CN106905475A - The ceramic diaphragm that a kind of lithium battery ceramic diaphragm is prepared with the preparation method of fluorine-containing adhesive and using the adhesive - Google Patents
The ceramic diaphragm that a kind of lithium battery ceramic diaphragm is prepared with the preparation method of fluorine-containing adhesive and using the adhesive Download PDFInfo
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- CN106905475A CN106905475A CN201710142072.3A CN201710142072A CN106905475A CN 106905475 A CN106905475 A CN 106905475A CN 201710142072 A CN201710142072 A CN 201710142072A CN 106905475 A CN106905475 A CN 106905475A
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
- C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
- C08F220/10—Esters
- C08F220/22—Esters containing halogen
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F2/00—Processes of polymerisation
- C08F2/12—Polymerisation in non-solvents
- C08F2/16—Aqueous medium
- C08F2/22—Emulsion polymerisation
- C08F2/24—Emulsion polymerisation with the aid of emulsifying agents
- C08F2/26—Emulsion polymerisation with the aid of emulsifying agents anionic
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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
- H01M50/446—Composite material consisting of a mixture of organic and inorganic materials
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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
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- Polymers & Plastics (AREA)
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- Inorganic Chemistry (AREA)
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Abstract
The invention discloses the ceramic diaphragm that a kind of lithium battery ceramic diaphragm is prepared with the preparation method of fluorine-containing adhesive and with the adhesive.The preparation method is：By fluoro-acrylate monomer, carboxylic monomer, organic acid monomer, vinyl monomer, reactive emulsifier, nertralizer, initiator and water are all added in pre-emulsification reactor, and mechanical agitation carries out the pre-emulsion that dispersion forms stabilization；Take in the pre-emulsion addition polymerization reaction kettle of part, 50~90 DEG C of polymeric reaction temperature is heated under nitrogen protection, react 0.1~1h, remaining pre-emulsion is added dropwise, dripped off in 0.5~4h, 1~6h of insulation reaction is cooled to room temperature, filtering, obtains final product.Aqueous binder agent emulsion of the present invention environmental protection, with excellent caking property, mechanical stability, heat resistance etc., the ceramic diaphragm water absorption rate prepared using it is low and with excellent heat resistance.
Description
Technical field
Prepared the present invention relates to a kind of preparation method of lithium battery ceramic diaphragm aqueous binder and using the adhesive
Ceramic diaphragm, particularly a kind of lithium battery ceramic diaphragm with the preparation method of fluorine-containing adhesive and ceramics prepared therefrom every
Film.
Background technology
With the continuous social and economic development, the mankind constantly increase the demand of the energy, traditional coal, oil, natural gas
Made a gift of to the greatest extent Deng what non-renewable energy resources will consume, and pollution on the environment is increasingly severe, finds new energy and Development of Novel
Energy instrument it is extremely urgent.At present, lithium ion battery have that easy to use, application cost is relatively low, service life compared with
Long, environmentally safe the advantages of, is increasingly subject to the pro-gaze of people, especially in automobile and high-end electronic product scope.
As the application of lithium ion battery is more and more wider, its security is also increasingly paid close attention to by people, and influences lithium
One of key factor of ion battery security is exactly barrier film, and the security performance for improving constantly barrier film has turned into current lithium electrical domain
One of study hotspot.At present, commercially general lithium battery diaphragm is mainly polyethene microporous membrane (PE) and polypropylene is micro-
Pore membrane (PP), its fusing point is relatively low, respectively 125 DEG C and 158 DEG C, thus the easy contraction distortion in the case where battery is overheated
Even melt, cause lithium battery short circuit and trigger serious security incident.In order to improve this defect, it has been developed that PP/
PE/PP sandwich diaphragms, while the ceramic diaphragm product of the coated ceramic coating on PE, PP membrane surface is also developed, especially
It is the appearance of ceramic diaphragm product, greatly improves its heat resistance, so as to improves the security of battery.At present, it is domestic
Outer some esbablished corporations to high temperature resistant, good permeability, protect liquid measure ceramic diaphragm high and researched and developed, Related product also land
It is continuous to introduce to the market.
Ceramic diaphragm needs that ceramic powder is bonded on barrier film with adhesive in fabrication, thus adhesive is in itself
Performance will directly affect the heat resistance of ceramic diaphragm and the chemical property of battery.Adhesive species in the market is various,
Physicochemical property difference is big, but can be few in the adhesive product of field of lithium application, and lithium battery adhesive will not only have
The adhesive property that has had, also there is outstanding heat resistance, electrolyte resistance and high voltage stability etc..
At present, there are polyvinylidene fluoride (PVDF), polytetrafluoroethylene (PTFE) in the adaptable adhesive of field of lithium
(PTFE), the modified acrylic ester aquosity adhesive of butadiene-styrene rubber (SBR), LA133 aqueous binders, epoxy resin graft is (special
Sharp publication No. CN103571420A), the aqueous binder (number of patent application of acrylic compounds soft monomer and hard monomer copolymerization
CN105778834A) etc..However, the binding agent of the organic system such as PVDF, PTFE, FEP is harmful to environment；Aqueous SBR bondings
Agent is primarily adapted for use in cathode of lithium battery coating；LA133 aqueous binders are acrylic acid aqueous with what patent CN103571420A was issued
Adhesive relative viscosity is big, the levelability of coating speed and product will be influenceed when being used on lithium battery ceramic diaphragm, when serious
The microscopic appearance of ceramic diaphragm will be influenceed, cause holiday etc.；The acrylic compounds that number of patent application CN105778834A is announced are aqueous
Adhesive has application viscosity relatively low, and heat endurance is good, adhesion strength is high, advantages of environment protection, is expected to turn into a outstanding
Ceramic diaphragm adhesive and in field of lithium application, but the test data provided according to it carries out 16+4 on PP barrier films
μ is coated, and its percent thermal shrinkage (150 DEG C/1h) is about 1.5%, and its heat resistance needs further raising.Further, since lithium battery
The water absorbing properties of each part are closely bound up with the chemical property of lithium battery, thus viscous as a outstanding ceramic diaphragm
Mixture product should also have low water absorption rate after drying in addition to performances such as above-mentioned adhesion strength high, heat resistances.
Therefore, a low water absorbable, low viscosity, high bond strength, high-fire resistance, high mechanical stability, Gao Nai electricity are developed
Solution matter, environment-friendly adhesive product have been become with meeting the application requirement of growing high-end lithium battery ceramic diaphragm
It is more and more important.
The content of the invention
It is an object of the invention to provide a kind of low water absorbable dedicated for lithium battery ceramic diaphragm, high-fire resistance, high viscous
Knotting strength, low application viscosity, high mechanical stability environment amenable fluorine-containing aqueous adhesive preparation method and viscous with this simultaneously
Ceramic diaphragm prepared by knot agent.
To achieve these goals, the invention provides a kind of lithium battery ceramic diaphragm preparation side of fluorine-containing adhesive
Method, it comprises the following steps：
By fluoro-acrylate monomer, carboxylic monomer, organic acid monomer, vinyl monomer, reactive emulsifier, nertralizer,
Initiator and water are all added in pre-emulsification reactor, and mechanical agitation carries out the pre-emulsion that dispersion forms stabilization；
Take in the pre-emulsion addition polymerization reaction kettle of part, 50~90 DEG C of polymeric reaction temperature be heated under nitrogen protection,
0.1~1h of reaction, is added dropwise remaining pre-emulsion, is dripped off in 0.5~4h, and 1~6h of insulation reaction is cooled to room temperature, and filtering is obtained final product
To lithium battery ceramic diaphragm adhesive agent emulsion.
The fluoro-acrylate monomer be acrylic acid trifluoro ethyl ester, trifluoroethyl methacrylate, hexafluorobutyl acrylate,
Hexafluorobutyl mathacrylate, acrylic acid octafluoro pentyl ester, methacrylic acid octafluoro pentyl ester, dodecafluorhe-ptylacrylate, methyl-prop
The difluoro heptyl ester of olefin(e) acid ten, perfluoro hexyl ethyl propylene acid esters, perfluorooctylethyl group acrylate, perfluoro butyl ethyl-methyl propylene
One or more in acid esters, perfluorooctyl ethylene.Preferably acrylic acid trifluoro ethyl ester, trifluoroethyl methacrylate, propylene
Sour hexafluoro butyl ester, Hexafluorobutyl mathacrylate, acrylic acid octafluoro pentyl ester, methacrylic acid octafluoro pentyl ester, the difluoro of acrylic acid ten
One kind in heptyl ester, dodecafluoroheptyl methacrylate.
The carboxylic monomer is ethylene glycol, glycerine, TEGDMA, diethylene glycol dimethyl allene
Acid esters, BDO dimethylacrylate, hydroxy-ethyl acrylate, hydroxyethyl methacrylate, hydroxypropyl acrylate, methyl
One or more in hydroxypropyl acrylate.Preferably ethylene glycol, TEGDMA, hydroxy-ethyl acrylate,
At least one in hydroxyethyl methacrylate, hydroxypropyl acrylate.
The organic acid monomer is one or more in acrylic acid, methacrylic acid, butene dioic acid.Preferably propylene
One kind in acid, methacrylic acid.
The vinyl monomer is N- vinyl pyrroles ketone, N- caprolactams, N- vinyl imidazoles, vinyl second
Base ether, isobutylvinyl ether, tert-Butyl vinyl ether, dodecyl vinyl, styrene, methyl styrene, hydroxyl butyl second
One or more in alkene ether.Preferably N- caprolactams, EVE, styrene, methyl styrene, hydroxyl
At least one in butyl vinyl ether.
The reactive emulsifier is acrylamido sodium isopropyl xanthate, pi-allyl hydroxypropyl azochlorosulfonate acid sodium, 2- acryloyls
Amido -2- methyl propane sulfonic acids sodium, sodium vinyl sulfonate, allyloxy fatty alcohol oxygen ethene ether ammonium sulfate, 2- allyl ether -3- hydroxyls
Base propane -1- sodium sulfonates, allyloxy nonyl phenol propyl alcohol polyoxyethylene (4) ether ammonium sulfate and alkyl phenol allyl polyether sulfate
In one or more.Preferably pi-allyl hydroxypropyl azochlorosulfonate acid sodium, 2- acrylamide-2-methylpro panesulfonic acids sodium, vinyl sulphur
In sour sodium, allyloxy fatty alcohol oxygen ethene ether ammonium sulfate, allyloxy nonyl phenol propyl alcohol polyoxyethylene (4) ether ammonium sulfate one
Kind.
The nertralizer is one or more in ammoniacal liquor, urea, lithium hydroxide, NaOH, potassium hydroxide.Preferably
One kind in ammoniacal liquor, urea, lithium hydroxide, NaOH, potassium hydroxide.
The initiator is one or more in ammonium persulfate, sodium peroxydisulfate, potassium peroxydisulfate.Initiator system of ammonium persulfate, mistake
One kind in sodium sulphate, potassium peroxydisulfate.
Present invention also offers the lithium battery ceramic diaphragm that the adhesive prepared using the above method is made.
Experiment is confirmed：
1st, lithium battery ceramic diaphragm prepared by the present invention external appearance characteristic of fluorine-containing adhesive is emulsion form, viscosity is 25~
600 centipoises (25 DEG C), the particle diameter D50 of copolymer is 0.2~2 μm, 60~80 DEG C of polymeric reaction temperature, the insulation reaction time 4~
6h。
2nd, lithium battery ceramic diaphragm prepared by the present invention soaks 24h, weight change after being dried with fluorine-containing adhesive in water
Less than 80%, 1000ppm is less than using its ceramic diaphragm moisture prepared, possesses good low water absorbable.
3rd, lithium battery ceramic diaphragm prepared by the present invention toasts 2h at 180 DEG C, and percent thermal shrinkage is less than 3%, with good
High-fire resistance.
4th, lithium battery ceramic diaphragm peel strength prepared by the present invention is higher than 60N/m.
5th, the lithium battery ceramic diaphragm that prepared by the present invention is low with fluorine-containing adhesive viscosities, and viscosity is less than 600 centipoises at room temperature,
And high-speed stirred is not demulsified with grinding 24h.
Compared with prior art, the advantageous effect of present invention is that：Not only viscosity is low for adhesive prepared by the present invention,
Viscosity is less than 600 centipoises at room temperature, and high-speed stirred is not demulsified with grinding 24h, is soaked 6 days in lithium battery electrolytes after drying
It is insoluble, it is good with ceramic powder compatibility, the ceramic size good leveling property come is made using it.By using fluorine-containing list
Body, makes the polymer to be formed have low water absorption rate after the drying, the ceramic diaphragm prepared using the adhesive is had very
Outstanding hydrophobicity.Further, since the use of fluoro-acrylate monomer so that the heat resistance and solvent resistance of copolymer are significantly
Improve.Invention adhesives carry out soap-free polymerization by using reactive emulsifier, make resulting polymers emulsion have low bubble excellent
Point, in use with outstanding processing characteristics.Again, adhesive of the invention is using water as solvent, environmental protection, and
Ceramic diaphragm drying temperature, energy saving, and preparation process is simple can effectively be reduced.
Brief description of the drawings
Fig. 1 is the lithium battery ceramic diaphragm for preparing of the embodiment of the present invention one with fluorine-containing adhesive size distribution collection of illustrative plates.
Fig. 2 is the lithium battery ceramic diaphragm for preparing of the embodiment of the present invention two with fluorine-containing adhesive size distribution collection of illustrative plates.
Specific embodiment
To be described in more detail by embodiment below, but protection scope of the present invention is not limited to these implementations
Example.
Embodiment 1：
The preparation method of the adhesive for lithium ion battery ceramic diaphragm is：By first count by weight percentage
Base acrylic acid trifluoro ethyl ester 18.6g, hydroxyethyl methacrylate 2.4g, acrylic acid 7.2g, styrene 13.5g, emulsifying agent allyl
Epoxide nonyl phenol propyl alcohol polyoxyethylene (4) ether ammonium sulfate 0.6g, NaOH 3.9g, ammonium persulfate 0.2g and water 140g wholes
Add in pre-emulsification reaction vessel, mechanical agitation 3h carries out the pre-emulsion that dispersion forms stabilization；Take 120g pre-emulsions and add polymerization
In reaction vessel, 70 DEG C of polymeric reaction temperature being heated under nitrogen protection, reacting 20min, remaining pre-emulsion is then added dropwise,
Dripped off in 1h, insulation reaction 3h is cooled to room temperature, filtered, that is, obtain lithium battery ceramic diaphragm adhesive agent emulsion.
Obtained ceramic diaphragm adhesive agent emulsion is white, and solid content is about 23%, and viscosity is less than 600 centipoises, copolymer
Grain diameter D50 is less than 1 μm, and the adhesive size distribution collection of illustrative plates of gained is as shown in Figure 1.
Embodiment 2：
In the present embodiment, ceramic diaphragm adhesive replaces trifluoroethyl methacrylate, water using acrylic acid trifluoro ethyl ester
Consumption 180g is increased to by 140g, remaining step is with embodiment 1.
Obtained ceramic diaphragm adhesive agent emulsion is white, and solid content is about 20%, and viscosity is less than 200 centipoises, copolymer
Grain diameter D50 is less than 0.5 μm, and the adhesive size distribution collection of illustrative plates of gained is as shown in Figure 2.
Embodiment 3：
In the present embodiment, ceramic diaphragm adhesive replaces hydroxyethyl methacrylate, emulsifying agent using hydroxy-ethyl acrylate
Allyloxy fatty alcohol oxygen ethene ether ammonium sulfate replaces allyloxy nonyl phenol propyl alcohol polyoxyethylene (4) ether ammonium sulfate, and consumption
0.8g is brought up to by 0.6g, potassium peroxydisulfate replaces the consumption of ammonium persulfate, water to be reduced to 100g by 140g, remaining step is with implementation
Example 1.
Obtained ceramic diaphragm adhesive agent emulsion is creamy white, and solid content is about 30%, and viscosity is less than 600 centipoises, copolymerization
Composition granule particle diameter D50 is less than 1 μm.
Embodiment 4：
In the present embodiment, ceramic diaphragm adhesive replaces trifluoroethyl methacrylate using hexafluorobutyl acrylate, and
Consumption is reduced to 13.2g by 18.6g, and methacrylic acid replaces the consumption of acrylic acid, NaOH to be reduced to 3.44g by 3.9g,
Remaining step is with embodiment 1.
Obtained ceramic diaphragm adhesive agent emulsion is white, and solid content is about 20%, and viscosity is less than 300 centipoises, copolymer
Grain diameter D50 is less than 1 μm.
Application Example 1：
The present embodiment is from the adhesive agent emulsion synthesized in embodiment 2, aluminum oxide of the ceramic powder from particle diameter less than 0.8 μm
Powder, thickener selects sodium carboxymethylcellulose, dispersant to select polyether silane, mixes it with water according to certain ratio, warp
Mechanical agitation dispersion is crossed, the slurry that solid content is 40% or so is obtained after grinding, filtering, vacuum froth breaking, obtained slurry is equal
Even to be coated on PE basement membranes, coating method is 16+2+2 μm, the thermal contraction performance of coating is determined after being dried at 60 DEG C, is peeled off by force
Degree and water absorbing properties, (180 DEG C/1h) of its percent thermal shrinkage are less than 2%, and the peel strength between ceramic coating and basement membrane is more than 60N/m,
Water content is less than 1000ppm, shows excellent heat resistance, adhesion strength and hydrophobicity performance.
Claims (10)
1. a kind of lithium battery ceramic diaphragm preparation method of fluorine-containing adhesive, it is characterised in that comprise the following steps：
Fluoro-acrylate monomer, carboxylic monomer, organic acid monomer, vinyl monomer, reactive emulsifier, nertralizer are triggered
Agent and water are all added in pre-emulsification reactor, and mechanical agitation carries out the pre-emulsion that dispersion forms stabilization；
Take in the pre-emulsion addition polymerization reaction kettle of part, 50~90 DEG C of polymeric reaction temperature is heated under nitrogen protection, react
0.1~1h, is added dropwise remaining pre-emulsion, is dripped off in 0.5~4h, and 1~6h of insulation reaction is cooled to room temperature, and filtering obtains lithium
Cell ceramic barrier film adhesive agent emulsion.
2. a kind of lithium battery ceramic diaphragm as claimed in claim 1 preparation method of fluorine-containing adhesive, it is characterised in that institute
Fluoro-acrylate monomer is stated for acrylic acid trifluoro ethyl ester, trifluoroethyl methacrylate, hexafluorobutyl acrylate, methacrylic acid
Hexafluoro butyl ester, acrylic acid octafluoro pentyl ester, methacrylic acid octafluoro pentyl ester, dodecafluorhe-ptylacrylate, the difluoro of methacrylic acid ten
Heptyl ester, perfluoro hexyl ethyl propylene acid esters, perfluorooctylethyl group acrylate, perfluoro butyl ethylmethyl acrylate, perfluor
One or more in octyl vinyl.
3. a kind of lithium battery ceramic diaphragm as claimed in claim 1 preparation method of fluorine-containing adhesive, it is characterised in that institute
State carboxylic monomer for ethylene glycol, glycerine, TEGDMA, dimethacrylate, Isosorbide-5-Nitrae-
Butanediol dimethylacrylate, hydroxy-ethyl acrylate, hydroxyethyl methacrylate, hydroxypropyl acrylate, hydroxyethyl methacrylate
One or more in propyl ester.
4. a kind of lithium battery ceramic diaphragm as claimed in claim 1 preparation method of fluorine-containing adhesive, it is characterised in that institute
It is one or more in acrylic acid, methacrylic acid, butene dioic acid to state organic acid monomer.
5. a kind of lithium battery ceramic diaphragm as claimed in claim 1 preparation method of fluorine-containing adhesive, it is characterised in that institute
The vinyl monomer stated is N- vinyl pyrroles ketone, N- caprolactams, N- vinyl imidazoles, EVE, different
In butyl vinyl ether, tert-Butyl vinyl ether, dodecyl vinyl, styrene, methyl styrene, hydroxy butyl vinyl ether
One or more.
6. a kind of lithium battery ceramic diaphragm as claimed in claim 1 preparation method of fluorine-containing adhesive, it is characterised in that institute
The reactive emulsifier stated is acrylamido sodium isopropyl xanthate, pi-allyl hydroxypropyl azochlorosulfonate acid sodium, 2- acrylamido -2- first
Base propanesulfonate, sodium vinyl sulfonate, allyloxy fatty alcohol oxygen ethene ether ammonium sulfate, 2- allyl ether -3- hydroxy propanes -1-
One kind in sodium sulfonate, allyloxy nonyl phenol propyl alcohol polyoxyethylene (4) ether ammonium sulfate and alkyl phenol allyl polyether sulfate
Or it is various.
7. a kind of lithium battery ceramic diaphragm as claimed in claim 1 preparation method of fluorine-containing adhesive, it is characterised in that institute
It is one or more in ammoniacal liquor, urea, lithium hydroxide, NaOH, potassium hydroxide to state nertralizer.
8. a kind of lithium battery ceramic diaphragm as claimed in claim 1 preparation method of fluorine-containing adhesive, it is characterised in that institute
It is one or more in ammonium persulfate, sodium peroxydisulfate, potassium peroxydisulfate to state initiator.
9. a kind of lithium battery ceramic diaphragm as claimed in claim 1 preparation method of fluorine-containing adhesive, it is characterised in that institute
The fluoro-acrylate monomer consumption stated be 3~15%, carboxylic monomer consumption be 0.5~3%, organic acid monomer c consumptions be 1~
5%, vinyl monomer d consumption are 4~11%, and reactive emulsifier e consumptions are 0.1~1%, the consumption of nertralizer f for 0.3~
The consumption of 4%, initiator g is the 0.1~1% of the total consumption of monomer, and the consumption of water is 55~90%, and above consumption is all by weight
Percentage is calculated.
10. the lithium battery ceramic diaphragm that prepared by fluorine-containing adhesive described in a kind of usage right requirement 1-10.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
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| CN201710142072.3A CN106905475B (en) | 2017-03-10 | 2017-03-10 | Preparation method of fluorine-containing adhesive for lithium battery ceramic diaphragm and ceramic diaphragm prepared by using adhesive |
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| CN201710142072.3A CN106905475B (en) | 2017-03-10 | 2017-03-10 | Preparation method of fluorine-containing adhesive for lithium battery ceramic diaphragm and ceramic diaphragm prepared by using adhesive |
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| CN111668429B (en) * | 2019-03-05 | 2022-11-22 | 三星Sdi株式会社 | Separator for rechargeable lithium battery and rechargeable lithium battery including the same |
| US11923496B2 (en) | 2019-03-05 | 2024-03-05 | Samsung Sdi Co., Ltd. | Separator for rechargeable lithium battery and rechargeable lithium battery including the same |
| CN111584799A (en) * | 2019-12-20 | 2020-08-25 | 湖南高瑞电源材料有限公司 | Preparation method of lithium battery coating diaphragm |
| CN111584799B (en) * | 2019-12-20 | 2022-08-16 | 湖南高瑞电源材料有限公司 | Preparation method of lithium battery coating diaphragm |
| CN114342124A (en) * | 2020-06-17 | 2022-04-12 | 广东省皓智科技有限公司 | Binder composition for secondary battery |
| CN114342124B (en) * | 2020-06-17 | 2024-04-09 | 广东省皓智科技有限公司 | Binder composition for secondary battery |
| CN114678532A (en) * | 2022-04-06 | 2022-06-28 | 天目湖先进储能技术研究院有限公司 | Binder, preparation method thereof and electrochemical device comprising binder |
| CN114678532B (en) * | 2022-04-06 | 2023-09-08 | 天目湖先进储能技术研究院有限公司 | Adhesive, preparation method thereof and electrochemical device comprising adhesive |
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