CN108963164A - Inorganic ceramic coating functions lithium ion battery isolation film, preparation method and its lithium ion battery - Google Patents
Inorganic ceramic coating functions lithium ion battery isolation film, preparation method and its lithium ion battery Download PDFInfo
- Publication number
- CN108963164A CN108963164A CN201810685986.9A CN201810685986A CN108963164A CN 108963164 A CN108963164 A CN 108963164A CN 201810685986 A CN201810685986 A CN 201810685986A CN 108963164 A CN108963164 A CN 108963164A
- Authority
- CN
- China
- Prior art keywords
- water
- lithium ion
- ion battery
- isolation film
- inorganic ceramic
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
Classifications
-
- 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
-
- 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
-
- 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
- H01M10/42—Methods or arrangements for servicing or maintenance of secondary cells or secondary half-cells
- H01M10/4235—Safety or regulating additives or arrangements in electrodes, separators or electrolyte
-
- 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
-
- 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
-
- 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
- H01M50/431—Inorganic material
-
- 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
A kind of inorganic ceramic coating functions lithium ion battery isolation film, preparation method and its lithium ion battery, wherein isolation film includes porous substrate and the inorganic ceramic functional coating that is attached at least one surface of the porous substrate, inorganic ceramic coating includes plate boehmite particles, water soluble polymer thickener, water milk type polymer binder and water-soluble polymeric binder, in parts by weight, the weight of plate boehmite particles accounts for 80~99.4%, water soluble polymer thickener accounts for 0.2~3.0%, the weight of water milk type polymer binder accounts for 0.2~15.0%, the weight of water-soluble polymeric binder accounts for 0.2~15.0%.Coated product of the present invention can be effectively reduced inorganic functional thickness degree and guarantee the homogeneity of thickness, while ensure to coat the excellent high temperature resistance of diaphragm.Due to the low feature of plate boehmite particles hardness, coating material is decreased for mechanical abrasion.
Description
Technical field
The present invention relates to technical field of lithium ion, it is more particularly related to which a kind of inorganic ceramic coats function
Lithium ion battery isolation film and preparation method thereof can be changed, and include the inorganic ceramic coating functions lithium ion battery isolation film
Lithium ion battery.
Background technique
Lithium ion battery with its high-energy density, high working voltage, has had extended cycle life, without note since being commercialized popularization
Recall effect, it is environmentally protective and can according to actual needs flexible design size shape size many advantages, such as be widely used in it is each
The power supply of kind portable consumer electronics product.In addition to this, as Environmental improves and the demand of Mobile energy storage device,
Lithium ion battery is widely used in the exploitation of power battery and energy-storage battery again, these wide application fields and a variety of different
Actual demand has greatly pushed the development of lithium ion battery.
Isolation film used in lithium ion battery and lithium ion polymer battery is largely polyolefin film at present, such as polyethylene
Film (PE), polypropylene screen (PP) or polypropylene, polyethylene/polypropylene composite film (PP/PE/PP), it is wide in lithium ion battery
General use；But encounter such as short circuit, overcharge, thermal shock or puncture when, the internal temperature of lithium ion battery can reach
100 oC or more leads to the volume change of diaphragm, Jin Eryin at this point, this polyolefin film just has biggish contraction or melting
The direct contact between anode and cathode is played, the phenomenon that internal short-circuit and thermal runaway occurs, lithium ion battery is made to be easy kindling very
To explosion.Further, since the surface tension of polyolefin film is very low, the leaching to the carbonic ester electrolyte that lithium ion secondary battery uses
Profit ability and imbibition ability are all poor, are not able to satisfy the requirement of lithium ion secondary battery long circulation life.Therefore, in order to
Guarantee battery uses safe and long circulation life, it is necessary to provide a kind of composite diaphragm of functional modification.
In response to this, existing way is the single or double coating alumina ceramic layer in polyolefine isolating film,
Organic/inorganic composite separator is formed, single side coating thickness is generally in 3~5um.Since inorganic oxide aluminized coating is with higher
Thermal stability, therefore the thermal contraction of entire composite diaphragm is inhibited significantly, while inorganic coating mechanical strength also with higher,
This can also reduce the probability that Li dendrite or particle and collector burr etc. in battery puncture isolation film and cause short circuit, Jin Erti
The reliability and security performance of high battery.But alumina material hardness is high, to mixing plant, coating equipment and slitting blade
Serious wear, cause the batch consistency of its coating layer thickness to be difficult to control and higher cost, it is difficult to carry out scale metaplasia
It produces.Moreover, the coating of thinner and lighter matter becomes following and answers with the exploitation and application of lithium ion battery with high energy density
With direction, aluminium oxide is difficult to carry out technical breakthrough in these areas because of the characteristic of itself material.
Based on the above reasons, it is necessory to provide a kind of thermal stability that not only can effectively improve diaphragm, but can manufacture at
There is the inorganic ceramic coating functionalization lithium ion of technical advantage in sheet, coated product consistency of thickness and coating layer thickness and weight
Battery isolating film, to reduce cost while the security performance for improving battery and the stability recycled for a long time and improve production
The competitiveness of product.
Summary of the invention
It is an object of the present invention to: the characteristics of being directed to current material performance, providing one kind both can effectively improve diaphragm
Thermal stability, and can have technical advantage in manufacturing cost, coated product consistency of thickness and coating layer thickness and weight
Inorganic ceramic coating functionalization lithium ion battery isolation film, so that in the surface density for improving battery, coating water content is reduced, and
The electrolyte for improving product protects liquid measure.
To achieve the goals above, the present invention adopts the following technical scheme: a kind of inorganic ceramic coating functions lithium ion
Battery isolating film, including porous substrate and the inorganic ceramic function being attached at least one surface of the porous substrate
Change coating, coating layer thickness is 1~10um；The inorganic ceramic coating includes plate boehmite particles, water soluble polymer thickening
Agent, water milk type polymer binder and water-soluble polymeric binder；The average grain diameter D50 of the plate boehmite particles is
0.3~2.0um, D10 > 0.05um, D90 < 6.0um, D99 < 8.0um, with a thickness of 0.05~1.5um；The inorganic ceramic applies
Layer slurry, calculates, plate boehmite particles 80.0~99.4%, water soluble polymer thickener 0.2~3.0% according to weight ratio,
Water milk type polymer binder 0.2~15.0%, water-soluble polymeric binder 0.2~15.0%；The water milk type polymer is viscous
Tying agent is the water droplet contact angle of its dry glue 80o~150oBetween hydrophobic polymer polymer, the water-soluble polymer is viscous
Tying agent is melting temperature 120oC~400oPolarity high-melting-point high molecular polymer between C.
Beneficial effect is: firstly, boehmite is selected to substitute traditional alumina particle as inorganic ceramic particle.Boehmite
Also known as boehmite, granule-morphology are uniform plate cube, have heat resisting temperature high, and hardness is low, chemistry and electrochemistry
Many performance characteristics such as stability height are a kind of ideal inorganic materials.Secondly, to the partial size ruler of plate boehmite particles
Selection, lesser particle size, relatively narrow size distribution and flat particle is optimized in very little and its distribution, thickness
On the one hand pattern is conducive to the processing and fabricating of slurry, it is often more important that be conducive to the tightly packed to improve inorganic coating of particle
Surface density, and then realize the purpose for maximizing and improving coating diaphragm heat resistance.Meanwhile the tightly packed of board-like material can reduce
The coating thickness of inorganic coating and realize same improved heat resistance effect.Finally, due to the Mohs' hardness of boehmite about 3.0,
Its density of material about 3.05g/cm3, and the Mohs' hardness of aluminium oxide about 9.0, density of material about 4.0g/cm3, boehmite slurry
And coating will be far smaller than aluminium oxide to the abrasion of mixing plant, coating equipment and slitting blade in process of production, apply thickness
The batch consistency of degree is easier to control, and the weight of coating can further decrease, and is more advantageous to lithium ion battery weight
The promotion of energy density.
As improvement of the present invention, the weight of the plate boehmite particles accounts for the inorganic functional total coating weight
Value range is 87.5~98.5%.
As improvement of the present invention, the water milk type polymer binder is the water droplet contact angle of its dry glue 100o~
130oBetween hydrophobic polymer polymer.Beneficial effect is: containing seldom on water milk type polymer binder emulsion particle surface
The polar hydrophilic group of amount, such as carboxyl, hydroxyl and amino, low polar water milk type polymer binder be conducive to its
Bonding on nonpolar polyalkene diaphragm surface, while it is possible to prevente effectively from binder under polarity electrolyte solvent system
Swelling, to guarantee preferable coating adhesion, to guarantee that the inorganic functional coating on porous substrate surface is not easy to take off
It falls.Higher dry glue water droplet contact angle means that inorganic coating surface has less hydrophilic radical, and painting can be effectively reduced
The water content of layer and absorption to polar water molecules.If the hydrophobicity of emulsion binder further increases, will affect aqueous
Slurry polyalkene diaphragm substrate surface wetting and sprawl, and then influence coating performance.
As improvement of the present invention, the water milk type polymer binder is phenylethylene ethylene/propenoic acid ester copolymer emulsion, vinegar
Sour ethene/acrylic ester copolymer emulsion, vinyl acetate/fatty acid vinyl ester copolymer emulsion, organosilicon acrylic ester copolymerization cream
At least one of liquid and acrylate copolymer emulsion.
As improvement of the present invention, the weight of the water milk type polymer binder accounts for the inorganic functional coating gross weight
The value range of amount is 0.5~10.0%.
As improvement of the present invention, the water-soluble polymeric binder is melting temperature 160oC~300oBetween C
Polarity high-melting-point high molecular polymer.Beneficial effect is: the use of water-soluble polymeric binder can be in inorganic particle table
Face forms hydrophily adsorption layer and generates electrostatic repulsion between particle, is conducive to suspension inorganic particle in aqueous solution
Disperse and stablizes.Secondly, its polarity high-melting-point high molecular polymer compared with high melt temperature, can make the organic matter in coating high
Molecularly Imprinted Polymer still keeps the structure of its macromolecular chain skeleton when inorganic compounding functionalization porous separation film encounters high temperature
Stability is unlikely to generate serious contraction and deformation, to further improve the high high-temp stability of composite diaphragm.
As improvement of the present invention, the water-soluble polymeric binder is polyacrylic acid, polyacrylate or is
The mixture of polyacrylic acid and polyacrylate.
As improvement of the present invention, the water-soluble polymeric binder is polyacrylic acid, Sodium Polyacrylate, polypropylene
Sour potassium, Lithium polyacrylate, calcium polyacrylate (CPA), polyacrylic acid and Sodium Polyacrylate mixture, polyacrylic acid and polyacrylic acid potassium
Mixture, in the mixture of polyacrylic acid and Lithium polyacrylate and the mixture of polyacrylic acid and calcium polyacrylate (CPA) extremely
Few one kind.
As improvement of the present invention, the weight of the water-soluble polymeric binder accounts for the inorganic functional coating gross weight
The value range of amount is 0.5~10.0%.
As improvement of the present invention, the pH value of the aqueous solution of 20% concentration of water-soluble polymeric binder is 4~6
In the range of.
As improvement of the present invention, the water milk type polymer binder and water-soluble polymeric binder are respective heavy
It is 0.5~10.0% that amount, which accounts for the value range of the inorganic functional total coating weight,.Beneficial effect is: in formula of size, bonding
The dosage of agent has large effect to the performance of inorganic functional coating and diaphragm, if the dosage of binder is very few, will lead to inorganic
The caking property of functional coating and diaphragm is deteriorated, and inorganic functional coating is easy to fall off in diaphragm and cell fabrication processes, influences nothing
The performance of machine functional coating performance.Conversely, binder may block up if the dosage of binder is excessive (mass fraction is greater than 20%)
The internal void of porous separation film is filled in, the inside lithium ion tunnel of lithium ion battery porous separation film is reduced, is increased internal
Polarization, eventually affect the performance of battery performance.
As improvement of the present invention, the water soluble polymer thickener is sodium carboxymethylcellulose, hydroxylmethyl cellulose
At least one of element, hydroxyethyl cellulose, polyacrylamide, sodium alginate and polyvinyl alcohol.
As improvement of the present invention, the weight of the water soluble polymer thickener accounts for the inorganic functional coating gross weight
The value range of amount is 0.5~2.0%.
As improvement of the present invention, the value range of the thickness of the inorganic functional coating is 2~6um.
As improvement of the present invention, the porous substrate is polyethylene film, polypropylene screen, polypropylene, polyethylene/poly-
Propylene composite membrane, cellulose membrane or be polyimide film.
As improvement of the present invention, the value range of the thickness of the porous substrate is 3~25um.
As improvement of the present invention, the value range of the porosity of the porous substrate is 20%~70%.
The present invention also provides a kind of preparation method of inorganic ceramic coating functions lithium ion battery isolation film simultaneously, including
Following steps:
Water-soluble binder dissolution is formed solution by the first step in deionized water；
Plate boehmite particles are dispersed in deionized water and the preparatory water soluble polymer thickener dissolved by second step,
And it is mixed and is formed uniformly mixed dispersion liquid；
Solution and water milk type polymer binder that the first step obtains are added into the mixed dispersion liquid of second step for third step, point
It dissipates uniformly, the weight for being adjusted to solid part accounts for the 10%~60% of the slurry total amount, obtains coating slurry；
4th step, the slurry that third step is obtained are coated in porous substrate at least by way of dimple version or extrusion coated
On one surface, the inorganic ceramic coating functionalization lithium ion battery isolation film is obtained after drying.
Another object of the present invention is to provide include anode, cathode, the coating being interval between the positive electrode and negative electrode
Functionalization porous separation film and electrolyte, the coating functions porous separation film are described in any of the above item
Inorganic ceramic coating functions lithium ion battery isolation film.
Relative to current organic/inorganic composite diaphragm, inorganic ceramic coating functions lithium ion battery of the invention every
It is had the following characteristics that from film and the lithium ion battery
One, lower inorganic coating thickness and weight and more stable coating layer thickness batch consistency.
It is in optimized selection by particle size to plate boehmite particles and its distribution, thickness, lesser particle ruler
On the one hand very little, relatively narrow size distribution and flat granule-morphology are conducive to the processing and fabricating of slurry, it is often more important that
Be conducive to the tightly packed surface density to improve inorganic coating of particle, and then realize to maximize and improve coating diaphragm heat resistance
Purpose.Meanwhile the tightly packed coating thickness that can reduce inorganic coating of board-like material and realize same improved heat resistance
Effect.Due to the Mohs' hardness about 3.0 of boehmite, density of material about 3.05g/cm3, and the Mohs' hardness of aluminium oxide about 9.0,
Its density of material about 4.0g/cm3, boehmite slurry and coating are in process of production to mixing plant, coating equipment and carving knife
The abrasion of piece will be far smaller than aluminium oxide, and the batch consistency of coating layer thickness is easier to control, and the weight of coating can be into
One step reduces, and is more advantageous to the promotion of lithium ion battery gravimetric energy density.
Two, extremely low coating water content and coating water absorption rate: since the present invention has selected the water of its dry glue
Contact angle is dripped 100o~130oBetween hydrophobicity emulsion type polymeric binder, can greatly reduce coating it is dry after
The hygroscopicity of the water content of inorganic functional coating and subsequent diaphragm in storage and cell fabrication processes.It therefore, can be most
Reduce to limits the decomposition reaction of electrolytic salt, it is ensured that the stabilization of battery performance, cycle life and security performance.
Three, excellent thermal stability: since the present invention has selected melting temperature 160oC~300oPolarity Gao Rong between C
Point high molecular polymer can make the organic matter high molecular polymer in coating in compound function as water-soluble polymeric binder
Can change the structural stability that its macromolecular chain skeleton is still kept when porous separation film encounters high temperature, inhibit serious contraction and
Deformation, to further improve the high high-temp stability of composite diaphragm.Good heat resistanceheat resistant shrinkage can reduce battery in height
The abnormal conditions such as temperature are because of positive and negative anodes short-circuit risks caused by diaphragm retracts.
Four, excellent coating adhesion: since the present invention has selected low polar emulsion type in adhesive coating system
The compound system of polymeric binder and water-soluble polymeric binder, can be between plate boehmite particles and boehmite
Grain porous isolating membrane between formed it is dotted and planar come into full contact with and bond, to guarantee preferable coating adhesion.
Five, the wetting of excellent electrolyte and water retainability: due to inorganic ceramic coating functions lithium-ion electric of the invention
The inorganic coating of pond isolation film has biggish porosity compared to organic porous substrate and has to electrolyte higher affine
Property, therefore, electrolyte can be significantly improved to the wetability inside battery interface and increases the electrolyte ownership of battery, from
And improve the cycle performance of battery.
Specific embodiment
Below in conjunction with specific embodiment, the content of the present invention will be further explained, but protection scope of the present invention is simultaneously
It is not limited solely to content described in embodiment.
Embodiment 1
The preparation of inorganic ceramic coating functions lithium ion battery isolation film
Coating slurry formula is based on siccative weight percent, and coating slurry is by 3 wt% phenylethylene ethylene/propenoic acid ester copolymer emulsions, 3
Wt% Lithium polyacrylate, 1 wt% sodium carboxymethylcellulose, 93 wt% plate boehmite particles, four part composition.Wherein, plate is vigorous
The average grain diameter D50 of nurse stone particle is 0.6um, D10 0.2um, D90 2.6um, D99 3.7um, with a thickness of 0.3um.Water
Newborn type polymeric binder selects phenylethylene ethylene/propenoic acid ester copolymer emulsion, and dry glue water droplet contact angle is 125o.Water-soluble polymerization
Object binder selects Lithium polyacrylate, and melting temperature is about 180oC.In slurry configuration process, solvent is deionized water,
In, the weight of solid part accounts for about 40 wt% of slurry total weight.
The preparation process of coating slurry is as follows:
(1) firstly, Lithium polyacrylate dissolution is formed the solution that concentration is 20 wt% in deionized water by the above formula；
(2) secondly, plate boehmite particles are dispersed in deionized water and the preparatory sodium carboxymethylcellulose dissolved, and will
It is uniformly mixed and forms mixed dispersion liquid；
(3) finally, the Lithium polyacrylate solution and water milk type polymer dissolved in advance is added into above mixed dispersion liquid
Binder phenylethylene ethylene/propenoic acid ester copolymer emulsion, is uniformly dispersed, and arrives required coating slurry to obtain the final product with 150 mesh net filtrations.
The coating slurry as made from the above method is coated in a thickness of the poly- of 12um using the micro- gravure coater of reverse roll
In the one side of ethylene microporous membrane (porosity 40%), coating layer thickness is about 2um, obtains the inorganic pottery that overall thickness is about 14um
Porcelain coating functions lithium ion battery isolation film.Porosity with mercury injection apparatus measurement composite porous film is 41%, micro- with polyethylene
The basic indifference of the porosity of hole film.
The preparation of cathode:
Using graphite as negative electrode active material, weight content is 95 wt%, and using butadiene-styrene rubber as polymeric binder, weight contains
Amount is 3 wt%；Using carbon black as conductive agent.
It is negative electrode active material that cathode, which selects graphite, feeds intake according to formula and prepares negative electrode slurry.It designs, starches by cathode formula
Expect that solid component includes the negative electrode active material of 94 wt%, butadiene-styrene rubber (SBR) polymeric binder of 3 wt%, the carboxylic of 1 wt%
The conductive black of sodium carboxymethylcellulose pyce polymer viscosifier and 2 wt%.Negative electrode slurry uses deionized water molten as dispersing
Agent, the solid content of slurry are 42 wt%.
Deionized water and sodium carboxymethylcellulose are added in blender by the above proportion, is sufficiently stirred and dissolves
To aqueous polymer solution.Conductive black is added in the aqueous polymer solution dissolved by formula again, is quickly stirred
Being ground to fineness is 5 μm hereinafter, graphite then is added by formula, and dispersion stirs evenly, and finally vacuumizes removing bubble.With 150
Mesh net filtration arrives required negative electrode slurry to obtain the final product.
The manufactured slurry is equably coated in the copper foil two sides with a thickness of 10 μm, then pole piece is compacted to one with roll squeezer
Determine thickness, cut-parts, soldering polar ear obtains cathode pole piece.
The preparation of anode:
Anode selects cobalt acid lithium (LiCoO2) it is active material, it feeds intake according to formula and prepares anode sizing agent.It is designed by anode formula,
Slurry solids ingredient includes the positive active material of 92 wt%, Kynoar (PVDF) binder of 5 wt% and 3 wt%
Conductive black.Anode sizing agent uses N-Methyl pyrrolidone (NMP) as dispersion solvent, and the solid content of slurry is 45
wt%。
N-Methyl pyrrolidone and Kynoar are added in mixer grinder by the above proportion, are sufficiently stirred
Dissolution obtains the polymer solution of Kynoar.The Kynoar dissolved is added in conductive black by formula again to gather
In polymer solution, quick agitation grinding to fineness is 5 μm hereinafter, cobalt acid lithium then is added by formula, and dispersion stirs evenly, finally
Vacuumize removing bubble.Required anode sizing agent is obtained with the filtering of 150 mesh stainless steel mesh.
Above-mentioned manufactured slurry is equably coated in the aluminium foil two sides with a thickness of 12 μm, is dried, then with roll squeezer by pole piece
It is compacted to certain thickness, cut-parts, soldering polar ear obtains anode pole piece.
The preparation of electrolyte:
Ethylene carbonate EC, propene carbonate PC and dimethyl carbonate DMC are configured to mixed solvent according to volume ratio 3:3:4,
Then lithium salts lithium hexafluoro phosphate (LiPF is added6), prepare LiPF6Concentration be 1M, obtain electrolyte after mixing evenly.
The assembling of battery:
Above-mentioned anode pole piece, inorganic/organic complex function porous separation film and cathode pole piece are wound into battery core, plastic-aluminum is multiple
Film encapsulation is closed, vacuum state baking injects quantitative electrolyte after removing moisture, carries out chemical conversion and volume test to battery, obtain thickness
The square flexible package lithium ion of width long respectively 3.4mm, 26mm, 90mm.
Embodiment 2
Coating slurry formula based on siccative weight percent, coating slurry by 10 wt% phenylethylene ethylene/propenoic acid ester copolymer emulsions,
0.5 wt% Lithium polyacrylate, 2 wt% sodium carboxymethylcelluloses, 87.5 wt% plate boehmite particles, four part composition.Wherein,
The average grain diameter D50 of plate boehmite particles be 0.6um, D10 0.2um, D90 2.6um, D99 3.7um, with a thickness of
0.3um.Water milk type polymer binder selects phenylethylene ethylene/propenoic acid ester copolymer emulsion, and dry glue water droplet contact angle is 125o.Water
Molten type polymeric binder selects Lithium polyacrylate, and melting temperature is about 180oC.In slurry configuration process, solvent be go from
Sub- water, wherein the weight of solid part accounts for about 40 wt% of slurry total weight.
The coating slurry as made from the above method is coated in a thickness of the poly- of 12um using the micro- gravure coater of reverse roll
In the one side of ethylene microporous membrane (porosity 40%), coating layer thickness is about 3um, obtains the inorganic pottery that overall thickness is about 15um
Porcelain coating functions lithium ion battery isolation film.Porosity with mercury injection apparatus measurement composite porous film is 41%, micro- with polyethylene
The basic indifference of the porosity of hole film.
Rest part is same as Example 1, no longer repeats herein.
Embodiment 3
Coating slurry formula is based on siccative weight percent, and coating slurry is by 2 wt% phenylethylene ethylene/propenoic acid ester copolymer emulsions, 2
Wt% Lithium polyacrylate, 1 wt% sodium carboxymethylcellulose, 95 wt% plate boehmite particles, four part composition.Wherein, plate is vigorous
The average grain diameter D50 of nurse stone particle is 0.6um, D10 0.2um, D90 2.6um, D99 3.7um, with a thickness of 0.3um.Water
Newborn type polymeric binder selects phenylethylene ethylene/propenoic acid ester copolymer emulsion, and dry glue water droplet contact angle is 125o.Water-soluble polymerization
Object binder selects Lithium polyacrylate, and melting temperature is about 180oC.In slurry configuration process, solvent is deionized water,
In, the weight of solid part accounts for about 40 wt% of slurry total weight.
The coating slurry as made from the above method is coated in a thickness of the poly- of 12um using the micro- gravure coater of reverse roll
In the one side of ethylene microporous membrane (porosity 40%), coating layer thickness is about 4um, obtains the inorganic pottery that overall thickness is about 16um
Porcelain coating functions lithium ion battery isolation film.Porosity with mercury injection apparatus measurement composite porous film is 41%, micro- with polyethylene
The basic indifference of the porosity of hole film.Rest part is same as Example 1, no longer repeats herein.
Embodiment 4
Coating slurry formula is based on siccative weight percent, and coating slurry is by 1 wt% phenylethylene ethylene/propenoic acid ester copolymer emulsion, 15
Wt% Lithium polyacrylate, 2 wt% sodium carboxymethylcelluloses, 82 wt% plate boehmite particles, four part composition.Wherein, plate is vigorous
The average grain diameter D50 of nurse stone particle is 1.0um, D10 0.3um, D90 2.8um, D99 4.0um, with a thickness of 0.3um.Water
Newborn type polymeric binder selects phenylethylene ethylene/propenoic acid ester copolymer emulsion, and dry glue water droplet contact angle is 125o.Water-soluble polymerization
Object binder selects Lithium polyacrylate, and melting temperature is about 180oC.In slurry configuration process, solvent is deionized water,
In, the weight of solid part accounts for about 40 wt% of slurry total weight.
The coating slurry as made from the above method is coated in a thickness of the poly- of 12um using the micro- gravure coater of reverse roll
In the one side of ethylene microporous membrane (porosity 40%), coating layer thickness is about 3um, obtains the inorganic pottery that overall thickness is about 15um
Porcelain coating functions lithium ion battery isolation film.Porosity with mercury injection apparatus measurement composite porous film is 41%, micro- with polyethylene
The basic indifference of the porosity of hole film.
Rest part is same as Example 1, no longer repeats herein.
Embodiment 5
Coating slurry formula based on siccative weight percent, coating slurry by 0.2 wt% phenylethylene ethylene/propenoic acid ester copolymer emulsion,
0.2 wt% Lithium polyacrylate, 0.2 wt% sodium carboxymethylcellulose, 99.4 wt% plate boehmite particles, four part composition.Its
In, the average grain diameter D50 of plate boehmite particles is 1.0um, D10 0.3um, D90 2.9um, D99 4.5um, with a thickness of
0.6um.Water milk type polymer binder selects phenylethylene ethylene/propenoic acid ester copolymer emulsion, and dry glue water droplet contact angle is 125o.Water
Molten type polymeric binder selects Lithium polyacrylate, and melting temperature is about 180oC.In slurry configuration process, solvent be go from
Sub- water, wherein the weight of solid part accounts for about 40 wt% of slurry total weight.
The coating slurry as made from the above method is coated in a thickness of the poly- of 12um using the micro- gravure coater of reverse roll
In the one side of ethylene microporous membrane (porosity 40%), coating layer thickness is about 3um, obtains the inorganic pottery that overall thickness is about 15um
Porcelain coating functions lithium ion battery isolation film.Porosity with mercury injection apparatus measurement composite porous film is 41%, micro- with polyethylene
The basic indifference of the porosity of hole film.
Rest part is same as Example 1, no longer repeats herein.
Embodiment 6
Coating slurry formula is based on siccative weight percent, and coating slurry is by 15 wt% phenylethylene ethylene/propenoic acid ester copolymer emulsions, 2
Wt% Lithium polyacrylate, 3 wt% sodium carboxymethylcelluloses, 80 wt% plate boehmite particles, four part composition.Wherein, plate is vigorous
The average grain diameter D50 of nurse stone particle is 1.0um, D10 0.3um, D90 2.9um, D99 4.5um, with a thickness of 0.6um.Water
Newborn type polymeric binder selects phenylethylene ethylene/propenoic acid ester copolymer emulsion, and dry glue water droplet contact angle is 125o.Water-soluble polymerization
Object binder selects Lithium polyacrylate, and melting temperature is about 180oC.In slurry configuration process, solvent is deionized water,
In, the weight of solid part accounts for about 40 wt% of slurry total weight.
The coating slurry as made from the above method is coated in a thickness of the poly- of 12um using the micro- gravure coater of reverse roll
In the one side of ethylene microporous membrane (porosity 40%), coating layer thickness is about 4um, obtains the inorganic pottery that overall thickness is about 16um
Porcelain coating functions lithium ion battery isolation film.Porosity with mercury injection apparatus measurement composite porous film is 41%, micro- with polyethylene
The basic indifference of the porosity of hole film.
Rest part is same as Example 1, no longer repeats herein.
Comparative example 1
Coating slurry formula is based on siccative weight percent, and coating slurry is by 3 wt% phenylethylene ethylene/propenoic acid ester copolymer emulsions, 3
Wt% Lithium polyacrylate, 1 wt% sodium carboxymethylcellulose, 93 wt% alumina particle, four part composition.Wherein, alumina particle
Average grain diameter D50 be 0.8um, D10 0.3um, D90 2.6um, D99 4.0um.Water milk type polymer binder is selected
Phenylethylene ethylene/propenoic acid ester copolymer emulsion, dry glue water droplet contact angle are 125o.Water-soluble polymeric binder selects polyacrylic acid
Lithium, melting temperature are about 180oC.In slurry configuration process, solvent is deionized water, wherein the weight of solid part accounts for described
About 40 wt% of slurry total weight.
The coating slurry as made from the above method is coated in a thickness of the poly- of 12um using the micro- gravure coater of reverse roll
In the one side of ethylene microporous membrane (porosity 40%), coating layer thickness is about 3um, obtains the inorganic pottery that overall thickness is about 15um
Porcelain coating functions lithium ion battery isolation film.Porosity with mercury injection apparatus measurement composite porous film is 41%, micro- with polyethylene
The basic indifference of the porosity of hole film.
Comparative example 2
Coating slurry formula based on siccative weight percent, coating slurry by 0.5 wt% phenylethylene ethylene/propenoic acid ester copolymer emulsion,
0.5 wt% Lithium polyacrylate, 0.5 wt% sodium carboxymethylcellulose, 98.5 wt% alumina particle, four part composition.Wherein, oxygen
The average grain diameter D50 for changing alumina particles is 0.8um, D10 0.3um, D90 2.6um, D99 4.0um.Water milk type polymer is viscous
It ties agent and selects phenylethylene ethylene/propenoic acid ester copolymer emulsion, dry glue water droplet contact angle is 125o.Water-soluble polymeric binder is selected
Lithium polyacrylate, melting temperature are about 180oC.In slurry configuration process, solvent is deionized water, wherein the weight of solid part
Amount accounts for about 40 wt% of slurry total weight.
The coating slurry as made from the above method is coated in a thickness of the poly- of 12um using the micro- gravure coater of reverse roll
In the one side of ethylene microporous membrane (porosity 40%), coating layer thickness is about 4um, obtains the inorganic pottery that overall thickness is about 16um
Porcelain coating functions lithium ion battery isolation film.Porosity with mercury injection apparatus measurement composite porous film is 41%, micro- with polyethylene
The basic indifference of the porosity of hole film.
Embodiment 1 to 6 and comparative example 1, the performance of comparative example 2 are compared as follows shown in table 1:
By above-mentioned table 1 it is found that (1) is in terms of the thermal contraction of composite diaphragm, under same coating thickness, embodiment 1 to embodiment 6
Being heat-shrinked both less than comparative example 1 and comparative example 2 can be under the coating layer thickness of 2um, 3um for plate boehmite coating
Reach the heat-resisting effect of aluminium oxide 3um, 4um coating layer thickness, it is possible thereby to significantly reduce diaphragm coating layer thickness, improves lithium-ion electric
The volume energy density in pond.In addition, the partial size and thickness of plate boehmite particles also have a certain impact to the heat resistance of coating.
It can be seen that plate boehmite particles affect the thermal contraction performance of lithium ion battery separator, and with its particle size, thickness and
Coating layer thickness is related.
(2) in terms of the surface density of inorganic coating, under same coating thickness, by embodiment 1 to embodiment 6 it is found that plate
The surface density of coating can be significantly reduced in the application of boehmite particles, improves the gravimetric energy density of lithium ion battery.
(3) in terms of the water content of inorganic coating, by embodiment 1 to embodiment 6 it is found that plate boehmite particles are due to it
Bulk density with higher can realize preferable coating heat resistance with relatively thin coating layer thickness, so while it applies thickness
The reduction of degree can equally be substantially reduced the moisture content of inorganic coating, and the long-term circulation for being more conducive to lithium ion battery is special
Property.
(4) in terms of the electrolyte of inorganic coating protects liquid measure, by embodiment 1 to embodiment 6 it is found that plate boehmite particles
It, can be real under same inorganic coating thickness due to the accumulation advantage of its electrolyte compatibility and plate-like particles with higher
Existing higher electrolyte liquid-keeping property, is more conducive to the long-term cycle characteristics of lithium ion battery.
Claims (18)
1. a kind of inorganic ceramic coating functions lithium ion battery isolation film, including porous substrate and it is attached to the porosity
Inorganic ceramic functional coating at least one surface of substrate, coating layer thickness are 1~10um；The inorganic ceramic coating packet
Rubbing board shape boehmite particles, water soluble polymer thickener, water milk type polymer binder and water-soluble polymeric binder；Its
Be characterized in that: the average grain diameter D50 of the plate boehmite particles be 0.3~2.0um, D10 > 0.05um, D90 < 6.0um,
D99 < 8.0um, with a thickness of 0.05~1.5um；The inorganic ceramic coating slurry, calculates according to weight ratio, plate boehmite
Grain 80.0~99.4%, water soluble polymer thickener 0.2~3.0%, water milk type polymer binder 0.2~15.0%, water-soluble
Polymeric binder 0.2~15.0%；The water milk type polymer binder is the water droplet contact angle of its dry glue 80o~150oIt
Between hydrophobic polymer polymer, the water-soluble polymeric binder be melting temperature 120oC~400oPole between C
Property high-melting-point high molecular polymer.
2. inorganic ceramic coating functions lithium ion battery isolation film according to claim 1, it is characterised in that: the plate
The average grain diameter D50 of shape boehmite particles be 0.6~1.0um, D10 > 0.1um, D90 < 3.0um, D99 < 4.0um, with a thickness of
0.1~0.7um, BET are 3~10m2/g。
3. inorganic ceramic coating functions lithium ion battery isolation film according to claim 1, it is characterised in that: the plate
The value range that the weight of shape boehmite particles accounts for the inorganic functional total coating weight is 87.5~98.5%.
4. inorganic ceramic coating functions lithium ion battery isolation film according to claim 1, it is characterised in that: the water
Newborn type polymeric binder be phenylethylene ethylene/propenoic acid ester copolymer emulsion, vinyl acetate/acrylate copolymer emulsion, vinyl acetate/
At least one of fatty acid vinyl ester copolymer emulsion, organosilicon acrylic ester copolymerization emulsion and acrylate copolymer emulsion.
5. inorganic ceramic coating functions lithium ion battery isolation film according to claim 1, it is characterised in that: the water
Newborn type polymeric binder is the water droplet contact angle of its dry glue 100o~130oBetween hydrophobic polymer polymer.
6. inorganic ceramic coating functions lithium ion battery isolation film according to claim 1, it is characterised in that: the water
The value range that the weight of newborn type polymeric binder accounts for the inorganic functional total coating weight is 0.5~10.0%.
7. inorganic ceramic coating functions lithium ion battery isolation film according to claim 1, it is characterised in that: the water
Molten type polymeric binder is polyacrylic acid, Sodium Polyacrylate, polyacrylic acid potassium, Lithium polyacrylate, calcium polyacrylate (CPA), polypropylene
Acid is mixed with the mixture of Sodium Polyacrylate, the mixture of polyacrylic acid and polyacrylic acid potassium, polyacrylic acid and Lithium polyacrylate
Close object and at least one of polyacrylic acid and the mixture of calcium polyacrylate (CPA)；Wherein, third is birdsed of the same feather flock together for polyacrylic acid and respectively
The mixture of olefin(e) acid salt, calculating its respective proportional region according to weight ratio is 20:80 to 80:20.
8. inorganic ceramic coating functions lithium ion battery isolation film according to claim 1, it is characterised in that: the water
Molten type polymeric binder is melting temperature 160oC~300oPolarity high-melting-point high molecular polymer between C.
9. inorganic ceramic coating functions lithium ion battery isolation film according to claim 1, it is characterised in that: the water
The pH value of the aqueous solution of molten 20% concentration of type polymeric binder is in the range of 4~6.
10. inorganic ceramic coating functions lithium ion battery isolation film according to claim 1, it is characterised in that: described
The value range that the weight of water-soluble polymeric binder accounts for the inorganic functional total coating weight is 0.5~10.0%.
11. inorganic ceramic coating functions lithium ion battery isolation film according to claim 1, it is characterised in that: described
Water soluble polymer thickener is sodium carboxymethylcellulose, hydroxymethyl cellulose, hydroxyethyl cellulose, polyacrylamide, seaweed
At least one of sour sodium and polyvinyl alcohol.
12. inorganic ceramic coating functions lithium ion battery isolation film according to claim 1, it is characterised in that: described
The value range that the weight of water soluble polymer thickener accounts for the inorganic functional total coating weight is 0.5~2.0%.
13. inorganic ceramic coating functions lithium ion battery isolation film according to claim 1, it is characterised in that: described
The value range of the thickness of inorganic functional coating is 2~6um.
14. inorganic ceramic coating functions lithium ion battery isolation film according to claim 1, it is characterised in that: described
Porous substrate is polyethylene film, polypropylene screen, polypropylene, polyethylene/polypropylene composite film, cellulose membrane or polyimides
Film.
15. inorganic ceramic coating functions lithium ion battery isolation film according to claim 14, it is characterised in that: described
The value range of the thickness of porous substrate is 3~25um.
16. inorganic ceramic coating functions lithium ion battery isolation film according to claim 14, it is characterised in that: described
The value range of the porosity of porous substrate is 20%~70%.
17. a kind of preparation method of inorganic ceramic coating functions lithium ion battery isolation film described in claim 1, feature
It is, comprising the following steps:
Water-soluble binder dissolution is formed solution by the first step in deionized water；
Plate boehmite particles are dispersed in deionized water and the preparatory water soluble polymer thickener dissolved by second step,
And it is mixed and is formed uniformly mixed dispersion liquid；
Solution and water milk type polymer binder that the first step obtains are added into the mixed dispersion liquid of second step for third step, point
It dissipates uniformly, the weight for being adjusted to solid part accounts for the 10%~60% of the slurry total amount, obtains coating slurry；
4th step, the slurry that third step is obtained are coated in porous substrate at least by way of dimple version or extrusion coated
On one surface, the inorganic ceramic coating functions lithium ion battery isolation film is obtained after drying.
18. a kind of lithium ion battery, including anode, cathode, the porous separation film being interval between the positive electrode and negative electrode, with
And electrolyte, it is characterised in that: the porous separation film is nothing described in any one of claims 1 to 16 claim
Machine ceramic coated functionalization lithium ion battery isolation film.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201810685986.9A CN108963164A (en) | 2018-06-28 | 2018-06-28 | Inorganic ceramic coating functions lithium ion battery isolation film, preparation method and its lithium ion battery |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201810685986.9A CN108963164A (en) | 2018-06-28 | 2018-06-28 | Inorganic ceramic coating functions lithium ion battery isolation film, preparation method and its lithium ion battery |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN108963164A true CN108963164A (en) | 2018-12-07 |
Family
ID=64487462
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201810685986.9A Pending CN108963164A (en) | 2018-06-28 | 2018-06-28 | Inorganic ceramic coating functions lithium ion battery isolation film, preparation method and its lithium ion battery |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN108963164A (en) |
Cited By (20)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109860478A (en) * | 2018-12-19 | 2019-06-07 | 上海纳米技术及应用国家工程研究中心有限公司 | Preparation method of organic-inorganic composite diaphragm material and products thereof and application |
| CN110498671A (en) * | 2019-06-03 | 2019-11-26 | 江西力能新能源科技有限公司 | A kind of ceramic coating and preparation method for lithium battery pole slice containing boehmite |
| CN110911620A (en) * | 2019-10-19 | 2020-03-24 | 东莞东阳光科研发有限公司 | Spotted coating diaphragm slurry, composite diaphragm and preparation method thereof |
| CN111200092A (en) * | 2020-01-10 | 2020-05-26 | 武汉中兴创新材料技术有限公司 | Preparation method of water-based coating slurry for battery diaphragm |
| CN111341982A (en) * | 2020-03-18 | 2020-06-26 | 江苏厚生新能源科技有限公司 | Coated diaphragm, preparation method, doped boehmite, ceramic slurry and lithium battery |
| CN111613761A (en) * | 2020-06-08 | 2020-09-01 | 德州东鸿制膜科技有限公司 | Lithium ion battery diaphragm and preparation method and application thereof |
| CN111725469A (en) * | 2020-06-24 | 2020-09-29 | 上海化工研究院有限公司 | High-temperature-resistant self-extinguishing lithium battery diaphragm and preparation method and application thereof |
| CN111933878A (en) * | 2020-07-06 | 2020-11-13 | 东莞市创明电池技术有限公司 | Lithium ion battery diaphragm and preparation method and application thereof |
| CN112670672A (en) * | 2020-12-28 | 2021-04-16 | 横店集团东磁股份有限公司 | Diaphragm for high-temperature storage, preparation method thereof and lithium ion battery |
| CN112876263A (en) * | 2021-02-01 | 2021-06-01 | 江苏厚生新能源科技有限公司 | High-specific-surface-area ceramic powder, preparation method thereof and high-liquid-retention-capacity ceramic diaphragm |
| CN112952297A (en) * | 2021-04-26 | 2021-06-11 | 乐凯胶片股份有限公司 | Ceramic diaphragm, preparation method thereof and lithium battery |
| CN113906597A (en) * | 2020-12-11 | 2022-01-07 | 东莞新能源科技有限公司 | Electrochemical device and electronic device |
| CN113972441A (en) * | 2021-09-26 | 2022-01-25 | 中材锂膜有限公司 | Lithium ion battery diaphragm with high heat resistance and high adhesion and preparation method thereof |
| CN114039166A (en) * | 2021-11-09 | 2022-02-11 | 深圳市旭然电子有限公司 | Diaphragm for lithium ion battery, preparation method of diaphragm and lithium ion battery |
| CN114128028A (en) * | 2019-07-30 | 2022-03-01 | 株式会社Lg化学 | Composite separator for electrochemical device and electrochemical device comprising the same |
| CN114361717A (en) * | 2022-02-18 | 2022-04-15 | 珠海冠宇电池股份有限公司 | Composite separator and electrochemical device |
| WO2022227345A1 (en) * | 2021-04-28 | 2022-11-03 | 惠州亿纬锂能股份有限公司 | Composite separator and preparation method therefor and use thereof |
| CN115347324A (en) * | 2022-09-19 | 2022-11-15 | 武汉微美新材料科技有限公司 | Ceramic coating, and diaphragm and lithium ion battery comprising same |
| EP4109660A4 (en) * | 2020-08-13 | 2023-11-22 | LG Energy Solution, Ltd. | Highly adhesive battery separator comprising pvac-pma copoylmer, and secondary battery comprising same |
| WO2023236401A1 (en) * | 2022-06-07 | 2023-12-14 | 中材锂膜有限公司 | Battery separator and preparation method therefor, and secondary battery |
Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103000848A (en) * | 2012-11-29 | 2013-03-27 | 东莞新能源科技有限公司 | Composite porous diaphragm and preparation method thereof |
| CN103915591A (en) * | 2014-04-09 | 2014-07-09 | 深圳市星源材质科技股份有限公司 | Water-based ceramic coating lithium ion battery diaphragm and processing method thereof |
| CN104838519A (en) * | 2012-11-30 | 2015-08-12 | 帝人株式会社 | Separator for nonaqueous secondary batteries, and nonaqueous secondary battery |
| CN105789523A (en) * | 2016-03-30 | 2016-07-20 | 深圳市旭冉电子有限公司 | Inorganic/organic compound functional porous isolating membrane and preparation method as well as lithium ion battery adopting inorganic/organic compound functional porous isolating membrane |
| CN107123767A (en) * | 2017-04-20 | 2017-09-01 | 深圳市旭冉电子有限公司 | A kind of organic functional porous separation film, preparation method and lithium ion battery |
| CN107895765A (en) * | 2017-10-13 | 2018-04-10 | 深圳市旭然电子有限公司 | Inorganic/organic composite porous barrier film, preparation method and its lithium ion battery |
-
2018
- 2018-06-28 CN CN201810685986.9A patent/CN108963164A/en active Pending
Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103000848A (en) * | 2012-11-29 | 2013-03-27 | 东莞新能源科技有限公司 | Composite porous diaphragm and preparation method thereof |
| CN104838519A (en) * | 2012-11-30 | 2015-08-12 | 帝人株式会社 | Separator for nonaqueous secondary batteries, and nonaqueous secondary battery |
| CN103915591A (en) * | 2014-04-09 | 2014-07-09 | 深圳市星源材质科技股份有限公司 | Water-based ceramic coating lithium ion battery diaphragm and processing method thereof |
| CN105789523A (en) * | 2016-03-30 | 2016-07-20 | 深圳市旭冉电子有限公司 | Inorganic/organic compound functional porous isolating membrane and preparation method as well as lithium ion battery adopting inorganic/organic compound functional porous isolating membrane |
| CN107123767A (en) * | 2017-04-20 | 2017-09-01 | 深圳市旭冉电子有限公司 | A kind of organic functional porous separation film, preparation method and lithium ion battery |
| CN107895765A (en) * | 2017-10-13 | 2018-04-10 | 深圳市旭然电子有限公司 | Inorganic/organic composite porous barrier film, preparation method and its lithium ion battery |
Cited By (26)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109860478A (en) * | 2018-12-19 | 2019-06-07 | 上海纳米技术及应用国家工程研究中心有限公司 | Preparation method of organic-inorganic composite diaphragm material and products thereof and application |
| CN110498671A (en) * | 2019-06-03 | 2019-11-26 | 江西力能新能源科技有限公司 | A kind of ceramic coating and preparation method for lithium battery pole slice containing boehmite |
| CN114128028A (en) * | 2019-07-30 | 2022-03-01 | 株式会社Lg化学 | Composite separator for electrochemical device and electrochemical device comprising the same |
| CN110911620A (en) * | 2019-10-19 | 2020-03-24 | 东莞东阳光科研发有限公司 | Spotted coating diaphragm slurry, composite diaphragm and preparation method thereof |
| CN110911620B (en) * | 2019-10-19 | 2022-04-29 | 东莞东阳光科研发有限公司 | Spotted coating diaphragm slurry, composite diaphragm and preparation method thereof |
| CN111200092B (en) * | 2020-01-10 | 2022-05-10 | 武汉中兴创新材料技术有限公司 | Preparation method of water-based coating slurry for battery diaphragm |
| CN111200092A (en) * | 2020-01-10 | 2020-05-26 | 武汉中兴创新材料技术有限公司 | Preparation method of water-based coating slurry for battery diaphragm |
| CN111341982A (en) * | 2020-03-18 | 2020-06-26 | 江苏厚生新能源科技有限公司 | Coated diaphragm, preparation method, doped boehmite, ceramic slurry and lithium battery |
| CN111341982B (en) * | 2020-03-18 | 2022-11-25 | 江苏厚生新能源科技有限公司 | Coated diaphragm, preparation method, doped boehmite, ceramic slurry and lithium battery |
| CN111613761A (en) * | 2020-06-08 | 2020-09-01 | 德州东鸿制膜科技有限公司 | Lithium ion battery diaphragm and preparation method and application thereof |
| CN111725469A (en) * | 2020-06-24 | 2020-09-29 | 上海化工研究院有限公司 | High-temperature-resistant self-extinguishing lithium battery diaphragm and preparation method and application thereof |
| CN111725469B (en) * | 2020-06-24 | 2022-12-09 | 上海化工研究院有限公司 | High-temperature-resistant self-extinguishing lithium battery diaphragm and preparation method and application thereof |
| CN111933878A (en) * | 2020-07-06 | 2020-11-13 | 东莞市创明电池技术有限公司 | Lithium ion battery diaphragm and preparation method and application thereof |
| EP4109660A4 (en) * | 2020-08-13 | 2023-11-22 | LG Energy Solution, Ltd. | Highly adhesive battery separator comprising pvac-pma copoylmer, and secondary battery comprising same |
| CN113906597A (en) * | 2020-12-11 | 2022-01-07 | 东莞新能源科技有限公司 | Electrochemical device and electronic device |
| CN112670672A (en) * | 2020-12-28 | 2021-04-16 | 横店集团东磁股份有限公司 | Diaphragm for high-temperature storage, preparation method thereof and lithium ion battery |
| CN112876263A (en) * | 2021-02-01 | 2021-06-01 | 江苏厚生新能源科技有限公司 | High-specific-surface-area ceramic powder, preparation method thereof and high-liquid-retention-capacity ceramic diaphragm |
| CN112952297B (en) * | 2021-04-26 | 2023-03-21 | 乐凯胶片股份有限公司 | Ceramic diaphragm, preparation method thereof and lithium battery |
| CN112952297A (en) * | 2021-04-26 | 2021-06-11 | 乐凯胶片股份有限公司 | Ceramic diaphragm, preparation method thereof and lithium battery |
| WO2022227345A1 (en) * | 2021-04-28 | 2022-11-03 | 惠州亿纬锂能股份有限公司 | Composite separator and preparation method therefor and use thereof |
| CN113972441A (en) * | 2021-09-26 | 2022-01-25 | 中材锂膜有限公司 | Lithium ion battery diaphragm with high heat resistance and high adhesion and preparation method thereof |
| CN114039166A (en) * | 2021-11-09 | 2022-02-11 | 深圳市旭然电子有限公司 | Diaphragm for lithium ion battery, preparation method of diaphragm and lithium ion battery |
| CN114361717A (en) * | 2022-02-18 | 2022-04-15 | 珠海冠宇电池股份有限公司 | Composite separator and electrochemical device |
| CN114361717B (en) * | 2022-02-18 | 2024-04-30 | 珠海冠宇电池股份有限公司 | Composite separator and electrochemical device |
| WO2023236401A1 (en) * | 2022-06-07 | 2023-12-14 | 中材锂膜有限公司 | Battery separator and preparation method therefor, and secondary battery |
| CN115347324A (en) * | 2022-09-19 | 2022-11-15 | 武汉微美新材料科技有限公司 | Ceramic coating, and diaphragm and lithium ion battery comprising same |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN108963164A (en) | Inorganic ceramic coating functions lithium ion battery isolation film, preparation method and its lithium ion battery | |
| CN105789523B (en) | A kind of inorganic/organic complex function porous separation film, preparation method and its lithium ion battery | |
| CN107895765A (en) | Inorganic/organic composite porous barrier film, preparation method and its lithium ion battery | |
| KR101868240B1 (en) | Binder for nonaqueous secondary batteries, resin composition for nonaqueous secondary batteries, nonaqueous secondary battery separator, nonaqueous secondary battery electrode, and nonaqueous secondary battery | |
| Bigoni et al. | Sodium alginate: a water-processable binder in high-voltage cathode formulations | |
| CN108389999A (en) | Organic and inorganic composite coated porous separation film, preparation method and its lithium ion battery | |
| CN109167012B (en) | Multilayer composite structure diaphragm, preparation method thereof and lithium-sulfur battery | |
| CN105958009B (en) | A kind of high security lithium ion battery composite pole piece and preparation method thereof, lithium ion battery | |
| CN107004859B (en) | Binder for nonaqueous secondary battery, composition for functional layer of nonaqueous secondary battery, functional layer for nonaqueous secondary battery, and nonaqueous secondary battery | |
| KR100450109B1 (en) | Non-aqueous electrolyte secondary battery and production method thereof | |
| CN102623658B (en) | Diaphragm and preparation method thereof, and lithium ion battery | |
| CN102329538B (en) | Water-based conductive ink of a lithium-ion battery | |
| CN104868084A (en) | Isolation membrane for lithium ion secondary battery | |
| CN106654125A (en) | Method for preparing modified ceramic diaphragm through dopamine compound adhesive and application thereof | |
| CN107565112A (en) | A kind of preparation method of graphene coated lithium ion secondary battery anode material | |
| CN109728300B (en) | Lithium battery conductive slurry containing different-defect graphene and preparation method thereof | |
| WO2021184790A1 (en) | Cathode and cathode slurry for secondary battery | |
| CN105914346B (en) | Non-aqueous electrolyte secondary battery and its manufacturing method | |
| CN112310344A (en) | Positive plate and lithium ion battery containing same | |
| US20230141592A1 (en) | Binder composition for secondary battery | |
| CA3183234A1 (en) | Cathode and cathode slurry for secondary battery | |
| CN109728301B (en) | Graphene-containing lithium battery conductive slurry and preparation method thereof | |
| KR102384939B1 (en) | Liquid adhesive coating for coating collector | |
| KR20140078027A (en) | Electrode for lithium secondary battery, lithium secondary battery using the same and fabrication method thereof | |
| CN104247098A (en) | Anode for secondary battery, method for producing same, and secondary battery |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| RJ01 | Rejection of invention patent application after publication | ||
| RJ01 | Rejection of invention patent application after publication |
Application publication date: 20181207 |