CN107492620A - A kind of high-temperature-reslithium lithium battery barrier film and preparation method thereof - Google Patents
A kind of high-temperature-reslithium lithium battery barrier film and preparation method thereof Download PDFInfo
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- CN107492620A CN107492620A CN201710699967.7A CN201710699967A CN107492620A CN 107492620 A CN107492620 A CN 107492620A CN 201710699967 A CN201710699967 A CN 201710699967A CN 107492620 A CN107492620 A CN 107492620A
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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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- 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
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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
- H01M50/411—Organic 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
- 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
- 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
- H01M50/449—Separators, membranes or diaphragms characterised by the material having a layered structure
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Abstract
The present invention discloses a kind of high-temperature-reslithium lithium battery barrier film and preparation method thereof, the high-temperature-reslithium lithium battery barrier film includes base material film and the alkaline metal oxide coating coated on base material film surface, the alkaline metal oxide coating layer thickness is 1 ~ 4 μm, and described alkaline metal oxide coating is made up of polymeric binder, modified alkaline metal oxide and solvent.The coating of the present invention has good adhesive force and uniformity, so that coating has good heat resistance, modified alkaline metal oxide therein has good compatibility with polymeric binder, and obtained barrier film has preferable dimensional stability, and it is indeformable at high temperature.
Description
Technical field
The present invention relates to battery diaphragm field, more particularly to the carbon negative electrode material of lithium ion cell of a species graphene-structured
Preparation method.
Background technology
With the development of electronic communication equipment, computer equipment and mobile communication equipment, it is to as these device power supply (DPS)s
Lithium secondary battery demand it is growing day by day.The research and development tide of one lithium secondary battery is started in worldwide, this
Outside, lithium secondary battery serves not only as the power supply of mobile electronic device, electric automobile, electric tool, satellite etc. can also be used as to set
Standby environmentally friendly power supply.
Lithium secondary battery include lithium transition alkaline metal oxide positive pole, can embedding lithium ionic insertion/deinsertion negative pole, positive pole and negative pole
Between barrier film, the electrolyte as lithium ion mobility carrier.
The main function of barrier film is to keep apart positive pole and negative pole, and electrolyte is remained to ensure high ion
Electrical conductivity.Currently, widely used barrier film is MIcroporous polyolefin film, such as polythene PE that melting temperature is 130 DEG C or melting
Temperature is 170 DEG C of microporous polypropylene membrane PP, such film reach after melting temperature can self closing micropore, play breaking effect.
However, when electric current is excessive, and temperature continues rise, due to the relatively low melting temperature of polyalkene diaphragm so that shunk under its high temperature
Deformation, cause battery short circuit, trigger bigger danger.
In order to improve the enterprise of the state such as barrier film temperature tolerance, Japan, South Korea successively report using ceramic coated polyolefin every
Film is to improve the temperature tolerance of barrier film.However, such ceramic coating is present, peel strength is poor, and ceramic particle is the same as binding agent poor compatibility
The shortcomings that.
Therefore, prior art has yet to be improved and developed.
The content of the invention
In view of above-mentioned the deficiencies in the prior art, it is an object of the invention to provide a kind of high-temperature-reslithium lithium battery barrier film and its system
Preparation Method, it is intended to solve the problems, such as that battery diaphragm heat resistance, compatibility are poor in the prior art.
Technical scheme is as follows：
A kind of high-temperature-reslithium lithium battery barrier film, the high-temperature-reslithium lithium battery barrier film include base material film and the alkali coated on base material film surface
Property coating of metal oxides, the alkaline metal oxide coating layer thickness be 1 ~ 4 μm, described alkaline metal oxide coating by
Polymeric binder, modified alkaline metal oxide and solvent are made.
Preferably, the base material film is polymer microporous film, and the polymer in the polymer microporous film gathers for low-density
Ethene, high density polyethylene (HDPE), low density linear polyethylene, ultra-high molecular weight polyethylene, polypropylene, poly terephthalic acid second two
One or more in ester, polybutylene terephthalate, polyamide, polyimides and polyurethane.
Preferably, the polymeric binder is polyamide, polyamide-polyimide, polyurethane, polyacrylic acid, epoxy
One or more in resin and polyvinyl acetate, the polymeric binder dosage are coating of metal oxides total solid
5-40%.
Preferably, the modified alkaline metal oxide is aluminum oxide, silica, titanium oxide, zirconium oxide, zinc oxide and vigorous
At least one of female stone.
Preferably, the solvent be acetone, butanone, ethyl acetate, butyl acetate, 1-METHYLPYRROLIDONE, N, N- diformazans
One or more in base formamide and DMAC N,N' dimethyl acetamide.
Preferably, alkoxysilyl group of the parent without generator terminal in the hydroxyl and silane coupler on alkaline metal oxide surface is utilized
Reaction generation modified alkaline metal oxide.
Preferably, described silane coupler one end carries amido, carbon-carbon double bond, sulfydryl, epoxy radicals or haloalkyl, another
End carries alkoxysilyl group.
Preferably, the silane coupler is γ-aminopropyltrimethoxysilane, gamma-aminopropyl-triethoxy-silane, 3-
Glycidyl ether oxygen propyl trimethoxy silicane, gamma-mercaptopropyltriethoxysilane, N- β-aminoethyl-γ-aminopropyltriethoxy two
Methoxy silane, N- β-aminoethyl-γ-aminopropyltriethoxy triethoxysilane, N- β-aminoethyl-γ-aminopropyltriethoxy front three
TMOS, γ-aminopropyltriethoxy diethoxy silane, anilinomethyl triethoxysilane, dichloromethyl triethoxysilane,
At least one of γ-methacryloxypropyl trimethoxy silane.
Preferably, described alkaline metal oxide coating by polymeric binder, modified alkaline metal oxide molten
Obtained after reaction is crosslinked in agent.
A kind of preparation method of high-temperature-reslithium lithium battery barrier film, wherein, including step：
Base material film is provided A,；
B, alkaline metal oxide coating is coated on the base material film, the alkaline metal oxide coating layer thickness is 1 ~ 4 μm,
Described alkaline metal oxide coating is made up of polymeric binder, modified alkaline metal oxide and solvent.
Beneficial effect：The coating of the present invention has good adhesive force and uniformity, so that coating has well
Heat resistance, modified alkaline metal oxide therein have good compatibility with polymeric binder, and obtained barrier film has
Preferable dimensional stability, it is indeformable at high temperature.
Brief description of the drawings
Fig. 1 is the structural representation of polymeric binder in the present invention.
Fig. 2 is the structural representation of neutral and alkali metal oxide of the present invention.
Fig. 3 is the structural representation of silane coupler in the present invention.
Fig. 4 is the reaction principle figure of silane coupler and alkaline metal oxide in the present invention.
Fig. 5 is polymeric binder and the reaction principle figure of modified alkaline metal oxide in the present invention.
Embodiment
The present invention provides a kind of high-temperature-reslithium lithium battery barrier film and preparation method thereof, to make the purpose of the present invention, technical scheme
And effect is clearer, clear and definite, the present invention is described in more detail below.It should be appreciated that specific implementation described herein
Example is not intended to limit the present invention only to explain the present invention.
A kind of high-temperature-reslithium lithium battery barrier film provided by the present invention, the high-temperature-reslithium lithium battery barrier film include base material film and painting
The alkaline metal oxide coating on base material film surface is overlying on, the alkaline metal oxide coating layer thickness is 1 ~ 4 μm, described alkali
Property coating of metal oxides is made up of polymeric binder, modified alkaline metal oxide and solvent.
Modified alkaline metal oxide has good compatibility, coating tool with polymeric binder in the coating of the present invention
There are strong adhesive force, preferable uniformity, so that coating has good heat resistance.With conventional membrane coating technology phase
Than the present invention has preferable size steady based on the reaction between coating each component, the tridimensional network of generation, obtained barrier film
Qualitative, it is indeformable at high temperature.
The high-temperature-reslithium lithium battery membrane thicknesses are preferably 10-40 microns, for example, 25 microns.The high-temperature-reslithium lithium battery
The porosity of barrier film is preferably 30-90%, and for example, 60%.
Preferably, the base material film is polymer microporous film, and the polymer in the polymer microporous film gathers for low-density
Ethene, high density polyethylene (HDPE), low density linear polyethylene, ultra-high molecular weight polyethylene, polypropylene, poly terephthalic acid second two
One or more in ester, polybutylene terephthalate, polyamide, polyimides and polyurethane.
Preferably, the polymeric binder is polyamide, polyamide-polyimide, polyurethane, polyacrylic acid, epoxy
One or more in resin and polyvinyl acetate, the polymeric binder dosage are that alkaline metal oxide coating is always solid
The 5-40% of the scale of construction.Polymeric binder structural formula of the present invention is as shown in figure 1, centre of sphere part is polymeric binder in figure
Main body framework structure, A are reactive group, and such as amido, carboxyl, NCO, hydroxyl, epoxy radicals, carbon-carbon double bond are anti-
Answer group.
Preferably, the modified alkaline metal oxide is aluminum oxide, silica, titanium oxide, zirconium oxide, zinc oxide and vigorous
At least one of female stone.
Preferably, the solvent be acetone, butanone, ethyl acetate, butyl acetate, 1-METHYLPYRROLIDONE, N, N- diformazans
One or more in base formamide and DMAC N,N' dimethyl acetamide.
Preferably, alkoxysilyl group of the parent without generator terminal in the hydroxyl and silane coupler on alkaline metal oxide surface is utilized
Reaction generation modified alkaline metal oxide.The above method is that have amphiphilic and double reactive functionalities based on silane coupler
Feature, chemical key connection can be formed with the hydroxyl reaction on alkaline metal oxide surface using alkoxysilyl group, utilize this reaction
Alkaline metal oxide is modified, makes its surface with the abundant oleophylic segment with reactive group, alkalescence therein
Metal oxide structures are as shown in Fig. 2 abundant hydroxyl is contained on medicine ball inorganic particle agent structure, its surface in structural formula.
The present invention utilizes silane coupler modified alkaline metal oxide, the modified alkaline metal oxide and polymeric binder of gained
With good compatibility.
Preferably, described silane coupler one end carries amido, carbon-carbon double bond, sulfydryl, epoxy radicals or haloalkyl, another
End carries alkoxysilyl group.
Silane coupler structure of the present invention is as shown in figure 3, wherein R1 is the same fragrance of alkyl chain, fragrant chain or alkyl chain
The combination segment of chain, R2, R3, R4 are alkyl, and they can be identical alkyl, or different alkyl, D are amido, carbon carbon pair
The lipophile reactive group such as key, sulfydryl, epoxy radicals and haloalkyl.
Preferably, the silane coupler is specially γ-aminopropyltrimethoxysilane, gamma-aminopropyl-triethoxy silicon
Alkane, 3- glycidyl ether oxygen propyl trimethoxy silicanes, gamma-mercaptopropyltriethoxysilane, N- β-aminoethyl-γ-aminopropyl
Methyl dimethoxysilane, N- β-aminoethyl-γ-aminopropyltriethoxy triethoxysilane, N- β-aminoethyl-γ-aminopropyl first
Base trimethoxy silane, γ-aminopropyltriethoxy diethoxy silane, anilinomethyl triethoxysilane, the ethoxy of dichloromethyl three
At least one of base silane, γ-methacryloxypropyl trimethoxy silane.
Silane coupler of the present invention is with alkaline metal oxide reaction equation as shown in figure 4, wherein alkalinous metal aoxidizes
Thing surface hydroxyl is even with alkoxysilyl group reaction generation modified alkaline metal oxide of the parent in silane coupler without generator terminal, silane
Lipophile reactive group D in connection agent is connected to alkaline metal oxide surface.
Preferably, described alkaline metal oxide coating by polymeric binder, modified alkaline metal oxide molten
Obtained after reaction is crosslinked in agent.Modified alkaline metal oxide reacts to be formed with the polymeric binder with reactive group
Stereochemical structure polymer is crosslinked, chemical cross-linking agent is used as by the use of alkaline metal oxide in reaction.Polymer of the present invention glues
Tie agent with modified alkaline metal oxide cross-linking reaction as shown in figure 5, wherein D and A combinations be respectively amido and epoxy radicals,
Amido and carboxyl, amido and NCO, carbon-carbon double bond and carbon-carbon double bond, sulfydryl and amido, sulfydryl and carboxyl, sulfydryl and hydroxyl
Base, haloalkyl and amido, haloalkyl and hydroxyl etc..After polymeric binder and the reaction of modified alkaline metal oxide cross-linked
Generate inorganic-organic cross-linked three D reticular structure.
Compared with conventional membrane coating technology, the present invention is used as polymeric binder by the use of modified alkaline metal oxide
Chemical cross-linking agent so that inorganic particle（Modified alkaline metal oxide）Realize that chemical bond is connected between organic polymer.
The present invention also provides a kind of preparation method of high-temperature-reslithium lithium battery barrier film, and it includes step：
S1, provide base material film；
S2, alkaline metal oxide coating is coated on the base material film, the alkaline metal oxide coating layer thickness is 1 ~ 4 μ
M, described alkaline metal oxide coating are made up of polymeric binder, modified alkaline metal oxide and solvent.
Embodiment 1
（1）Alkaline metal oxide is modified：The gamma-aminopropyl-triethoxy-silane of the aluminum oxide of 38 mass parts, 2 mass parts is mixed
Together in the N of 60 mass parts, in N- dimethyl pyrrolidones, 120 DEG C of return stirring 2h, then filter, be dried to obtain modified oxidized
Aluminium.
（2）Slurry preparation：The epoxy adhesive of 5 mass parts is dissolved in the 1-METHYLPYRROLIDONE solvent of 30 mass parts
In, the modified aluminas of 35 mass parts is then added, stirs 90min（It is preferred that high-speed stirred）, then add 30 mass parts
1-METHYLPYRROLIDONE solvent, stir 30min（It is preferred that moderate-speed mixer）, cross screen cloth and obtain ceramic slurry.
（3）Coating：Roll coating model is used to coat thickness respectively on 20 microns thick of polyethylene film two sides as 2 microns of coating
（Ceramic slurry）, first it is placed in 90 DEG C of baking ovens and toasts 120min to remove most of solvent, is then placed on 120 DEG C again
Middle dry solidification 60min, obtain barrier film sample S1（That is high-temperature-reslithium lithium battery barrier film）.
Embodiment 2
（1）Alkaline metal oxide is modified：By the aluminum oxide of 38 mass parts, the 3- glycidyl ether oxygen propyl front threes of 2 mass parts
TMOS is mixed in the N of 60 mass parts, in N- dimethyl pyrrolidones, 120 DEG C of return stirring 2h, then filters, dry
To modified aluminas.
（2）Slurry preparation：The 1-METHYLPYRROLIDONE that the polyamide-imides of 5 mass parts is dissolved in 30 mass parts is molten
In agent, the modified aluminas of 35 mass parts is then added, stirs 90min（It is preferred that high-speed stirred）, then add 30 mass parts
1-METHYLPYRROLIDONE solvent, stir 30min（It is preferred that moderate-speed mixer）, cross screen cloth and obtain ceramic slurry.
（3）Coating：Roll coating model is used to coat thickness respectively on 20 microns thick of polyethylene film two sides as 2 microns of coating
（Ceramic slurry）, first it is placed in 90 DEG C of baking ovens and toasts 120min to remove most of solvent, is then placed on 120 DEG C again
Middle dry solidification 60min, obtain barrier film sample S2.
Embodiment 3
（1）Alkaline metal oxide is modified：By the aluminum oxide of 38 mass parts, γ-methacryloxypropyl three of 2 mass parts
Methoxy silane is mixed in the acetone of 60 mass parts, 60 DEG C of return stirring 2h, is then filtered, is dried to obtain modified aluminas.
（2）Slurry preparation：Acrylic acid-vinyl acetate co-polymer of 5 mass parts is dissolved in the N- methyl of 30 mass parts
In pyrrolidinone solvent, the modified aluminas of 35 mass parts is then added, stirs 90min（It is preferred that high-speed stirred）, then add again
Enter the 1-METHYLPYRROLIDONE solvent of 30 mass parts, moderate-speed mixer 30min（It is preferred that moderate-speed mixer）, cross screen cloth and obtain ceramic slurry
Material.
（3）Coating：Roll coating model is used to coat thickness respectively on 20 microns thick of polyethylene film two sides as 2 microns of coating
（Ceramic slurry）, first it is placed in 90 DEG C of baking ovens and toasts 120min to remove most of solvent, is then placed on 120 DEG C again
Middle dry solidification 60min, obtain barrier film sample S3.
Embodiment 4
（1）Alkaline metal oxide is modified：The dichloromethyl triethoxysilane of the aluminum oxide of 38 mass parts, 2 mass parts is mixed
Together in the acetone of 60 mass parts, 60 DEG C of return stirring 2h, then filter, be dried to obtain modified aluminas.
（2）Slurry preparation：The polyvinyl alcohol of 5 mass parts is dissolved in the 1-METHYLPYRROLIDONE solvent of 30 mass parts,
Then the modified aluminas of 35 mass parts is added, stirs 90min（It is preferred that high-speed stirred）, then add the N- first of 30 mass parts
Base pyrrolidinone solvent, stir 30min（It is preferred that moderate-speed mixer）, cross screen cloth and obtain ceramic slurry.
（3）Coating：Roll coating model is used to coat thickness respectively on 20 microns thick of polyethylene film two sides as 2 microns of coating
（Ceramic slurry）, first it is placed in 90 DEG C of baking ovens and toasts 120min to remove most of solvent, is then placed on 120 DEG C again
Middle dry solidification 60min, obtain barrier film sample S4.
Comparative example 1
（1）Slurry preparation：Acrylic acid-vinyl acetate co-polymer of 5 mass parts is dissolved in the N- methylpyrroles of 30 mass parts
In alkanone solvent, the aluminum oxide of 35 mass parts is then added, stirs 90min（It is preferred that high-speed stirred）, then add 30 mass
The 1-METHYLPYRROLIDONE solvent of part, stir 30min（It is preferred that moderate-speed mixer）, cross screen cloth and obtain ceramic slurry.
（2）Coating：Roll coating model is used to coat thickness respectively 20 microns thick of polyethylene film both sides as 2 microns of coating
（Ceramic slurry）, first it is placed in 90 DEG C of baking ovens and toasts 120min to remove solvent, is then placed in 120 DEG C and dries again
Solidify 60min, obtain contrasting barrier film sample DS1.
Performance test
（1）Barrier film thermal contraction test
Barrier film sample is placed in airtight oven, tests percent thermal shrinkage at different temperatures respectively, its result is as shown in table 1：
| Sample | 150℃/1h | 200℃/1h | 250℃/1h |
| S1 | <3% | <5% | <5% |
| S2 | <3% | <5% | <5% |
| S3 | <3% | <5% | <5% |
| S4 | <3% | <5% | <5% |
| DS1 | >10% | Melting completely | Melting completely |
The percent thermal shrinkage of the different barrier film samples of table 1 at different temperatures
（2）Barrier film coating stripping strength test
Barrier film coating is affixed on the soft double faced adhesive tapes of 3M, tests 180 degree peeling force, its result is as shown in table 2：
| Sample | Peel strength（N/m） |
| S1 | 50 |
| S2 | 50 |
| S3 | 45 |
| S4 | 45 |
| DS1 | 20 |
The peel strength test result of the different coating of table 2
（3）Cycle performance of battery is tested
Sample S1-S4 in embodiment and comparative example DS1 is subjected to charge-discharge performance test, normal temperature 1C/1C charge and discharge
Electric loop test, circulation post-modification coating capability retention is higher by least 3% compared with comparative example battery capacity conservation rate within 1000 weeks.
It should be appreciated that the application of the present invention is not limited to above-mentioned citing, for those of ordinary skills, can
To be improved or converted according to the above description, all these modifications and variations should all belong to the guarantor of appended claims of the present invention
Protect scope.
Claims (10)
- A kind of 1. high-temperature-reslithium lithium battery barrier film, it is characterised in that：The high-temperature-reslithium lithium battery barrier film includes base material film and is coated on The alkaline metal oxide coating on base material film surface, the alkaline metal oxide coating layer thickness are 1 ~ 4 μm, described alkalescence gold Category oxide coating is made up of polymeric binder, modified alkaline metal oxide and solvent.
- 2. high-temperature-reslithium lithium battery barrier film according to claim 1, it is characterised in that：The base material film is polymer micro Film, the polymer in the polymer microporous film is low density polyethylene (LDPE), high density polyethylene (HDPE), low density linear polyethylene, super High molecular weight polyethylene, polypropylene, PET, polybutylene terephthalate, polyamide, polyimides and One or more in polyurethane.
- 3. high-temperature-reslithium lithium battery barrier film according to claim 1, it is characterised in that：The polymeric binder is polyamides One or more in amine, polyamide-polyimide, polyurethane, polyacrylic acid, epoxy resin and polyvinyl acetate, it is described Polymeric binder dosage is the 5-40% of coating of metal oxides total solid.
- 4. high-temperature-reslithium lithium battery barrier film according to claim 1, it is characterised in that：The modified alkaline metal oxide is At least one of aluminum oxide, silica, titanium oxide, zirconium oxide, zinc oxide and boehmite.
- 5. high-temperature-reslithium lithium battery barrier film according to claim 1, it is characterised in that：The solvent is acetone, butanone, acetic acid One kind or more in ethyl ester, butyl acetate, 1-METHYLPYRROLIDONE, N,N-dimethylformamide and DMAC N,N' dimethyl acetamide Kind.
- 6. high-temperature-reslithium lithium battery barrier film according to claim 1, it is characterised in that：Utilize alkaline metal oxide surface Hydroxyl and alkoxysilyl group reaction generation modified alkaline metal oxide of the parent in silane coupler without generator terminal.
- 7. high-temperature-reslithium lithium battery barrier film according to claim 6, it is characterised in that：Described silane coupler one end carries amine Base, carbon-carbon double bond, sulfydryl, epoxy radicals or haloalkyl, the other end carry alkoxysilyl group.
- 8. high-temperature-reslithium lithium battery barrier film according to claim 7, it is characterised in that：The silane coupler is γ-ammonia third Base trimethoxy silane, gamma-aminopropyl-triethoxy-silane, 3- glycidyl ether oxygen propyl trimethoxy silicanes, γ-mercapto propyl group Triethoxysilane, N- β-aminoethyl-γ-aminopropyltriethoxy dimethoxysilane, N- β-aminoethyl-γ-aminopropyltriethoxy three Ethoxysilane, N- β-aminoethyl-γ-aminopropyltriethoxy trimethoxy silane, γ-aminopropyltriethoxy diethoxy silane, benzene In amine MTES, dichloromethyl triethoxysilane, γ-methacryloxypropyl trimethoxy silane It is at least one.
- 9. high-temperature-reslithium lithium battery barrier film according to claim 1, it is characterised in that：Described alkaline metal oxide coating Obtained after crosslinking reaction in a solvent by polymeric binder, modified alkaline metal oxide.
- 10. a kind of preparation method of high-temperature-reslithium lithium battery barrier film, it is characterised in that including step：Base material film is provided A,；B, alkaline metal oxide coating is coated on the base material film, the alkaline metal oxide coating layer thickness is 1 ~ 4 μm, Described alkaline metal oxide coating is made up of polymeric binder, modified alkaline metal oxide and solvent.
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| CN112563470A (en) * | 2020-12-09 | 2021-03-26 | 惠州亿纬锂能股份有限公司 | Lithium battery positive plate and preparation method and application thereof |
| CN113795974A (en) * | 2019-05-07 | 2021-12-14 | 赢创运营有限公司 | Lithium ion battery separator coated with surface treated alumina |
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| CN110660947B (en) * | 2018-06-28 | 2021-11-12 | 比亚迪股份有限公司 | Battery diaphragm and preparation method thereof, lithium ion battery and electric automobile |
| CN110660947A (en) * | 2018-06-28 | 2020-01-07 | 比亚迪股份有限公司 | Battery diaphragm and preparation method thereof, lithium ion battery and electric automobile |
| 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 |
| US20220166105A1 (en) * | 2018-12-13 | 2022-05-26 | Hyundai Motor Company | Lithium secondary battery including separator with ceramic layer having first ceramic particle bonded to second ceramic particle and manufacturing method the same |
| CN109860479A (en) * | 2018-12-26 | 2019-06-07 | 欣旺达电子股份有限公司 | The preparation method of lithium battery diaphragm coating, diaphragm and diaphragm coating |
| CN109950452A (en) * | 2019-02-21 | 2019-06-28 | 威海星宜新材料科技有限公司 | A kind of lithium ion battery ceramics apply cloth diaphragm and preparation method thereof |
| CN113795974A (en) * | 2019-05-07 | 2021-12-14 | 赢创运营有限公司 | Lithium ion battery separator coated with surface treated alumina |
| CN110690396A (en) * | 2019-11-12 | 2020-01-14 | 湖南艾威尔新能源科技有限公司 | Lithium battery diaphragm, preparation method thereof and lithium battery |
| CN111029514B (en) * | 2019-11-14 | 2021-09-28 | 珠海冠宇电池股份有限公司 | Diaphragm and high-voltage battery comprising same |
| CN111029514A (en) * | 2019-11-14 | 2020-04-17 | 珠海冠宇电池有限公司 | Diaphragm and high-voltage battery comprising same |
| CN111370630A (en) * | 2020-03-13 | 2020-07-03 | 江苏厚生新能源科技有限公司 | High-adsorption electrolyte diaphragm, preparation method thereof and lithium battery |
| CN111370630B (en) * | 2020-03-13 | 2022-06-17 | 江苏厚生新能源科技有限公司 | High-adsorption electrolyte diaphragm, preparation method thereof and lithium battery |
| CN111969160A (en) * | 2020-08-31 | 2020-11-20 | 佛山市金辉高科光电材料股份有限公司 | Composite lithium ion battery diaphragm and preparation method thereof, lithium ion battery and electronic product |
| CN112563470A (en) * | 2020-12-09 | 2021-03-26 | 惠州亿纬锂能股份有限公司 | Lithium battery positive plate and preparation method and application thereof |
| WO2023005291A1 (en) * | 2021-07-30 | 2023-02-02 | 中材锂膜有限公司 | Composite separator, manufacturing method therefor, and secondary battery |
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