CN110408075A - A kind of composite isolated film and preparation method thereof - Google Patents
A kind of composite isolated film and preparation method thereof Download PDFInfo
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- CN110408075A CN110408075A CN201910804346.XA CN201910804346A CN110408075A CN 110408075 A CN110408075 A CN 110408075A CN 201910804346 A CN201910804346 A CN 201910804346A CN 110408075 A CN110408075 A CN 110408075A
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/052—Li-accumulators
- H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
- H01M50/40—Separators; Membranes; Diaphragms; Spacing elements inside cells
- H01M50/403—Manufacturing processes of separators, membranes or diaphragms
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- H—ELECTRICITY
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- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
- H01M50/40—Separators; Membranes; Diaphragms; Spacing elements inside cells
- H01M50/409—Separators, membranes or diaphragms characterised by the material
- H01M50/446—Composite material consisting of a mixture of organic and inorganic materials
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- C08J2323/00—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers
- C08J2323/02—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers not modified by chemical after treatment
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- C08J2405/00—Characterised by the use of polysaccharides or of their derivatives not provided for in groups C08J2401/00 or C08J2403/00
- C08J2405/16—Cyclodextrin; Derivatives thereof
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- D06M2101/16—Synthetic fibres, other than mineral fibres
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Abstract
The invention belongs to the technical fields of high-performance lithium battery isolating film, and in particular to a kind of composite isolated film and preparation method thereof.The invention discloses a kind of preparation methods of composite isolated film, comprising the following steps: step 1, after mixing pretreated metal-oxide powder and organic lubricant, ball milling dispersion obtains surface-hydrophobicized metal oxide；Step 2 mixes the surface-hydrophobicized metal oxide, binder and water, obtains coating slurry；Step 3, the surface that the coating slurry is coated in isolation film, it is dry, obtain composite isolated film.This application provides a kind of composite diaphragms, the big technological deficiency of the water imbibition for solving traditional isolation film.
Description
Technical field
The invention belongs to the technical fields of high-performance lithium battery isolating film, and in particular to a kind of composite isolated film and its preparation
Method.
Background technique
Isolation film is received significant attention as the important component of lithium ion battery, the high performance of lithium ion battery with
The property of isolation film is closely bound up, especially big multiplying power, fast charging and discharging lithium battery in, the performance requirement of isolation film is more bright
It is aobvious.There is vital influence to the performance of actual battery in view of isolation film, it is steady must to have good chemistry, electrochemistry
Interface phase qualitative and during repeated charge to electrolyte holding height wellability, between barrier material and electrode
Capacitive, isolation film have larger impact to the charge-discharge performance of lithium ion battery, cycle performance etc. to the retentivity of electrolyte.This
Outside, with the fast development of power vehicle, safety to lithium-ion-power cell, especially heat resistance proposes higher want
One of ask, and influence the key factor of security of lithium-ion-power cell be exactly isolation film safety.
For lithium ion battery, influence of the moisture content of raw material to the performance of battery is great.Ceramics aqueous at present apply
The important component that isolation film is power battery isolation film is covered, by coating one layer on the surface of common polyolefine isolating film
Functional layer containing ceramic powder greatly improves the electrolyte imbibition rate of isolation film, guarantor's liquid rate, isolation film internal resistance decline, electricity
The cycle performance in pond improves.But since coat is the mixture of water-soluble polymer and ceramic powder, in wet condition can
Substantially moisture absorption, making the moisture content of isolation film is more than 2000ppm, much higher than the SC service ceiling of lithium battery isolation membrane, although isolation film
Also needing drying to remove water before, but mutually glue glutinous surface layer to bring the peeling of isolation film surface covering in separation,
This damage is irreversible.In addition the effect of dry water removal is limited, it is also necessary to and longer time can be only achieved requirement, by
This improves the performance on coated insulation film surface, and the water imbibition for reducing coated insulation film itself is to improve the major technique of this problem
Method.
Future, with the fast development of Large-scale Mobile power supply, electric car, power battery, power battery lithium battery every
Usage amount from film will increase substantially, and high-performance lithium battery isolating film will become necessary, and it is electric to lithium is improved to reduce isolation film water suction
Pond performance is significant.Using environmentally protective method preparation there is the battery isolating film of low water absorbable will become from now on
Important development direction.
Summary of the invention
It is an object of the invention to overcome the effect of dry water removal in the prior art limited, provide a kind of with low water absorbable
Composite diaphragm.
Another object of the present invention be to provide a kind of low water absorbable, preparation method it is simple, the preparation side of composite isolated film
Method.
To achieve the goals above, technical scheme is as follows:
The invention discloses a kind of preparation methods of composite isolated film, comprising the following steps:
Step 1, after pretreated metal-oxide powder and organic lubricant are mixed, ball milling dispersion obtains surface
The metal oxide of hydrophobization；
Step 2 mixes the surface-hydrophobicized metal oxide, binder and water, obtains coating slurry；
Step 3, the surface that the coating slurry is coated in isolation film, it is dry, obtain composite isolated film.
Preferably, metal-oxide powder is selected from one of aluminium oxide, calcium oxide, magnesia and titanium dioxide or more
Kind.
Preferably, the pretreatment includes calcining the metal-oxide powder, the temperature of the calcining in step 1
Degree is 1300~1800 DEG C；The time of the calcining is 12-48h；The average grain diameter of the metal-oxide powder be 0.5~
1.5μm。
Wherein, when pretreatment, metal-oxide powder obtains full alpha-crystal form metal oxide powder using the method for high-temperature calcination
Body, and utilize the water suction of calcination temperature and the crystallization integrity adjustment fission itself of calcination time regulation metal-oxide powder
Property.
Specifically, being cooled to room temperature after metal-oxide powder calcining, the mixing of step 1 is carried out.
Specifically, ball milling dispersion is specially to add pretreated metal-oxide powder and organic lubricant in step 1
Enter in ball mill, the quantitative proportion of big ball and bead is 3:5 in ball mill, and ball milling 12~24 hours, obtain after sieving at room temperature
Surface-hydrophobicized metal oxide.
Preferably, the organic lubricant is selected from stearic acid, oleic acid, zinc stearate, magnesium stearate, tristearin in step 1
One of sour calcium, barium stearate, oleic acid acid acyl and erucyl amide are a variety of.
Wherein, in step 1, ball milling dispersion is blended in calcined metal-oxide powder and organic lubricant, so that forging
Hydrophobic lubricant layer is contained on metal-oxide powder surface after burning, forms the high hydrophobic metal oxide powder in surface.
Preferably, in step 1, the mass ratio of the pretreated metal-oxide powder and the organic lubricant
For 100:(3~12).
Preferably, in step 2, the mass ratio of the surface-hydrophobicized metal oxide and the binder solution is
(10~200): 1.
It is furthermore preferred that the mass ratio of the surface-hydrophobicized metal oxide and the binder is (17 in step 2
~23): 1.
Preferably, the preparation method of the binder includes obtaining cyclodextrin and oxidant hybrid reaction after dry
Binder；The reaction temperature is 70~100 DEG C；The reaction time is 24~48 hours；The cyclodextrin and the oxidation
The mass ratio of agent is 1:1.5~5.
Specifically, the binder is the controllable water-soluble binder of water imbibition, the oxidation of cyclodextrin is for adjusting surface
The water imbibition of the metal oxide of hydrophobization.
Specifically, the cyclodextrin is beta-cyclodextrin；The oxidant is hydrogen peroxide.
Preferably, the solubility of the binder in water is 1.85~6wt%, i.e., binder reaches in 100g water
When saturation, the parts by weight percentage of binder is 1.85%-6%.
Specifically, being mixed into and being stirred in step 2, mixing time is 12 hours.
Preferably, the isolation film is polyolefin micropore barrier diaphragm.
Specifically, the surface that the coating slurry is coated in isolation film is specifically included immersion or coating method in step 3
It realizes；The step of mode of immersion includes being immersed directly in polyolefin micropore barrier diaphragm in the coating slurry, wherein immersion
Time is 5~60min.
Specifically, the temperature of the drying of step 3 is 80~110 DEG C；Drying time is 5~60min.
Specifically, the isolation film of step 3 is polyolefin micropore barrier diaphragm；Polyolefin micropore barrier diaphragm is single-layer polypropylene or highly dense
The compound micro-pore septum of degree two layers of PP/PE of polyethylene micropore diaphragm compound micro-pore septum or three layers of PP/PE/PP,
According to heating consumers method, that is, wet process manufacture polyolefin micropore barrier diaphragm or according to melt drawn principle, that is, dry method
The polyolefin micropore barrier diaphragm of manufacture or the non-woven polyolefin composite microporous separator prepared by spinning process.
The present invention also provides a kind of composite isolated films, including composite isolated film made from the preparation method.
Preferably, the water imbibition of the composite isolated film is lower than 400~2000ppm.
Beneficial effects of the present invention are as follows, and the composite isolated film preparation method of the application aoxidizes surface-hydrophobicized metal
Object selects suitable auxiliary agent in water-soluble polymer binder, can stablize the painting of storage by the method configuration of high speed dispersion
Cover slurry.By coating method, slurry is coated on isolation film, can be obtained the compound organic/inorganic diaphragm of low water absorbable,
Surface-hydrophobicized metal oxide can regulate and control from the water imbibition of powder itself, and binder itself has water imbibition, binder
Water imbibition regulates and controls the water imbibition that these two aspects inhibits diaphragm.The composite isolated film of the application can provide efficient anti-flammability and higher
Dimensional stability, the simple process of the preparation method of the composite isolated film of the application, low for equipment requirements, condition is easily-controllable, at
This is cheap, is suitable for industrialized production.
It is a discovery of the invention that surface-hydrophobicized metal oxide, binder and water are directly mixed, reduce intermediate drying
The step of separation, by the re-coating of mixed coating slurry on isolation film, drying can be obtained composite isolated film, preparation side
Method simple process, low for equipment requirements, condition is easily-controllable, low in cost, is suitable for industrialized production.Wherein, surface-hydrophobicized gold
Membrane surface can be laid in by belonging to oxide, controlled the contraction of coat, after coating, can be effectively reduced the water suction of composite isolated film
Property.Aqueous binders system has non-volatile, pollution-free, high stable feature, keeps stabilization to deposit within the coating work range time
There is a phenomenon where settle.The surface of composite isolated film after coating is smooth, coats the saturation water suction of composite isolated film
Rate is only 400ppm, heat resistance can be improved the water imbibition that all kinds of diaphragms used today are substantially improved to 170 DEG C or more and
Heat resistance.
Specific embodiment
This application provides a kind of composite diaphragms, the big technological deficiency of the water imbibition for solving traditional isolation film.
Below by the technical scheme in the embodiment of the application is clearly and completely described, it is clear that described implementation
Example is merely a part but not all of the embodiments of the present application.Based on the embodiment in the application, this field is common
Technical staff's every other embodiment obtained without making creative work belongs to the model of the application protection
It encloses.
Wherein, it is commercially available or self-control that following embodiment is raw materials used.
Embodiment 1
Present embodiments provide the first composite isolated film, specific preparation process are as follows:
S11, the aluminium oxide of 0.5 μm of average grain diameter (D50) is selected to calcine 12 hours at 1400 DEG C of high temperature Muffle furnace, after calcining
Furnace cooling obtains pretreated alumina powder.
S12, pretreated alumina powder and stearic acid are added in ball mill jointly with the mass ratio of 100:3,
The number ratio of big ball (5~8mm of diameter) and bead (2~4mm of diameter) is 3:5 in ball mill, at room temperature ball milling 12 hours, mistake
Surface-hydrophobicized aluminium oxide is obtained after sieve.
S13, binder, water are uniformly mixed at room temperature with surface-hydrophobicized aluminium oxide, stir 12 hours, is applied
Cover slurry, wherein the preparation method of binder is to react beta-cyclodextrin 24 hours at 70 DEG C with hydrogen peroxide, after drying to obtain the final product
To binder.The mass ratio of cyclodextrin and hydrogen peroxide is 1:1.5, and the solubility of cyclodextrin in water is after reaction
1.85wt%；The mass ratio of surface-hydrophobicized aluminium oxide and binder is 17:1.
S14, dry method PP microporous barrier is immersed in 30min in coating slurry, 90 DEG C of dryings in a vacuum drying oven after taking-up
30min prepares composite isolated film.
Water imbibition detection carried out to the composite isolated film of the present embodiment, the water imbibition of the composite isolated film of the present embodiment compared with
It is low, reach 1700ppm, dimensional stability improves obvious.
Embodiment 2
Present embodiments provide second of composite isolated film, specific preparation process are as follows:
S21, select the aluminium oxide of 1.5 μm of average grain diameter (D50) to calcine 48 hours at 1700 DEG C of high temperature Muffle, after calcining with
Furnace is cooling, obtains pretreated alumina powder.
S22, pretreated alumina powder and oleic acid are added in ball mill jointly with the mass ratio of 100:12, ball
The number ratio of big ball (5~8mm of diameter) and bead (2~4mm of diameter) is 3:5 in grinding machine, at room temperature ball milling 24 hours, sieving
Surface-hydrophobicized aluminium oxide is obtained afterwards.
S23, binder, water are uniformly mixed at room temperature with surface-hydrophobicized aluminium oxide, stir 12 hours, is applied
Cover slurry, wherein the preparation method of binder is to react beta-cyclodextrin 48 hours at 100 DEG C with hydrogen peroxide, is after dry
Obtain binder.The mass ratio of cyclodextrin and hydrogen peroxide is 1:5, and the solubility of cyclodextrin in water is 6wt% after reaction；Table
The aluminium oxide of face hydrophobization and the mass ratio of binder are 23:1.
S24, dry method PE microporous barrier is immersed in 30min in coating slurry, 90 DEG C of dryings in a vacuum drying oven after taking-up
30min prepares composite isolated film.
Water imbibition detection carried out to the composite isolated film of the present embodiment, the water imbibition of the composite isolated film of the present embodiment compared with
It is low, reach 2000ppm, dimensional stability improves obvious.
Embodiment 3
Present embodiments provide the third composite isolated film, specific preparation process are as follows:
S31, the aluminium oxide of 1 μm of average grain diameter (D50) is selected to calcine 24 hours at 1500 DEG C of high temperature Muffle, with furnace after calcining
It is cooling, obtain pretreated alumina powder.
S32, ball mill is added with the mass ratio of 100:8 in pretreated alumina powder and zinc stearate jointly
In, the number ratio of big ball (5~8mm of diameter) and bead (2~4mm of diameter) is 3:5 in ball mill, and ball milling 48 is small at room temperature
When, surface-hydrophobicized aluminium oxide is obtained after sieving.
S33, binder, water are uniformly mixed at room temperature with surface-hydrophobicized aluminium oxide, stir 12 hours, is applied
Cover slurry, wherein the preparation method of binder is to react beta-cyclodextrin 48 hours at 90 DEG C with hydrogen peroxide, after drying to obtain the final product
To binder.The mass ratio of cyclodextrin and hydrogen peroxide is 1:3, and the solubility of cyclodextrin in water is 4wt% after reaction；Surface
The aluminium oxide of hydrophobization and the mass ratio of binder are 20:1.
S34: being immersed in 30min in coating slurry for PP/PE composite micro porous film, after taking-up in a vacuum drying oven 90 DEG C it is dry
Dry 30min, prepares composite isolated film.
Water imbibition detection carried out to the composite isolated film of the present embodiment, the water imbibition of the composite isolated film of the present embodiment compared with
It is low, reach 1100ppm, dimensional stability improves obvious.
Embodiment 4
Present embodiments provide the 4th kind of composite isolated film, specific preparation process are as follows:
S41, select the aluminium oxide of 1 μm of average grain diameter (D50) to calcine 24 hours at 1300 DEG C of high temperature Muffle furnace, after calcining with
Furnace is cooling, obtains pretreated alumina powder.
S42, ball mill is added with the mass ratio of 100:6 in pretreated alumina powder and magnesium stearate jointly
In, the number ratio of big ball (5~8mm of diameter) and bead (2~4mm of diameter) is 3:5 in ball mill, and ball milling 48 is small at room temperature
When, surface-hydrophobicized aluminium oxide is obtained after sieving.
S43, binder, water are uniformly mixed at room temperature with surface-hydrophobicized aluminium oxide, stir 12 hours, is applied
Cover slurry, wherein the preparation method of binder is to react beta-cyclodextrin 48 hours at 80 DEG C with hydrogen peroxide, after drying to obtain the final product
To binder.The mass ratio of cyclodextrin and hydrogen peroxide is 1:3, and the solubility of cyclodextrin in water is 4wt% after reaction；Surface
The aluminium oxide of hydrophobization and the mass ratio of binder are 20:1.
S44: being immersed in 30min in coating slurry for PP/PE/PP composite micro porous film, in a vacuum drying oven 90 after taking-up
DEG C dry 30min, prepares composite isolated film.
Water imbibition detection carried out to the composite isolated film of the present embodiment, the water imbibition of the composite isolated film of the present embodiment compared with
It is low, reach 600ppm, dimensional stability improves obviously, and the performance improvement of the composite isolated film of the present embodiment is best.
Embodiment 5
Present embodiments provide the 5th kind of composite isolated film, specific preparation process are as follows:
S51, the aluminium oxide of 1.2 μm of average grain diameter (D50) is selected to calcine 24 hours at 1300 DEG C of high temperature Muffle furnace, after calcining
Furnace cooling obtains pretreated alumina powder.
S52, ball mill is added with the mass ratio of 100:3 in pretreated alumina powder and calcium stearate jointly
In, the number ratio of big ball (5~8mm of diameter) and bead (2~4mm of diameter) is 3:5 in ball mill, and ball milling 48 is small at room temperature
When, surface-hydrophobicized aluminium oxide is obtained after sieving.
S53, binder, water are uniformly mixed at room temperature with surface-hydrophobicized aluminium oxide, stir 12 hours, is applied
Cover slurry, wherein the preparation method of binder is to react beta-cyclodextrin 48 hours at 90 DEG C with hydrogen peroxide, after drying to obtain the final product
To binder.The mass ratio of cyclodextrin and hydrogen peroxide is 1:3, and the solubility of cyclodextrin in water is 3wt% after reaction；Surface
The aluminium oxide of hydrophobization and the mass ratio of binder are 14:1.
S54, wet process PP composite micro porous film is immersed in 30min in coating slurry, 90 DEG C in a vacuum drying oven after taking-up
Dry 30min, prepares composite isolated film.
Water imbibition detection carried out to the composite isolated film of the present embodiment, the water imbibition of the composite isolated film of the present embodiment compared with
It is low, reach 700ppm, dimensional stability improves obvious.
Embodiment 6
Present embodiments provide the 6th kind of composite isolated film, specific preparation process are as follows:
S6 selects the aluminium oxide of 0.7 μm of average grain diameter (D50) to calcine 24 hours at 1600 DEG C of high temperature Muffle furnace, after calcining with
Furnace is cooling, obtains pretreated alumina powder.
Pretreated alumina powder and barium stearate are added in ball mill S62 jointly with the mass ratio of 100:6,
The number ratio of big ball (5~8mm of diameter) and bead (2~4mm of diameter) is 3:5 in ball mill, at room temperature ball milling 48 hours, mistake
Surface-hydrophobicized aluminium oxide is obtained after sieve.
S63, binder, water are uniformly mixed at room temperature with surface-hydrophobicized aluminium oxide, stir 12 hours, is applied
Cover slurry, wherein the preparation method of binder is to react beta-cyclodextrin 48 hours at 80 DEG C with hydrogen peroxide, after drying to obtain the final product
To binder.The mass ratio of cyclodextrin and hydrogen peroxide is 1:3, and the solubility of cyclodextrin in water is 4wt% after reaction；Surface
The aluminium oxide of hydrophobization and the mass ratio of binder are 11:1.
S64, polypropylene non-woven fabric composite micro porous film is immersed in 30min in coating slurry, in vacuum oven after taking-up
In 90 DEG C of dry 30min, prepare composite isolated film.
Water imbibition detection carried out to the composite isolated film of the present embodiment, the water imbibition of the composite isolated film of the present embodiment compared with
It is low, reach 1300ppm, dimensional stability improves obvious.The present embodiment is using polypropylene non-woven fabric composite micro porous film, aperture
Larger, voidage is higher.
Embodiment 7
Present embodiments provide the 7th kind of composite isolated film, specific preparation process are as follows:
S71, the aluminium oxide of 0.9 μm of average grain diameter (D50) is selected to calcine 36 hours at 1500 DEG C of high temperature Muffle furnace, after calcining
Furnace cooling obtains pretreated alumina powder.
S72, ball mill is added with the mass ratio of 100:6 in pretreated alumina powder and magnesium stearate jointly
In, the number ratio of big ball (5~8mm of diameter) and bead (2~4mm of diameter) is 3:5 in ball mill, and ball milling 48 is small at room temperature
When, surface-hydrophobicized aluminium oxide is obtained after sieving.
S73, binder, water are uniformly mixed at room temperature with surface-hydrophobicized aluminium oxide, stir 12 hours, is applied
Cover slurry, wherein the preparation method of binder is to react beta-cyclodextrin 48 hours at 80 DEG C with hydrogen peroxide, after drying to obtain the final product
To binder.The mass ratio of cyclodextrin and hydrogen peroxide is 1:3, and the solubility of cyclodextrin in water is 4wt% after reaction；Surface
The aluminium oxide of hydrophobization and the mass ratio of binder are 20:1.
S74, PP/PE/PP composite micro porous film is impregnated into 30min in the slurry, after taking-up in a vacuum drying oven 90 DEG C it is dry
Dry 30min, prepares composite isolated film.
Water imbibition detection carried out to the composite isolated film of the present embodiment, the water imbibition of the composite isolated film of the present embodiment compared with
It is low, reach 600ppm, dimensional stability improves obvious.
Embodiment 8
Present embodiments provide the 8th kind of composite isolated film, specific preparation process are as follows:
S81, select the aluminium oxide of 1 μm of average grain diameter (D50) to calcine 24 hours at 1700 DEG C of high temperature Muffle furnace, after calcining with
Furnace is cooling, obtains pretreated alumina powder.
S82, ball mill is added with the mass ratio of 100:6 in pretreated alumina powder and oleic acid acid acyl jointly
In, the number ratio of big ball (5~8mm of diameter) and bead (2~4mm of diameter) is 3:5 in ball mill, and ball milling 48 is small at room temperature
When, surface-hydrophobicized aluminium oxide is obtained after sieving.
S83, binder, water are uniformly mixed at room temperature with surface-hydrophobicized aluminium oxide, stir 12 hours, is applied
Cover slurry, wherein the preparation method of binder is to react beta-cyclodextrin 48 hours at 80 DEG C with hydrogen peroxide, after drying to obtain the final product
To binder.The mass ratio of cyclodextrin and hydrogen peroxide is 1:3, and the solubility of cyclodextrin in water is 4wt% after reaction；Surface
The aluminium oxide of hydrophobization and the mass ratio of binder are 13:1.
S84, wet process PE microporous barrier is immersed in 30min in coating slurry, 90 DEG C of dryings in a vacuum drying oven after taking-up
30min prepares composite isolated film.
Water imbibition detection carried out to the composite isolated film of the present embodiment, the water imbibition of the composite isolated film of the present embodiment compared with
It is low, reach 700ppm, dimensional stability improves obvious.
Embodiment 9
Present embodiments provide the 9th kind of composite isolated film, specific preparation process are as follows:
S91, select the aluminium oxide of 1 μm of average grain diameter (D50) to calcine 24 hours at 1700 DEG C of high temperature Muffle furnace, after calcining with
Furnace is cooling, obtains pretreated alumina powder.
S92, ball mill is added with the mass ratio of 100:4 in pretreated alumina powder and erucyl amide jointly
In, the number ratio of big ball (5~8mm of diameter) and bead (2~4mm of diameter) is 3:5 in ball mill, and ball milling 48 is small at room temperature
When, surface-hydrophobicized aluminium oxide is obtained after sieving.
S93, binder, water are uniformly mixed at room temperature with surface-hydrophobicized aluminium oxide, stir 12 hours, is applied
Cover slurry, wherein the preparation method of binder is to react beta-cyclodextrin 48 hours at 80 DEG C with hydrogen peroxide, after drying to obtain the final product
To binder.The mass ratio of cyclodextrin and hydrogen peroxide is 1:3, and the solubility of cyclodextrin in water is 4wt% after reaction；Surface
The aluminium oxide of hydrophobization and the mass ratio of binder are 13:1.
S94, wet process PE microporous barrier is immersed in 30min in coating slurry, 90 DEG C of dryings in a vacuum drying oven after taking-up
30min prepares composite isolated film.
Water imbibition detection carried out to the composite isolated film of the present embodiment, the water imbibition of the composite isolated film of the present embodiment compared with
It is low, reach 400ppm, dimensional stability improves obvious.
Comparative example 1
The first comparative example is present embodiments provided, commercially available PP microporous barrier, thickness 20um are directly acquired.
Comparative example 2
Present embodiments provide second of comparative example, specific preparation process are as follows:
D21, select the aluminium oxide of 1 μm of average grain diameter (D50) to calcine 24 hours at 1300 DEG C of high temperature Muffle furnace, after calcining with
Furnace is cooling, obtains calcined alumina.
D22, calcined aluminium oxide is added in ball mill, big ball (5~8mm of diameter) and bead (diameter 2 in ball mill
~4mm) number ratio be 3:5, ball milling 48 hours, obtain surface-hydrophobicized aluminium oxide at room temperature after sieving.
D23, binder, water are uniformly mixed at room temperature with surface-hydrophobicized aluminium oxide, stir 12 hours, is applied
Cover slurry, wherein the preparation method of binder is to react beta-cyclodextrin 48 hours at 80 DEG C with hydrogen peroxide, after drying to obtain the final product
To binder.The mass ratio of cyclodextrin and hydrogen peroxide is 1:3, and the solubility of cyclodextrin in water is 4wt% after reaction；Surface
The aluminium oxide of hydrophobization and the mass ratio of binder are 20:1.
D24, PP/PE/PP composite micro porous film is immersed in 30min in coating slurry, in a vacuum drying oven 90 after taking-up
DEG C dry 30min, prepares comparative example 2.
Water imbibition detection is carried out to the product of this comparative example, the water imbibition of the product of this comparative example is up to 2500ppm.
Embodiment 4 and comparative example 1 and comparative example 2 is selected to be tested for the property experiment, the results are shown in Table 1, and table 1 is
Embodiment 4, the gas permeability of the composite isolated film of comparative example 1 and comparative example 2, coating thickness, oxygen index (OI) and flame retardant rating table,
In, the "-" of table 1 indicates that data can not measure.
Table 1
By the result of above-mentioned performance test analysis it is found that the preparation method of composite isolated film provided in an embodiment of the present invention,
It can be obtained composite isolated film, so that the composite isolated film of the application has extremely low water imbibition, dimensional stability, improve it
Safety.In addition, the composite isolated film preparation method simple process of the present embodiment, low for equipment requirements, condition is easily-controllable, at low cost
It is honest and clean, it is suitable for industrialized production.
The above is only the preferred embodiment of the application, it is noted that for the ordinary skill people of the art
For member, under the premise of not departing from the application principle, several improvements and modifications can also be made, these improvements and modifications are also answered
It is considered as the protection scope of the application.
Claims (10)
1. a kind of preparation method of composite isolated film, which comprises the following steps:
Step 1, after pretreated metal-oxide powder and organic lubricant are mixed, ball milling dispersion obtains surface hydrophobicity
The metal oxide of change；
Step 2 mixes the surface-hydrophobicized metal oxide, binder and water, obtains coating slurry；
Step 3, the surface that the coating slurry is coated in isolation film, then dry, obtain composite isolated film.
2. preparation method according to claim 1, which is characterized in that in step 1, the pretreatment includes by the metal
Oxide powder calcining, the temperature of the calcining are 1300~1800 DEG C；The time of the calcining is 12-48h；The metal oxygen
The average grain diameter of compound powder is 0.5~1.5 μm.
3. preparation method according to claim 1, which is characterized in that in step 1, the organic lubricant is selected from tristearin
One of acid, oleic acid, zinc stearate, magnesium stearate, calcium stearate, barium stearate, oleic acid acid acyl and erucyl amide are a variety of.
4. preparation method according to claim 1, which is characterized in that in step 1, the pretreated metal oxide
The mass ratio of powder and the organic lubricant is 100:(3~12).
5. preparation method according to claim 1, which is characterized in that in step 2, the surface-hydrophobicized metal oxidation
The mass ratio of object and the binder is (10~200): 1.
6. preparation method according to claim 5, which is characterized in that the preparation method of the binder includes by cyclodextrin
With oxidant hybrid reaction, binder is obtained after dry；The reaction temperature is 70~100 DEG C；The reaction time be 24~
48 hours；The mass ratio of the cyclodextrin and the oxidant is 1:(1.5~5).
7. preparation method according to claim 1, which is characterized in that the solubility of the binder in water be 1.85~
6wt%.
8. preparation method according to claim 7, which is characterized in that the isolation film is polyolefin micropore barrier diaphragm.
9. a kind of composite isolated film, which is characterized in that including made from the preparation method as described in claim 1-8 any one
Composite isolated film.
10. the water imbibition of composite isolated film according to claim 9, the composite isolated film is lower than 400~2000ppm.
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