino cross-linking agent in an organic solvent for condensation reaction to obtain a polyamide acid solution; preferably, the organic solvent may be selected from N, N-Dimethylformamide (DMF), N-dimethylacetamide (DMAc) or N-methylpyrrolidone (NMP), and the amount of the organic solvent used is preferably 400 to 700 parts.
S2, adding a pore-forming agent into the polyamic acid solution in the step S1, uniformly stirring, and defoaming to obtain a coating liquid; the usage amount of the pore-forming agent is preferably 30-50 parts;
s3, coating the coating liquid in the step S2 on a substrate to form a polyamic acid film, solidifying in a coagulating bath, and removing a pore-forming agent to obtain a solidified film; the coating liquid is coated by a scraper.
And S4, carrying out imidization reaction on the solidified film in the step S3 to obtain the polyimide lithium ion battery diaphragm.
Preferably, the pore-forming agent in step S2 is at least one selected from the group consisting of ethylene glycol benzoate, ethylene glycol, propylene glycol, glycerin, butyl benzoate, polyethylene glycol, polyvinylpyrrolidone, diethylene glycol and triethylene glycol.
Preferably, the thickness of the polyamic acid film in step S3 is 60 to 300. Mu.m. More preferably, the thickness of the polyamic acid film is 100 to 150. Mu.m.
Preferably, the imidization reaction in step S4 is carried out at a temperature of 270 to 350 ℃ for a time of 2 to 4 hours. The imidization reaction can be controlled by temperature programming, the temperature is kept at 60-100 ℃ for 2-3 hours, the temperature is kept at 120-150 ℃ for 1-2 hours, the temperature is kept at 200-220 ℃ for 1-2 hours, the temperature is kept at 270-300 ℃ for 1-2 hours, the temperature is kept at 330-350 ℃ for 1-2 hours, and the temperature rising rate is 1-3 ℃/min.
A lithium ion battery comprising a polyimide lithium ion battery separator according to any one of the embodiments described above.
The beneficial effects of the invention are as follows: the surface of the ceramic micro powder modified by the aminosilane coupling agent is provided with a plurality of amino groups, and the amino groups can participate in the polyamic acid reaction to form a cross-linking point-like effect. The invention utilizes two ceramic micro powder with larger particle size difference, and the second ceramic micro powder has higher amino group density per unit area on the surface of the micro powder due to small particle size, so that the cross-linking density per unit area can be formed. The different crosslinking densities of the second ceramic micro powder and the first ceramic micro powder on the unit area of the surface can form a similar concentrated crosslinking effect, and the external force can be dispersed when the diaphragm is subjected to external force such as puncture and the like, so that higher puncture strength can be obtained.
Drawings
FIG. 1 is a schematic cross-linking structure of a polyimide lithium ion battery separator according to example 5 of the present invention,
wherein the first ceramic powder is 1-second ceramic powder, the second ceramic powder is 2-first ceramic powder, and the third ceramic powder is 3-PI polymer chain.
Figure 2 is a schematic cross-linked structure of a polyimide lithium ion battery separator of comparative example 1,
wherein the 1-ceramic micropowder and the 2-PI polymer chain.
Detailed Description
The technical scheme of the invention is further illustrated and described through the following specific embodiments.
Unless otherwise indicated, parts in the following embodiments are parts by weight.
Example 1
The average grain diameter of the first alumina micro powder is 1.5 mu m, and the first alumina micro powder is modified by 3-aminopropyl trimethoxy silane.
The average grain diameter of the second alumina micro powder is 0.03 mu m, and the second alumina micro powder is modified by 3-aminopropyl trimethoxy silane.
The formula is as follows: 30 parts of 4,4' -diaminodiphenyl ether, 30 parts of pyromellitic dianhydride, 2 parts of 1,3, 5-diaminobenzene, 5 parts of first alumina powder modified by an aminosilane coupling agent and 3 parts of second alumina powder modified by the aminosilane coupling agent.
Dispersing first alumina micropowder modified by an aminosilane coupling agent, second alumina micropowder modified by the aminosilane coupling agent, 4' -diaminodiphenyl ether, pyromellitic dianhydride and 1,3, 5-triaminobenzene in 450 parts of DMF (dimethyl formamide), and carrying out condensation reaction to obtain a polyamide acid solution;
adding 30 parts of Kong Jiben ethylene glycol formate, stirring uniformly, and defoaming to obtain a coating solution;
coating the coating liquid on a substrate to form a polyamide acid film with the film thickness of 70 mu m, solidifying in a coagulating bath, and removing the benzoic acid ethylene glycol ester to obtain a solidified film;
and (3) preserving the temperature of the solidified film at 60 ℃ for 2 hours, preserving the temperature at 120 ℃ for 1.5 hours, preserving the temperature at 200 ℃ for 1 hour, preserving the temperature at 270 ℃ for 1.5 hours, preserving the temperature at 330 ℃ for 1 hour, and obtaining the polyimide lithium ion battery diaphragm, namely PI-1.
Example 2
The first silica micropowder has an average particle diameter of 2.2 μm and is modified by 3-aminopropyl trimethoxysilane.
The second silicon dioxide micro powder has an average particle diameter of 0.05 mu m and is modified by 3-aminopropyl trimethoxy silane.
The formula is as follows: 40 parts of p-phenylenediamine, 40 parts of pyromellitic dianhydride, 3 parts of 1,3, 5-tris (4-aminophenoxy) benzene, 8 parts of first silica powder modified with an aminosilane coupling agent and 5 parts of second silica powder modified with an aminosilane coupling agent.
Dispersing first silica micropowder modified by an aminosilane coupling agent, second silica micropowder modified by the aminosilane coupling agent, p-phenylenediamine, pyromellitic dianhydride and 1,3, 5-tris (4-aminophenoxy) benzene in 550 parts of NMP, and carrying out condensation reaction to obtain a polyamic acid solution;
adding 40 parts of pore-forming agent polyethylene glycol-600 into the polyamic acid solution, uniformly stirring, and defoaming to obtain a coating liquid;
coating the coating liquid on a substrate to form a polyamide acid film with the film thickness of 90 mu m, solidifying in a coagulating bath, and removing a pore-forming agent to obtain a solidified film;
and (3) preserving the temperature of the solidified membrane at 80 ℃ for 2 hours, preserving the temperature at 130 ℃ for 2 hours, preserving the temperature at 220 ℃ for 2 hours, preserving the temperature at 300 ℃ for 2 hours, preserving the temperature at 340 ℃ for 1 hour, and obtaining the polyimide lithium ion battery diaphragm, namely PI-2.
Example 3
The first alumina micropowder has an average particle diameter of 2.7 μm and is modified by N- (2-aminoethyl) -3-aminopropyl trimethoxysilane.
The second silicon carbide micro powder has an average particle diameter of 0.06 mu m and is modified by N- (2-aminoethyl) -3-aminopropyl trimethoxysilane.
The formula is as follows: 50 parts of 4,4' -bis (4-aminophenoxy) biphenyl, 50 parts of biphenyl tetracarboxylic dianhydride, 3 parts of 1,3, 5-triaminobenzene, 15 parts of first alumina powder modified by an aminosilane coupling agent and 8 parts of second silicon carbide powder modified by the aminosilane coupling agent.
Dispersing first alumina micropowder modified by an aminosilane coupling agent, second silicon carbide micropowder modified by the aminosilane coupling agent, 4' -bis (4-aminophenoxy) biphenyl, biphenyl tetracarboxylic dianhydride and 1,3, 5-triaminobenzene into 700 parts of DMAc, and carrying out condensation reaction to obtain a polyamic acid solution;
adding 50 parts of pore-forming agent glycol into the polyamic acid solution, uniformly stirring, and defoaming to obtain a coating liquid;
coating the coating liquid on a substrate to form a polyamide acid film with the film thickness of 130 mu m, solidifying in a coagulating bath, and removing a pore-forming agent to obtain a solidified film;
and (3) preserving the heat of the solidification film at 100 ℃ for 2 hours, preserving the heat of the solidification film at 150 ℃ for 1 hour, preserving the heat of the solidification film at 210 ℃ for 1 hour, preserving the heat of the solidification film at 300 ℃ for 1.5 hours, preserving the heat of the solidification film at 350 ℃ for 1 hour, and obtaining the polyimide lithium ion battery diaphragm, namely PI-3, at a heating rate of 3 ℃/min.
Example 4
The average grain diameter of the first alumina micro powder is 2.2 mu m, and the first alumina micro powder is modified by 3-aminopropyl trimethoxy silane.
The second silicon dioxide micro powder has an average particle diameter of 0.06 mu m and is modified by 3-aminopropyl trimethoxy silane.
The formula is as follows: 40 parts of 4,4' -diaminodiphenyl ether, 42 parts of pyromellitic dianhydride, 3.5 parts of 1,3, 5-diaminobenzene, 10 parts of first alumina powder modified by an aminosilane coupling agent and 6 parts of second silica powder modified by the aminosilane coupling agent.
Dispersing first alumina micropowder modified by an aminosilane coupling agent, second silica micropowder modified by the aminosilane coupling agent, 4' -diaminodiphenyl ether, pyromellitic dianhydride and 1,3, 5-diaminobenzene in 500 parts of DMF (dimethyl formamide), and carrying out condensation reaction to obtain a polyamide acid solution;
45 parts of Kong Jibing glycol is added into the polyamic acid solution, and the mixture is stirred uniformly and defoamed to obtain coating liquid;
coating the coating liquid on a substrate to form a polyamide acid film with the film thickness of 100 mu m, solidifying in a coagulating bath, and removing a pore-forming agent to obtain a solidified film;
and (3) preserving the temperature of the solidified film at 70 ℃ for 2 hours, preserving the temperature at 130 ℃ for 1 hour, preserving the temperature at 200 ℃ for 1 hour, preserving the temperature at 280 ℃ for 1.5 hours, preserving the temperature at 330 ℃ for 1.5 hours, and obtaining the polyimide lithium ion battery diaphragm, namely PI-4, at a heating rate of 2 ℃/min.
Example 5
The formula is as follows: 35 parts of 4,4' -diaminodiphenyl ether, 45 parts of pyromellitic dianhydride, 4 parts of 1,3, 5-diaminobenzene, 12 parts of the aminosilane coupling agent-modified first alumina powder of example 4 and 6 parts of the aminosilane coupling agent-modified second silica powder of example 4.
Dispersing first alumina micropowder modified by an aminosilane coupling agent, second silica micropowder modified by the aminosilane coupling agent, 4' -diaminodiphenyl ether, pyromellitic dianhydride and 1,3, 5-diaminobenzene in 500 parts of DMF (dimethyl formamide), and carrying out condensation reaction to obtain a polyamide acid solution;
adding 40 parts of Kong Jiben butyl formate into the polyamic acid solution, uniformly stirring, and defoaming to obtain a coating solution;
coating the coating liquid on a substrate to form a polyamic acid film with the film thickness of 80 mu m, solidifying in a coagulating bath, and removing a pore-forming agent to obtain a solidified film;
and (3) preserving the heat of the solidified film at 60 ℃ for 2 hours, preserving the heat of the solidified film at 120 ℃ for 1 hour, preserving the heat of the solidified film at 210 ℃ for 1 hour, preserving the heat of the solidified film at 290 ℃ for 2 hours, preserving the heat of the solidified film at 340 ℃ for 1 hour, and obtaining the polyimide lithium ion battery diaphragm which is marked as PI-5, wherein the heating rate is 2 ℃/min. A schematic of the cross-linked structure of the separator is shown in fig. 1.
Comparative example 1
12 parts of the aminosilane coupling agent-modified first alumina powder of example 4 and 6 parts of the aminosilane coupling agent-modified second silica powder of example 4 were changed to 18 parts of the aminosilane coupling agent-modified first alumina powder of example 4, and the other was designated PI-6. A schematic of the cross-linked structure of the separator is shown in fig. 2.
Comparative example 2
12 parts of the aminosilane coupling agent-modified first alumina powder of example 4 and 6 parts of the aminosilane coupling agent-modified second silica powder of example 4 were changed to 18 parts of the aminosilane coupling agent-modified second silica powder of example 4, and the other was designated PI-7.
Comparative example 3
12 parts of the aminosilane coupling agent-modified first alumina powder of example 4 and 6 parts of the aminosilane coupling agent-modified second silica powder of example 4 in example 5 were changed to 6 parts of the aminosilane coupling agent-modified first alumina powder of example 4 and 12 parts of the aminosilane coupling agent-modified second silica powder of example 4, and the other is denoted PI-8.
Comparative example 4
The average grain diameter of the first alumina micro powder is 1.8 mu m, and the first alumina micro powder is modified by 3-aminopropyl trimethoxy silane.
The second silica micropowder has an average particle diameter of 0.2 μm and is modified by 3-aminopropyl trimethoxysilane. The remainder, consistent with example 5, was designated PI-9.
The mechanical properties of PI1-9 are shown in the following table.
Comparison of mechanical Properties of the Table
| Film thickness/. Mu.m | Tensile Strength/MPa | Elongation at break/% | Puncture strength/N | |
| PI-1 | 23 | 60 | 28 | 4.4 |
| PI-2 | 26 | 63 | 29 | 4.7 |
| PI-3 | 31 | 69 | 31 | 5.2 |
| PI-4 | 27 | 63 | 28 | 4.6 |
| PI-5 | 23 | 61 | 29 | 4.6 |
| PI-6 | 23 | 62 | 30 | 3.6 |
| PI-7 | 23 | 64 | 32 | 3.8 |
| PI-8 | 23 | 61 | 31 | 3.5 |
| PI-9 | 23 | 62 | 30 | 3.9 |
Therefore, the polyimide lithium ion battery diaphragm has higher puncture strength under the conditions of similar tensile strength and elongation at break.
As described above, the basic principles, main features and advantages of the present invention are shown and described. It will be appreciated by persons skilled in the art that the present invention is not limited to the embodiments described above, which are preferred embodiments of the present invention, and the scope of the invention is not limited thereto, i.e. equivalent changes and modifications as defined by the claims and the description herein should be made while remaining within the scope of the invention. The scope of the invention is defined by the appended claims and equivalents thereof.
Claims (10)
1. The polyimide lithium ion battery diaphragm is characterized by comprising the following raw materials, by weight, 30-50 parts of aromatic binary organic amine, 30-50 parts of aromatic binary organic anhydride, 2-4 parts of aromatic polyamino cross-linking agent, 5-15 parts of first ceramic powder modified by an aminosilane coupling agent and 3-8 parts of second ceramic powder modified by the aminosilane coupling agent;
the average grain diameter of the first ceramic powder is 1-3 mu m;
the average particle diameter of the second ceramic powder is 0.01-0.06 mu m.
2. The lithium ion battery separator according to claim 1, wherein the aromatic binary organic amine is selected from at least one of 4,4 '-diaminodiphenyl ether, p-phenylenediamine, m-phenylenediamine, 4' -bis (4-aminophenoxy) biphenyl, and 1, 3-bis (4-aminophenoxy) benzene; the aromatic binary organic anhydride is at least one selected from pyromellitic dianhydride, biphenyl tetracarboxylic dianhydride and benzophenone tetracarboxylic dianhydride; the aromatic polyamino crosslinking agent is at least one selected from 1,3, 5-triaminobenzene and 1,3, 5-tris (4-aminophenoxy) benzene.
3. The lithium ion battery separator of claim 1, wherein the aminosilane coupling agent is selected from at least one of 3-aminopropyl trimethoxysilane, 3-aminopropyl triethoxysilane, 3-aminopropyl methyldimethoxysilane, 3-aminopropyl methyldiethoxysilane, N- (2-aminoethyl) -3-aminopropyl trimethoxysilane, N- (2-aminoethyl) -3-aminopropyl triethoxysilane, N- (2-aminoethyl) -3-aminopropyl methyldimethoxysilane, N- (2-aminoethyl) -3-aminopropyl methyldiethoxysilane, 3-diethylenetriaminopropyl trimethoxysilane, 3-diethylenetriaminopropyl triethoxysilane, 3-diethylenetriaminopropyl methyldimethoxysilane, and 3-diethylenetriaminopropyl methyldiethoxysilane.
4. The lithium ion battery separator of claim 1, wherein the first ceramic powder is selected from at least one of alumina, silicon carbide, aluminum carbide, boron carbide, aluminum nitride, boron nitride, and silicon dioxide.
5. The lithium ion battery separator of claim 1, wherein the second ceramic powder is selected from at least one of alumina, silicon carbide, aluminum carbide, boron carbide, aluminum nitride, boron nitride, and silicon dioxide.
6. A method for preparing a lithium ion battery separator according to any one of claim 1 to 5, comprising the steps of,
s1, dispersing the first ceramic micro powder modified by the aminosilane coupling agent, the second ceramic micro powder modified by the aminosilane coupling agent, aromatic binary organic amine, aromatic binary organic anhydride and aromatic polyamino cross-linking agent in an organic solvent for condensation reaction to obtain a polyamide acid solution;
s2, adding a pore-forming agent into the polyamic acid solution in the step S1, uniformly stirring, and defoaming to obtain a coating liquid;
s3, coating the coating liquid in the step S2 on a substrate to form a polyamic acid film, solidifying in a coagulating bath, and removing a pore-forming agent to obtain a solidified film;
and S4, carrying out imidization reaction on the solidified film in the step S3 to obtain the polyimide lithium ion battery diaphragm.
7. The method according to claim 6, wherein the pore-forming agent in step S2 is at least one selected from the group consisting of ethylene glycol benzoate, ethylene glycol, propylene glycol, glycerin, butyl benzoate, polyethylene glycol, polyvinylpyrrolidone, diethylene glycol and triethylene glycol.
8. The method according to claim 6, wherein the thickness of the polyamic acid film in step S3 is 60 to 300. Mu.m.
9. The process according to claim 6, wherein the imidization reaction is carried out at a temperature of 270 to 350℃for a time of 2 to 4 hours in step S4.
10. A lithium ion battery comprising the polyimide lithium ion battery separator of any one of claims 1-5.
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| CN112457629B (en) * | 2020-11-30 | 2021-10-15 | 吉林大学 | Carbon fiber surface grafted two-dimensional network structure reinforced polyether-ether-ketone composite material and preparation method thereof |
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| CN109119572A (en) * | 2018-08-01 | 2019-01-01 | 乳源东阳光氟树脂有限公司 | Polyimides lithium battery diaphragm and preparation method thereof and lithium battery comprising the diaphragm |
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