CN109103394A - A kind of lithium battery diaphragm and the preparation method and application thereof for removing ultra micro modified filler containing height - Google Patents
A kind of lithium battery diaphragm and the preparation method and application thereof for removing ultra micro modified filler containing height Download PDFInfo
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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
- H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
- H01M50/40—Separators; Membranes; Diaphragms; Spacing elements inside cells
- H01M50/409—Separators, membranes or diaphragms characterised by the material
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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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Abstract
The present invention relates to technical field of lithium ion, and in particular to a kind of lithium battery diaphragm and the preparation method and application thereof that ultra micro modified filler is removed containing height.By being dispersed with stirring nanoscale or/and submicron order or/and micron-sized layered inorganic particulate in deionized water, then sufficient standing, after so that the layered inorganic particulate in suspension is carried out sufficient ion-exchange reactions, it chooses its middle layer suspension and repeats that deionized water cleaning is used for multiple times, filtering, after taking insoluble matter to be dried in vacuo, obtain the modified sheeted structured packing of ultra micro, and and methyl methacrylate, soft monomer, hard monomer, emulsifier, initiator, the copolymer emulsion of acetone preparation, reaction obtains coating slurry under 65-80 DEG C of ultrasonication, single or double is evenly applied to polyolefin micropore barrier diaphragm surface, it is dry through vacuum drying oven, the coat that single face is formed is with a thickness of 4-15 μm, and coat has the lithium battery diaphragm of high removing two-dimensional nano lamella.Preferable cohesive force is kept between the lithium battery diaphragm coat and polyalkene diaphragm, while ensureing that diaphragm has good mechanical properties, has and battery core internal resistance and interface impedance is greatly lowered, the security performance of battery improves.
Description
Technical field
The present invention relates to technical field of lithium ion, and in particular to a kind of lithium electricity of the ultra micro modified filler of removing containing height
Pond diaphragm and the preparation method and application thereof.
Background technique
Currently, lithium ion battery has developed into fields such as mobile traffic, energy storage systems, this requires electricity
Pond has high energy density and power density.It is challenged greatly however, exploitation heavy-duty battery must just focus on associated two:
The problem that security hidden trouble and battery performance are limited.In lithium ion battery structure, diaphragm main function is to prevent positive and negative anodes
Physical contact, while promoting ionic conduction as electrolyte repository.However, currently used battery diaphragm multidigit polypropylene
(PP) and polyethylene (PE) microporous barrier, the thermal contraction of high temperature lower diaphragm plate cause positive and negative anodes to contact, and bring the rapid heat release in part, cause
Bring huge security risk.Polyolefins diaphragm is poor to the wellability of polarity electrolyte simultaneously, puncture resistance is poor, this
A little defects have become the problem urgently overcome during lithium battery high performance.
Based on this, a large number of researchers coat resistance to height to diagram modification, such as membrane surface using various physics and chemical method
The inorganic nanoparticles of temperature are a kind of simplicity that can effectively solve the above problem to enhance thermal dimensional stability and wettability
Method, the application for a patent for invention file of Publication No. CN103236511A disclose a kind of super heat-resisting organic/inorganic it is compound every
The preparation method of film prepares coating slurry by using binder and two-dimensional sheet filler, and in polyolefin micropore barrier diaphragm table
Face applying coating, because the addition of binder causes coating slurries entirety viscosity higher, this method processes the composite diaphragm to be formed
The thickness for coating layer surface and polyalkene diaphragm is thicker, after mutually being removed between another coating layer surface and polyalkene diaphragm,
Because the adherency polyalkene diaphragm and two-dimensional sheet filler of portion of binder lead to attachment zone occur, polyalkene diaphragm at attachment zone
There is the phenomenon that is blocked in ion duct.
Korean Patent KR101125013 describe using water-soluble ionic polymers manufacture crosslinking ceramics-coating every
The method of film, the method also uses water-soluble ionomer, but ionomer is not scattered in water, but is completely dissolved
Yu Shui, therefore the removing rate of coat is higher, but also based on this, not can avoid solvent and be kept in detention to the solvent of ionomer.
In consideration of it, the present invention provides a kind of lithium battery diaphragm and preparation method thereof that ultra micro modified filler is removed containing height,
Height removing is carried out to layered inorganic particulate by using intercalator and forms the modified sheeted structured packing of ultra micro, coat obtained
Preferable cohesive force is kept between polyalkene diaphragm, while ensureing that diaphragm has good mechanical properties, is had significantly
Battery core internal resistance and interface impedance are reduced, the security performance of battery improves.
Summary of the invention
To achieve the above object, the present invention is implemented using following technological means:
A kind of preparation method of the lithium battery diaphragm of the ultra micro modified filler of removing containing height, it is characterised in that following steps:
(1) preparation of the modified sheeted structured packing of ultra micro: by nanoscale or/and submicron order or/and micron-sized layered inorganic
Particle is dispersed with stirring in deionized water, then sufficient standing, and under 65-80 DEG C of water bath with thermostatic control, is continued into deionized water
Low speed, which is passed through nitrogen, makes liquid level keep disturbance, and is slowly added dropwise and is inserted to layered inorganic particulate with the ratio of 1:2.5-3.5g/mmol
Layer agent stops after abundant ion-exchange reactions being passed through nitrogen, chooses its middle layer suspension and repeats deionized water is used for multiple times clear
It washes, filter, until taking insoluble matter to carry out vacuum dry after addition silver nitrate solution does not generate flocculent deposit into deionized water cleaning solution
After dry, i.e. the acquisition modified sheeted structured packing of ultra micro.
(2) preparation of coating slurry: will be under methyl methacrylate, soft monomer, hard monomer, emulsifier, initiator stirring
It is configured to blending emulsion, the modified sheeted structured packing of ultra micro is slowly added into blending emulsion and under 65-80 DEG C of ultrasonication
I.e. acquisition coating slurry is added after the acetone of blending emulsion mass ratio 4%-8%, stirring in reaction 1.5-4 hour；
(3) preparation of battery diaphragm: being evenly applied to polyolefin micropore barrier diaphragm surface for the coating slurry single or double,
Dry in 55-70 DEG C of progress vacuum drying oven, for the coat that single face is formed with a thickness of 4-15 μm, the coat for being made described can be complete
The lithium battery diaphragm of fully stripped.
In the above method, such as montmorillonite, hydrotalcite, kaolinite, sepiolite, mica is may be selected wherein in layered inorganic particulate
A kind of or compounding.
Further, in the step (1), the intercalator be cetyl ammonium bromide, octadecyl bromination ammonium,
The one or more of them such as neopelex, dodecyl ammonium bromide compounding.
Further, in the step (2), the soft monomer is that ethyl acrylate, butyl acrylate, acrylic acid are different
Monooctyl ester, the hard monomer are vinylacetate, methyl acrylate, any one or compounding in styrene, and metering system
Sour methyl esters: soft monomer: hard monomer is deployed with the weight ratio of 5-8:2-6:2-6.
Further, in the step (2), the emulsifier is lauryl sodium sulfate, odium stearate, rosin
The one or more of them such as sour sodium, alkyl diphenyl ether sodium sulfonate, alkylphenol polyethylene oxide ether are used in compounding；The initiator
For azodiisobutyronitrile, azobisisoheptonitrile, ammonium persulfate, potassium peroxydisulfate, benzoyl peroxide, lauroyl peroxide, isopropyl
The one or more of them such as benzene hydrogen peroxide, tert-butyl hydroperoxide are used in compounding；Emulsifier: initiator: methyl methacrylate
The overall weight ratio with 0.5-1:1:1000-1500 of ester and soft monomer and hard monomer is deployed.
As a kind of effective scheme, in the step (2), the modified sheeted structured packing of the ultra micro be blended it is single
The weight ratio of body is 1:20-50.
Further, in the step (2), the frequency of the above-mentioned ultrasonic wave of ultrasound is 5-10MHz, ultrasonic disperse
Time is 1.5-4 hours.
As a kind of effective scheme, in the step (3), the polyolefin porous separator is PP porous septum or PE
Porous septum or PP and PE MULTILAYER COMPOSITE porous septum, or the non-woven polyolefin prepared by spinning process, the film layer
With a thickness of 5-20 μm.
As a kind of effective scheme, in the step (3), using non-contact type high-precision coating machine by the painting
It covers slurry and polyolefin micropore barrier diaphragm surface is evenly applied to curtain flow coat cloth single or double.
Height removing is contained using the lithium battery diaphragm and this of the ultra micro modified filler of removing containing height of above method preparation
Application of the lithium battery diaphragm of ultra micro modified filler in lithium ion battery separator is also within protection scope of the present invention.
The invention has the beneficial effects that:
Using intercalator to and to nanoscale in suspension or/and submicron order or/and micron-sized layered inorganic particulate into
Row ion-exchange reactions can be efficiently entering in the lamella of layered inorganic particulate and be carried out to it using the intercalator of rational proportion
While layer removing, formation is modified layered inorganic particulate two sides and avoids piece strata attached, forms the ultra micro of surface hydrophobicity
Modified sheeted structured packing partial size is superfine, and after vacuum drying, preparation coating slurry tool lower thickness is coated on thin layer polyene
Hydrocarbon diaphragm, and good mechanical strength can be still kept under (135-150 DEG C) under high temperature environment, coat does not take off
Powder does not result in blockage phenomenon to the duct of polyalkene diaphragm.
Material using methyl methacrylate as blending emulsion, the coating slurry that cooperation acetone is prepared as solvent,
It can keep fully dispersed after being added to the blending emulsion that soft monomer, hard monomer, emulsifier, initiator are equipped with, and subsequent
In drying process, acetone can dissolve methyl methacrylate and part soft monomer, hard monomer, initiator, and in evaporation process
Irregular Nano grade microchannel is formed, the ion permeable of diaphragm is improved.
Preferably, using non-contact type high-precision coating machine, the coating slurry double-faced uniform is coated with curtain stream method
It in polyolefin porous separator surface, avoids in coating procedure, because of coating slurry jet apparatus and relatively thin polyolefin porous
Contact between diaphragm, generating additional force causes the shrinkage between polyolefin porous separator and coat to deform, and another control applies
It covers the curtain stream flow velocity of slurry and the opposite of polyolefin porous separator moves speed, submicron order or/and micron-sized high-precision can be formed
Coating is suitble to the production of the battery diaphragm of this thin layer coat.
Detailed description of the invention
Fig. 1 is the electron microscope of 1 interval film surface of the embodiment of the present invention；
Fig. 2 is the XRD state diagram that coat is removed in the embodiment of the present invention 1.
Specific embodiment
The contents of the present invention are further illustrated with specific embodiment with reference to the accompanying drawings of the specification, but should not be construed as to this
The limitation of invention.Unless otherwise specified, the conventional hand that technological means used in embodiment is well known to those skilled in the art
Section.Unless stated otherwise, the present invention uses reagent, method and apparatus is the art conventional reagents, method and apparatus.
In the performance test of following each embodiments and comparative example final products, comparative example 1 is commercially available certain ceramic coated electricity
Pond diaphragm, together with the lithium battery diaphragm in embodiment 1 ~ 4 referring to DB44/T 1152-2013 " lithium ion battery polyethylene every
Film " method is measured.The performance test of the above various examples and comparative examples carries out five parallel tests and is averaged.
Embodiment 1
The lithium battery diaphragm that the coat can be completely exfoliated is prepared using following step:
(1) preparation of the modified sheeted structured packing of ultra micro: nanoscale or/and submicron order or/and micron-sized stratiform are covered de-
Stone is dispersed with stirring in deionized water, then sufficient standing, and under 75 DEG C of waters bath with thermostatic control, and it is logical to continue low speed into deionized water
Enter nitrogen to liquid surface fluctuation, and the nitrogen low speed is kept to be passed through state；It is calculated with the amount of every 100g layered inorganic particulate, it is slowly right
300mmol intercalator should be added dropwise, in the present embodiment, using 0.1mol/L dodecyl ammonium bromide as intercalator, and carry out
Sufficient ion-exchange reactions, as shown in Fig. 2, wherein A lines are the diffraction maximum of layered inorganic particulate, B lines are modified
The diffraction maximum of intermediate, C lines are the diffraction maximum of inorganic sheet coating film.Fig. 2 (A-B) is as it can be seen that modified laminate granular layer
Spacing, which increases, (utilizes Bragg law λ=2dsinθInterlamellar spacing is calculated, interlamellar spacing is increased to by original about 1.2nm as the result is shown
1.9nm or so), this illustrates that intercalator is modified the compatibility successfully improved between inorganic particle and organic substrate；Fig. 2 C result is aobvious
Show, 001 face diffraction maximum of layered inorganic particulate disappears substantially, this illustrates that its lamella is obtained than more completely removing, and two-dimensional nano covers
De- flag layer is removed in height, and is evenly distributed, to be effectively improved the comprehensive performance of end product.
After abundant ion-exchange reactions, stopping is passed through nitrogen, takes the suspension of its middle layer part and uses deionized water
Cleaning, filtering collect deionized water cleaning solution and the silver nitrate solution of 0.1mol/L are added, after there is flocculent deposit, to outstanding
Much filtrate in supernatant liquid is cleaned once again using deionized water, collects deionized water cleaning solution again and the nitric acid of 0.1mol/L is added
Silver-colored solution detection, above steps may be repeated multiple times into deionized water cleaning solution without after flocculent deposit, and insoluble matter is taken to carry out vacuum
After drying, i.e. the acquisition modified sheeted structured packing of ultra micro.
(2) preparation of coating slurry: by methyl methacrylate 500g and butyl acrylate 200g, styrene 300g, ten
Sodium dialkyl sulfate 0.5g, azodiisobutyronitrile 0.5g, tert-butyl hydroperoxide 0.5g stir to form blending emulsion, newborn to being blended
It is slowly added to the modified sheeted structured packing of 25g ultra micro in liquid, and reacts 2 h under 65-73 DEG C of temperature, 5-10MHz ultrasonication,
It is well-dispersed in ultra micro modified sheeted structured packing in blending emulsion, after the acetone of blending emulsion mass ratio 5%, stirring is added
Obtain coating slurry；
(3) the coating slurry double-faced uniform preparation of battery diaphragm: is coated on by PE micropore using micro gravure printing machine
Membrane surface, lithium battery diaphragm that the coat that is made described can be completely exfoliated dry in 55-70 DEG C of progress vacuum drying oven.
Embodiment 2
On the basis of embodiment 1, using non-contact type high-precision coating machine as working equipment, with curtain stream method by the painting
Slurry double-faced uniform is covered coated on PE porous septum surface, the obtained coat dry in 55-70 DEG C of progress vacuum drying oven
The lithium battery diaphragm that can be completely exfoliated.
Embodiment 3
The lithium battery diaphragm that the coat can be completely exfoliated is prepared using following step:
(1) preparation of the modified sheeted structured packing of ultra micro: nanoscale or/and submicron order or/and micron-sized stratiform are covered de-
Stone, hydrotalcite, kaolinite arbitrary proportion mixture are dispersed with stirring in deionized water, then sufficient standing, and in 75 DEG C of constant temperature
Under water-bath, continues low speed into deionized water and be passed through nitrogen to liquid surface fluctuation, and the nitrogen low speed is kept to be passed through state；With every
The amount of 100g layered inorganic particulate calculates, and 280mmol intercalator is slowly added dropwise in correspondence；In the present embodiment, using 0.1mol/L
Neopelex and 0.1mol/L cetyl ammonium bromide are being carried out sufficiently using the ratio mixing of 1:1 as intercalator
Ion-exchange reactions after, take the suspension of its middle layer part and using deionized water cleaning, filtering, collect deionized water cleaning
Liquid and the silver nitrate solution that 0.1mol/L is added use deionized water to the much filtrate in suspension after there is flocculent deposit
It cleans once again, collect deionized water cleaning solution again and the silver nitrate solution detection of 0.1mol/L is added, above-mentioned step is repeated several times
Suddenly into deionized water cleaning solution without after flocculent deposit, after taking insoluble matter to be dried in vacuo, i.e. acquisition ultra micro is modified sheeted
Structured packing.
(2) preparation of coating slurry: by methyl methacrylate 600g and butyl acrylate 150g, ethyl acrylate 50g,
Styrene 200g, lauryl sodium sulfate 0.5g, lauroyl peroxide 0.5g, potassium peroxydisulfate 0.5g stir to form blending emulsion,
The modified sheeted structured packing of 25g ultra micro is slowly added into blending emulsion, and under 76-80 DEG C of temperature, 5-10MHz ultrasonication
2 h are reacted, are well-dispersed in ultra micro modified sheeted structured packing in blending emulsion, the third of blending emulsion mass ratio 5% is added
Coating slurry is obtained after ketone, stirring；
(3) preparation of battery diaphragm: use non-contact type high-precision coating machine with curtain stream method that the coating slurry is two-sided
It is even to be coated on PP and PE MULTILAYER COMPOSITE porous septum surface, it is dry in 55-70 DEG C of progress vacuum drying oven, the coat is made
The lithium battery diaphragm that can be completely exfoliated.
Embodiment 4
The lithium battery diaphragm that the coat can be completely exfoliated is prepared using following step:
(1) preparation of the modified sheeted structured packing of ultra micro: by nanoscale or/and submicron order or/and micron-sized stratiform Hai Pao
Stone, hydrotalcite, kaolinite arbitrary proportion mixture are dispersed with stirring in deionized water, then sufficient standing, and in 75 DEG C of constant temperature
Under water-bath, continues low speed into deionized water and be passed through nitrogen to liquid surface fluctuation, and the nitrogen low speed is kept to be passed through state；And with every
The amount of 100g layered inorganic particulate calculates, and 320mmol intercalator is slowly added dropwise in correspondence；In the present embodiment, using 0.1mol/L
Neopelex and 0.1mol/L dodecyl ammonium bromide are being carried out sufficiently using the ratio mixing of 1:1 as intercalator
Ion-exchange reactions after, take the suspension of its middle layer part and using deionized water cleaning, filtering, collect deionized water cleaning
Liquid and the silver nitrate solution that 0.1mol/L is added use deionized water to the much filtrate in suspension after there is flocculent deposit
It cleans once again, collect deionized water cleaning solution again and the silver nitrate solution detection of 0.1mol/L is added, above-mentioned step is repeated several times
Suddenly into deionized water cleaning solution without after flocculent deposit, after taking insoluble matter to be dried in vacuo, i.e. acquisition ultra micro is modified sheeted
Structured packing.
(2) preparation of coating slurry: by methyl methacrylate 600g and butyl acrylate 100g, ethyl acrylate
100g, styrene 200g, lauryl sodium sulfate 0.5g, lauroyl peroxide 0.5g, isopropyl benzene hydroperoxide 0.5g stir shape
At blending emulsion, the modified sheeted structured packing of 25g ultra micro is slowly added into blending emulsion, and in 68-72 DEG C of temperature, 5-
2 h are reacted under 10MHz ultrasonication, are well-dispersed in ultra micro modified sheeted structured packing in blending emulsion, are added and cream is blended
Coating slurry is obtained after the acetone of liquid mass ratio 5%, stirring.
(3) preparation of battery diaphragm: using non-contact type high-precision coating machine, with curtain stream method that the coating slurry is double
Face is evenly applied to PP and PE MULTILAYER COMPOSITE porous septum surface, dry in 55-70 DEG C of progress vacuum drying oven, and the painting is made
The lithium battery diaphragm that coating can be completely exfoliated.
Comparative example 1 and the properties of sample test result of embodiment 1-4 such as table 1.
Table 1
The above described is only a preferred embodiment of the present invention, be not intended to limit the invention, thus it is all according to the present invention
The practical any modification, equivalent substitution, improvement and etc. to the above embodiments of technology, still fall within the model of technical solution of the present invention
In enclosing.
Claims (10)
1. a kind of preparation method of the lithium battery diaphragm of the ultra micro modified filler of removing containing height, it is characterised in that following steps:
Step (1): the preparation of the modified sheeted structured packing of ultra micro: by nanoscale or/and submicron order or/and micron-sized stratiform
Inorganic particle is dispersed with stirring in deionized water, then sufficient standing, and under 65-80 DEG C of water bath with thermostatic control, into deionized water
Lasting low speed, which is passed through nitrogen, makes liquid level keep disturbance, and is slowly dripped to layered inorganic particulate with the ratio of 1:2.5-3.5g/mmol
Add intercalator, stop logical nitrogen after abundant ion-exchange reactions, choose its middle layer suspension and repeats that deionized water is used for multiple times
Cleaning, filtering, until taking insoluble matter to carry out vacuum after addition silver nitrate solution does not generate flocculent deposit into deionized water cleaning solution
After drying, i.e. the acquisition modified sheeted structured packing of ultra micro；
Step (2): the preparation of coating slurry: will be under methyl methacrylate, soft monomer, hard monomer, emulsifier, initiator stirring
It is configured to blending emulsion, the modified sheeted structured packing of ultra micro is slowly added into blending emulsion and under 65-80 DEG C of ultrasonication
I.e. acquisition coating slurry is added after the acetone of blending emulsion mass ratio 4%-8%, stirring in reaction 1.5-4 hour；
Step (3): the coating slurry single or double preparation of battery diaphragm: is evenly applied to polyolefin micropore barrier diaphragm
Surface, dry in 55-70 DEG C of progress vacuum drying oven, the coating is made with a thickness of 4-15 μm in the coat that single face is formed
The lithium battery diaphragm that layer can be completely exfoliated.
2. a kind of preparation method of the lithium battery diaphragm of ultra micro modified filler of removing containing height as described in claim 1, special
Sign is, in the step (1), the intercalator is cetyl ammonium bromide, octadecyl bromination ammonium, detergent alkylate
The one or more of them such as sodium sulfonate, dodecyl ammonium bromide compounding.
3. a kind of preparation method of the lithium battery diaphragm of ultra micro modified filler of removing containing height as described in claim 1, special
Sign is, in the step (2), the soft monomer be ethyl acrylate, butyl acrylate, Isooctyl acrylate monomer, it is described
Hard monomer be vinylacetate, methyl acrylate, any one or compounding in styrene, and methyl methacrylate: it is soft
Monomer: hard monomer is deployed with the weight ratio of 5-8:2-6:2-6.
4. a kind of preparation method of the lithium battery diaphragm of ultra micro modified filler of removing containing height as claimed in claim 3, special
Sign is, in the step (2), the emulsifier is lauryl sodium sulfate, odium stearate, sodium abietate, alkyl two
The one or more of them such as phenylate sodium sulfonate, alkylphenol polyethylene oxide ether are used in compounding, and the initiator is that azo two is different
Butyronitrile, azobisisoheptonitrile, ammonium persulfate, potassium peroxydisulfate, benzoyl peroxide, lauroyl peroxide, isopropyl benzene hydroperoxide,
The one or more of them such as tert-butyl hydroperoxide are used in compounding；Emulsifier: initiator: methyl methacrylate and soft monomer and
The overall weight ratio with 0.5-1:1:1000-1500 of hard monomer is deployed.
5. a kind of system of the lithium battery diaphragm of the ultra micro modified filler of removing containing height as described in claim 1-4 any one
Preparation Method, which is characterized in that the ultra micro modified sheeted structured packing and weight that monomer is blended in the step (2)
Than for 1:20-50.
6. a kind of preparation method of the lithium battery diaphragm of ultra micro modified filler of removing containing height as claimed in claim 5, special
Sign is, in the step (2), the frequency of the ultrasonic wave is 5-10MHz, and the ultrasonic disperse time is 1.5-4 hours.
7. a kind of system of the lithium battery diaphragm of the ultra micro modified filler of removing containing height as described in claim 1-4 any one
Preparation Method, which is characterized in that in the step (3), the polyolefin porous separator is PP porous septum or PE porous septum
Or PP and PE MULTILAYER COMPOSITE porous septum, or the non-woven polyolefin prepared by spinning process, the thicknesses of layers are 5-
20 μm。
8. a kind of system of the lithium battery diaphragm of the ultra micro modified filler of removing containing height as described in claim 1-4 any one
Preparation Method, which is characterized in that in the step (3), use non-contact type high-precision coating machine by the coating slurry with
Curtain flow coat cloth single or double is evenly applied to polyolefin micropore barrier diaphragm surface.
9. it is a kind of by any one of claim 1-8 the method preparation containing height removing ultra micro modified filler lithium battery every
Film.
10. the lithium battery diaphragm of the ultra micro modified filler of removing containing height is in lithium ion battery separator as claimed in claim 9
Using.
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| CN201810854465.1A CN109103394B (en) | 2018-07-30 | 2018-07-30 | Lithium battery diaphragm containing highly-stripped ultra-micro modified filler and preparation method and application thereof |
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| CN201810854465.1A CN109103394B (en) | 2018-07-30 | 2018-07-30 | Lithium battery diaphragm containing highly-stripped ultra-micro modified filler and preparation method and application thereof |
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111072317A (en) * | 2019-12-04 | 2020-04-28 | 乐凯胶片股份有限公司 | Ceramic slurry, ceramic diaphragm and lithium ion battery |
| CN114142168A (en) * | 2021-11-09 | 2022-03-04 | 惠州锂威电子科技有限公司 | Preparation method of composite diaphragm, composite diaphragm and lithium ion battery |
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| CN114142168A (en) * | 2021-11-09 | 2022-03-04 | 惠州锂威电子科技有限公司 | Preparation method of composite diaphragm, composite diaphragm and lithium ion battery |
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