CN109422890A - A kind of composite polypropylene microporous barrier and its preparation method and application - Google Patents
A kind of composite polypropylene microporous barrier and its preparation method and application Download PDFInfo
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- CN109422890A CN109422890A CN201710744074.XA CN201710744074A CN109422890A CN 109422890 A CN109422890 A CN 109422890A CN 201710744074 A CN201710744074 A CN 201710744074A CN 109422890 A CN109422890 A CN 109422890A
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- C08J7/00—Chemical treatment or coating of shaped articles made of macromolecular substances
- C08J7/04—Coating
- C08J7/0427—Coating with only one layer of a composition containing a polymer binder
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- C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
- C08J5/18—Manufacture of films or sheets
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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
- H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
- H01M50/40—Separators; Membranes; Diaphragms; Spacing elements inside cells
- H01M50/409—Separators, membranes or diaphragms characterised by the material
- H01M50/411—Organic material
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
- H01M50/40—Separators; Membranes; Diaphragms; Spacing elements inside cells
- H01M50/409—Separators, membranes or diaphragms characterised by the material
- H01M50/449—Separators, membranes or diaphragms characterised by the material having a layered structure
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- C—CHEMISTRY; METALLURGY
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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
- C08J2323/10—Homopolymers or copolymers of propene
- C08J2323/12—Polypropene
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- C08J2433/00—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Derivatives of such polymers
- C08J2433/04—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Derivatives of such polymers esters
- C08J2433/06—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Derivatives of such polymers esters of esters containing only carbon, hydrogen, and oxygen, the oxygen atom being present only as part of the carboxyl radical
- C08J2433/10—Homopolymers or copolymers of methacrylic acid esters
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- C08J2483/00—Characterised by the use of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing silicon with or without sulfur, nitrogen, oxygen, or carbon only; Derivatives of such polymers
- C08J2483/04—Polysiloxanes
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Abstract
The invention discloses a kind of composite polypropylene microporous barriers and its preparation method and application, additionally provide a kind of device for preparing composite polypropylene microporous barrier.The preparation method is to introduce coat by coating system on diaphragm one or both sides surface in the preparation process of Biaxially oriented polypropylene microporous barrier, coat is passed through in vertical/horizontal both direction or only to be stretched in a lateral direction, realizes the preparation of composite polypropylene microporous barrier.The method simplifies the production technology of composite polypropylene microporous barrier, improves the performance of microporous polypropylene membrane.The composite polypropylene microporous barrier is for that since coat is the polymer or composition that can form gel with electrolyte, can improve the circulation and security performance of lithium battery in lithium battery.The composite polypropylene microporous barrier is separated for gas, and since infiltration coefficient of the coat to gas with various is different, the separation and enrichment of gas with various may be implemented.
Description
Technical field
The invention belongs to microporous membrane technology fields, and in particular to a kind of composite polypropylene microporous barrier and preparation method thereof and use
On the way.
Background technique
MIcroporous polyolefin film is a kind of polymeric membrane, is perforated membrane of the aperture between 5nm~1000nm, by widely
Applied to poromeric material such as diaper, medical dressing, clothes wadding etc., liquid separation material, ultrafiltration material, film filter material
In material and the fields such as supercapacitor and battery diaphragm material.
There are mainly two types of the preparation methods of existing MIcroporous polyolefin film, one is melting extrusion pulling method (dry method), one
Kind is thermally induced phase separation (TIPS, wet process).Wherein, dry-stretch process is further divided into simple tension technique and two-way drawing
Stretching process.Wet method preparation process is to be added in polyolefin higher boiling small-molecule substance as pore-foaming agent and be dissolved in organic solvent
Slab is formed, then cooling occurs mutually to separate, and extracts small molecule with organic solvent, forms microcellular structure after carrying out biaxial tension.
Using solvent, microporous barrier, direction intensity is relatively high and obtain and widely answer in length and breadth due to not needing for dry method stretch processes
With.
Dry method stretch processes are mainly by the way that the beta crystal modifier with nucleation, shape are added in polypropylene
At the polypropylene diaphragm with high-beta crystal content, during stretching, the transformation of β crystal orientation α crystalline substance occurs, utilizes polypropylene difference
The difference of density forms microcellular structure between phase, for producing single-layer polypropylene microporous barrier.First research (CN1062357A)
Middle to propose a kind of microporous barrier that uniformly original diaphragm drawn obtains of the polypropylene with high beta-crystalline form content, the microporous barrier is to adopt
It is obtained with the method for nucleating agent is added in acrylic resin with Beta-crystalline polyacrylic with method prepared by melt-processed in film forming
Diaphragm.The diaphragm being prepared using the method as lithium ion battery separator in application, since polypropylene is low table
Face can non-polar material, the carbonates polarity electrolyte in battery is poor to the wellability of non-polar polypropylene diaphragm.Meanwhile
It is also easy to cause to be bonded not due to polar difference between nonpolar polypropylene diaphragm and battery pole piece in battery assembling process
It is good.These factors can all influence capacity, circulation and the service performance of battery.Therefore, many researchs are devoted to connect by surface
Branch polymerization is coated to be modified polyolefin micropore barrier diaphragm and improves the circulation of battery and service performance on surface.
Summary of the invention
In order to solve the deficiencies in the prior art, an object of the present invention be to provide a kind of composite polypropylene microporous barrier and its
Preparation method and purposes have been prepared in the preparation method described by the way of introducing coating liquid before cross directional stretch
Composite polypropylene microporous barrier, the composite polypropylene microporous barrier include biaxial tension polypropylene microporous basal layer and be located at substrate
The simple tension coat of layer at least one side.When the composite polypropylene microporous barrier is used for the diaphragm of lithium ion battery, coat
Gel can be formed in the electrolytic solution, improve electrolyte to the heat resistance of the wellability of diaphragm or raising polypropylene microporous basal layer
Energy.When the composite polypropylene microporous barrier is separated for gas, coat is different to the transmission coefficient of gas with various, may be implemented
The separation and enrichment of gas.
The second object of the present invention is to provide a kind of device for preparing composite polypropylene microporous barrier.
The third object of the present invention is to provide a kind of lithium ion battery separator comprising above-mentioned composite polypropylene micropore
Film.
The fourth object of the present invention is to provide a kind of gas separation membrane comprising above-mentioned composite polypropylene microporous barrier.
The purpose of the present invention is what is be achieved through the following technical solutions:
The first aspect of the invention is to provide a kind of preparation method of composite polypropylene microporous barrier, the preparation method packet
Include following steps:
(S1) nucleating agent that beta crystal can be promoted to be formed is added into polypropylene；
(S2) by the polypropylene for being mixed with nucleating agent of step (S1) through melting extrusion, molding obtains high β epitaxial piece；
(S3) high β epitaxial piece is obtained into longitudinal stretching film through longitudinal stretching, coating liquid is applied to the longitudinal stretching film
One or both sides surface；
(S4) the longitudinal stretching film for being coated with coating liquid obtains the composite polypropylene microporous barrier through cross directional stretch.
According to the present invention, may also include the steps of: between the step of preparation method (S2) and step (S3)
Coating liquid is applied to the one or both sides surface of the resulting high β epitaxial piece of step (S2) by (S2 '), is coated with
The high β epitaxial piece of coating liquid.
In the present invention, the composite polypropylene microporous barrier refers to high β epitaxial piece in the longitudinal drawing obtained through longitudinal stretching
The one or both sides surface coating coating liquid for stretching film, through after stretching horizontally, obtaining composite polypropylene microporous barrier；Alternatively, described
Composite polypropylene microporous barrier refers to be indulged after longitudinal stretching in the one or both sides surface of high β epitaxial piece coating coating liquid
To stretched film；It is coated with coating liquid on the one or both sides surface of longitudinal stretching film, through after stretching horizontally, it is micro- to obtain composite polypropylene
Pore membrane.
According to the present invention, in step S1, the polypropylene can be homopolypropylene, be also possible to copolymer polypropylene；
Preferably, the polyacrylic isotacticity is 90-98%；Melt index is 1-10g/10min.
Preferably, the polyacrylic isotacticity is 95-98%；Melt index is 2-5g/10min.
According to the present invention, in step S1, the nucleating agent that beta crystal can be promoted to be formed is imitated selected from nucleation with higher
Rate, and nucleating agent of the beta crystal content 50% or more under conditions of stationary crystallization.
As illustratively, the nucleating agent is selected from commercial goods or is synthesized according to method known in the art
Product.
According to the present invention, the type of the nucleating agent and nucleation efficiencies can be found in document (Varga J.Journal of
Macromolecular Science:Physics 2002,41,1121.)。
As illustratively, the nucleating agent either one pack system small organic molecule such as N, N- dicyclohexyl is to benzene two
Formamide, N, N- dicyclohexyl -2,6 naphthalene diamides or γ-Kui bifurcation pyridine etc., be also possible to double/multi-component inorganic salts such as oneself two
Acid and/or the hydrazine salt of suberic acid, the calcium salt of pimelic acid and/or suberic acid, the calcium salt of tetrahydrophthalic anhydride or barium salt, hexahydrophthalic anhydride
Calcium salt or barium salt etc.；The nucleating agent can be used in mixed way, it will be understood by those skilled in the art that the mixing ratio of the nucleating agent
Example does not have particular/special requirement, is suitable for system of the present invention.
According to the present invention, in step S1, the nucleating agent that beta crystal can be promoted to be formed is with polyacrylic amount ratio
0.001-0.1wt%.
According to the present invention, in step S2, the melting extrusion carries out preferably in screw extruder；Those skilled in the art
It is appreciated that being not particularly limited to the screw extruder, it can be single screw extrusion machine and be also possible to double screw extruder,
Suitable for system of the present invention.
According to the present invention, in step S2, the melting temperature of the screw extruder is 200~260 DEG C, it is preferable that described
The melting temperature of screw extruder is 220~250 DEG C；
According to the present invention, in step S2, the molding is preferably formed through die head；It will be understood by those skilled in the art that right
The die head is not particularly limited, and be can be adjustable die head and is also possible to uncontrollable die head, and institute of the present invention is suitable for
The system stated.
According to the present invention, further include being crystallized on curtain coating slab roller in step S2, after the molding, obtain high β epitaxial piece.
According to the present invention, in step S2, the high β epitaxial piece with a thickness of 80-300 microns, it is preferable that the high β is brilliant
Diaphragm with a thickness of 100-200 microns；
According to the present invention, in step S2, the content of β crystalline substance is higher than 80% in the high β epitaxial piece, it is preferable that the high β is brilliant
The content of β crystalline substance is higher than 85% in diaphragm；
According to the present invention, in step S3, the temperature of the longitudinal stretching is 60-120 DEG C, it is preferable that the longitudinal stretching
Temperature be 80-110 DEG C；The multiplying power of the longitudinal stretching is 2.5-5.5 times, it is preferable that the multiplying power of the longitudinal stretching is 3-5
Times；
According to the present invention, in step S3 and step S2 ', the coating liquid include using organic solvent as the solution of medium or with
Water is the solution or dispersion liquid of medium；
Described using organic solvent as the solution of medium includes that polymer or polymer composition are dissolved shape with organic solvent
At solution；Described using water as the solution of medium includes that water-soluble polymer or water-soluble polymer composition are dissolved shape with water
At solution；Described by the dispersion liquid of medium of water includes by polymer not soluble in water or polymer composition not soluble in water
The lotion of polymer or polymer composition is obtained by the method for emulsion polymerization, or by polymer not soluble in water or is not dissolved in
The aqueous dispersion containing polymer or polymer composition that the polymer composition of water is obtained by the method ground or crushed.
Preferably, described to include using organic solvent as the solution of medium or by the solution of medium or dispersion liquid of water
Inorganic filler.
Preferably, the inorganic filler include silica, titanium dioxide, lanthana, zirconium dioxide, aluminum oxide,
One of barium sulfate, calcium carbonate, carbonitride, boehmite, silicon carbide, molecular sieve, talcum powder, montmorillonite are a variety of.
Preferably, described using organic solvent as in the solution of medium, the polymer or polymer composition include poly-
Vinylidene, vinylidene fluoride-hexafluoropropylene copolymer, polyacrylonitrile, polyvinylidene chloride, polymethacrylates, polyethylene,
The copolymerization of polyethylene wax, the polyethylene of chlorination, the polypropylene of chlorination, polyvinyl alcohol, polyurethane, methacrylate and acrylonitrile
Object, polyoxyethylene ether, sodium alginate, cellulose derivative, dimethyl silicone polymer, polyimides, polyurethane, polystyrene sulphur
Sour sodium, sulfonated polyether-ether-ketone, polyvinyl alcohol vinyl sulfonic acid graft copolymer, sulfonated polysulfone, sulfonate polybenzimidazole, sulfonation are poly-
One or more of phenylchinoline, perfluorinated sulfonic acid polymer (such as Nafion).
Preferably, described using organic solvent as in the solution of medium, the organic solvent can be selected from the solvent of ketone such as
Acetone, butanone etc., can also selected from alcohols solvent such as methanol, ethyl alcohol etc., can also selected from halogenated hydrocarbon solvent such as monochloro methane,
Methylene chloride, chloroform, carbon tetrachloride etc. can also be selected from amide solvent such as n,N-Dimethylformamide, N, N- dimethyl second
Amide etc., can also be selected from benzene kind solvent such as benzene,toluene,xylene etc. and tetrahydrofuran, N-Methyl pyrrolidone, diformazan
Base sulfoxide, ether etc..
Preferably, described using water as in the solution of medium, the water-soluble polymer or water-soluble polymer composition
Including polyvinyl alcohol, polyoxyethylene ether, sodium alginate, sodium carboxymethylcellulose, polyacrylamide, chitosan, Amorphophallus rivieri glucomannan sugar
One or more of Deng.
Preferably, described using water as in the dispersion liquid of medium, the polymer not soluble in water or not soluble in water poly-
Polymer composition includes Kynoar, polyvinylidene chloride, polytetrafluoroethylene (PTFE), vinylidene fluoride-hexafluoropropylene copolymer, polyphenyl
One or more of ethylene, polymethyl methacrylate, polyurethane, perfluorinated sulfonic acid polymer (such as Nafion).
According to the present invention, in step S3, the coating layer thickness obtained after the coating liquid is dry is 0.3-10 microns；It is preferred that
Ground, the coating layer thickness obtained after the coating liquid is dry are 2-10 microns, preferably 3-5 microns.
According to the present invention, in step S4, the temperature stretching in the transverse direction is 120-150 DEG C；Preferably, the cross directional stretch
Temperature be 130-140 DEG C；The multiplying power stretching in the transverse direction is 2-5 times；Preferably, the multiplying power stretching in the transverse direction is 2.5-
4.5 again.
According to the present invention, in step S4, the composite polypropylene microporous barrier with a thickness of 10-60 microns, preferably 15-30
Micron.
According to the present invention, in step S4, in the composite polypropylene microporous barrier surface covering with a thickness of 0.1-4 microns,
Preferably 1-2 microns.
The second aspect of the invention is to provide a kind of composite polypropylene microporous barrier, and the composite polypropylene microporous barrier includes
The polypropylene microporous basal layer of biaxial tension and simple tension coat positioned at the basal layer at least one side.
According to the present invention, the composite polypropylene microporous barrier further includes the biaxial tension positioned at the basal layer at least one side
Coat.
According to the present invention, the composite polypropylene microporous barrier further includes between the basal layer and simple tension coat
At least one side biaxial tension coat.
According to the present invention, the simple tension coat positioned at the basal layer at least one side can be porous coating
Layer, is also possible to non-porous closely knit coat.
According to the present invention, the biaxial tension coat positioned at the basal layer at least one side can be porous coating
Layer, is also possible to non-porous closely knit coat.
Preferably, it when the coating liquid of coat is using organic solvent as the solution of medium, is formed after coating liquid is dry
Coat forms non-porous closely knit coat during stretching.The non-porous compact structure is by the polymer shape in coating liquid
At.
Preferably, when the coating liquid of coat is using organic solvent as the composite coated liquid of the solution of medium and inorganic filler
When, the coat formed after coating liquid is dry forms porous coat during stretching.The porous structure is due to applying
Caused by the interface tension rupture of polymer and inorganic filler in covering liquid.
Preferably, when the coating liquid of coat is using water as the dispersion liquid, that is, polymer lotion or aqueous dispersion of medium
When, the coat formed after coating liquid is dry forms porous coat during stretching.The porous structure is due to poly-
Polymer beads accumulation generates caused by gap.
Preferably, when the coating liquid of coat be using water as the dispersion liquid, that is, polymer lotion or aqueous dispersion of medium with
When the composite coated liquid of inorganic filler, the coat formed after coating liquid is dry forms porous coat during stretching.
The porous structure is to accumulate generation gap and polymer and the rupture of inorganic filler interface tension due to polymer beads to cause
's.
Preferably, when the coating liquid of coat is using water as the water-soluble polymer solution of medium, after coating liquid is dry
The coat of formation forms non-porous closely knit coat during stretching.The non-porous compact structure is by poly- in coating liquid
Close what object was formed.
Preferably, when the coating liquid of coat is using water as the compound of the water-soluble polymer solution of medium and inorganic filler
When coating liquid, the coat formed after coating liquid is dry forms porous coat during stretching.The porous structure is
As caused by the polymer in coating liquid and the rupture of the interface tension of inorganic filler.
According to the present invention, the polypropylene microporous basal layer is biaxial stretching film.
According to the present invention, the porosity of the polypropylene microporous basal layer is 25-60%；Gurley gas permeability value is 100-
400s。
According to the present invention, the longitudinal tensile strength of the composite polypropylene microporous barrier is 60-130MPa；Longitudinal elongation at break
Rate is 5-70%；Transverse tensile strength is 15-60MPa；Transverse breakage elongation is 10-100%.
According to the present invention, the composite polypropylene microporous barrier is prepared using the above method.
The third aspect of the invention is to provide the purposes of above-mentioned composite polypropylene microporous barrier, can be used for preparing lithium from
In the fields such as sub- battery diaphragm, gas separation membrane.
The fourth aspect of the invention is to provide a kind of lithium battery diaphragm, and the diaphragm includes that above-mentioned composite polypropylene is micro-
Pore membrane.
Preferably, the composite polypropylene microporous barrier include biaxial tension polypropylene microporous basal layer and be located at the base
The simple tension coat of bottom at least one side.
Preferably, the composite polypropylene microporous barrier further includes the biaxial tension coating positioned at the basal layer at least one side
Layer.
Preferably, the composite polypropylene microporous barrier further include between the basal layer and simple tension coat extremely
The biaxial tension coat of few one side.
According to the present invention, the polymer in the coat of the diaphragm at least one side can be with the electrolyte shape of lithium ion battery
At gel or there is lithium ion conduction performance.
According to the present invention, the simple tension coat of at least one side can be porous coat, be also possible to nothing
The closely knit coat in hole.
According to the present invention, the biaxial tension coat of at least one side can be porous coat, be also possible to nothing
The closely knit coat in hole.
Preferably, when the diaphragm at least one side coat is non-porous closely knit coat, the diaphragm as lithium-sulfur cell,
The non-porous closely knit coat can prevent the shuttle in the polysulfide anion cyclic process in lithium-sulfur cell, weaken and " fly
Capacity caused by shuttle effect " is decayed rapidly, and the cycle performance of lithium-sulfur cell is improved.
The fifth aspect of the invention is to provide a kind of gas separation membrane, and the gas separation membrane includes above-mentioned compound poly-
Propylene microcellular film.
Preferably, the composite polypropylene microporous barrier include biaxial tension polypropylene microporous basal layer and be located at the base
The simple tension coat of bottom at least one side.
Preferably, the composite polypropylene microporous barrier further includes the biaxial tension coating positioned at the basal layer at least one side
Layer.
Preferably, the composite polypropylene microporous barrier further include between the basal layer and simple tension coat extremely
The biaxial tension coat of few one side.
According to the present invention, the main component for preparing the coating liquid of the coat is to have different diffusion coefficients to gas
Material.
Preferably, the material to gas with different diffusion coefficients includes silicon rubber, polyimides, polysulfones, polyphenyl
The macromolecules such as ether, cellulose acetate.
According to the present invention, the gas separation membrane can be used for preparing the gas separation membrane with gas separating. functional layer.
The sixth aspect of the invention is to provide a kind of device for preparing above-mentioned composite polypropylene microporous barrier, described device packet
Include feeding extrusion system, curtain coating chill roll system, longitudinal stretching system, the second coating system and cross directional stretch system；
The feeding extrusion system is connected by being cast chill roll system with longitudinal stretching system, and the longitudinal stretching system is logical
The second coating system is crossed to connect with cross directional stretch system.
According to the present invention, the feeding extrusion system includes feeder, screw extruder, the first melt pipe, filter
With the second melt pipe；
Preferably, second melt pipe is connected with curtain coating chill roll system；
Preferably, the feeder is located at the top of the feed inlet of the screw extruder；The screw extruder passes through
First melt pipe is connected with filter；The filter is connected by the second melt pipe with curtain coating chill roll system；
Preferably, metering pump is additionally provided in first melt pipe；
According to the present invention, the curtain coating chill roll system includes die head and slab roller；
Preferably, the die head is selected from that thickness is self-adjustable gets to know；The slab roller is selected from what temperature accurately controlled
Slab roller；
According to the present invention, described device further includes the first coating system.
According to the present invention, first coating system is set between curtain coating chill roll system and longitudinal stretching system.
According to the present invention, first coating system includes the first coated member；
According to the present invention, second coating system includes the second coated member；
According to the present invention, the longitudinal stretching system includes preheating, stretching and the thermal finalization roller group that temperature accurately controls.
According to the present invention, the cross directional stretch system includes track, chain pincers, baking oven and transmission mechanism.
According to the present invention, described device further includes traction winding system, the composite polypropylene that the purpose is to will be prepared
Microporous barrier obtains coiled composite polypropylene microporous barrier by the traction winding system.
According to the present invention, described device further includes thickness measuring feedback control system.The thickness measuring feedback control system includes surveying
Thick instrument and control system；The calibrator carries out on-line measurement to the thickness of film, and can be automatically adjusted by control system control
Die head realizes the automatic control to polypropylene microporous film thickness.
According to the present invention, the thickness measuring feedback control system includes that the first thickness measuring feedback control system and the second thickness measuring are fed back
Control system.
According to the present invention, the first thickness measuring feedback control system be set to curtain coating chill roll system and longitudinal stretching system it
Between.
Preferably, the first thickness measuring feedback control system is set between the first coating system and longitudinal stretching system.
According to the present invention, the second thickness measuring feedback control system is set to after cross directional stretch system.
Preferably, the second thickness measuring feedback control system is set between cross directional stretch system and traction winding system.
According to the present invention, the first thickness measuring feedback control system includes diaphragm calibrator, and the purpose is to unstretched
Diaphragm thickness measure and control or at least one side be coated with the unstretched diaphragm of coating liquid thickness carry out
Measurement and control.
According to the present invention, the second thickness measuring feedback control system includes THICKNESS GAUGE FOR THE MEASUREMENT OF THIN FOILS, and the purpose is to stretched
The thickness of film measure and control.
According to the present invention, described device further includes automatic control system；
According to the present invention, the automatic control system includes pressure and temperature control module, PLC, frequency converter, sensor,
It is controlled for realizing temperature, pressure, tension and the speed etc. to device.
The seventh aspect of the invention is to provide a kind of preparation method of composite polypropylene microporous barrier, is using above-mentioned
What device was prepared.
According to the present invention, the preparation method includes the following steps:
A) polypropylene containing the nucleating agent that beta crystal can be promoted to be formed is entered into screw extruder melting through feeder, melted
Body flows through metering pump through the first melt pipe, and after accurate metering, the second melt pipe is entered after being filtered；
B) melt through die of step a) is cast to the diaphragm that crystallization on slab roller forms high β crystalline substance；
C) diaphragm of the high β crystalline substance of step b) is removed from slab roller；
Optionally, coating liquid is applied to the one or both sides surface of diaphragm through the first coating system；
Optionally, the diaphragm of high β crystalline substance is monitored through diaphragm calibrator, measures the thickness or at least one of unstretched diaphragm
Face is coated with the thickness of the unstretched diaphragm of coating liquid；
D) the unstretched diaphragm of step c) or one or both sides surface are coated with to the unstretched film of coating liquid
Piece obtains the diaphragm of longitudinal stretching by longitudinal stretching system；
E) coating liquid is applied to the one or both sides surface of the diaphragm of the longitudinal stretching of step d) through the second coating system；
F) diaphragm of step e) is obtained into diaphragm stretching in the transverse direction by cross directional stretch system, be prepared described compound poly-
Propylene microcellular film.
According to the present invention, the preparation method further includes following steps:
G) the composite polypropylene microporous barrier of step f) is obtained into coiled composite polypropylene micropore by traction winding system
Film；
Optionally, before through traction winding system, the thickness through THICKNESS GAUGE FOR THE MEASUREMENT OF THIN FOILS monitoring composite polypropylene microporous barrier.
According to the present invention, the coating liquid coating can be implemented using any mode well known in the prior art, such as
Implemented using modes such as spraying, blade coating, intaglio plate coatings.
Beneficial effects of the present invention:
1. the present invention provides a kind of composite polypropylene microporous barrier and its preparation method and application, the preparation method be
Coat is introduced by coating system on diaphragm one or both sides surface in the preparation process of Biaxially oriented polypropylene microporous barrier, is applied
Coating is passed through in vertical/horizontal both direction or only to be stretched in a lateral direction, realizes the preparation of the composite polypropylene microporous barrier.Using
Method of the invention simplifies the production technology of composite polypropylene microporous barrier, improves the performance of microporous polypropylene membrane.It is described multiple
It closes microporous polypropylene membrane to be used in lithium battery, since coat is the polymer or composition that can form gel with electrolyte, energy
Improve the circulation and security performance of lithium battery.The composite polypropylene microporous barrier is separated for gas, since coat is to difference
The infiltration coefficient of gas is different, and the separation and enrichment of gas with various may be implemented.
2. described device includes that feeding squeezes out system the present invention also provides a kind of device for preparing composite polypropylene microporous barrier
System, curtain coating chill roll system, longitudinal stretching system, the second coating system, cross directional stretch system；Described device being prepared property
The energy preferable composite polypropylene microporous barrier of parameter, and the method simple process, preparation is convenient, is suitable for industrialized production.
3. the lithium battery diaphragm includes above-mentioned the present invention also provides a kind of lithium battery diaphragm and a kind of gas separation membrane
Composite polypropylene microporous barrier；The gas separation membrane includes above-mentioned composite polypropylene microporous barrier；The composite polypropylene micropore
Film is used in lithium battery as diaphragm in application, coat can form gel in the electrolytic solution, improve leaching of the electrolyte to diaphragm
Lubricant nature or the heat resistance for improving polypropylene microporous basal layer.When the composite polypropylene microporous barrier is separated for gas, coating
Layer is different to the transmission coefficient of gas with various, and the separation and enrichment of gas may be implemented.
Detailed description of the invention
Fig. 1 is the device of the present invention for preparing composite polypropylene microporous barrier；
Wherein, 1 is feeder；2 be screw extruder；3 be metering pump；4 be filter；5 be the second melt pipe；6 are
Die head；7 be slab roller；8 be the first coated member；9 be diaphragm calibrator；10 be longitudinal stretching system；11 be the second coating structure
Part；12 be cross directional stretch system；13 be THICKNESS GAUGE FOR THE MEASUREMENT OF THIN FOILS；14 be traction winding system；15 be automatic control system.
Specific embodiment
Present invention will be further explained below with reference to specific examples.It should be understood that these embodiments are merely to illustrate the present invention
Rather than it limits the scope of the invention.Furthermore, it is to be understood that after having read documented content of the invention, this field skill
Art personnel can make various changes or modifications the present invention, and such equivalent forms equally fall within limited range of the present invention.
In the description of the present invention, it should be noted that term " first ", " second " etc. are used for description purposes only, and simultaneously
Non- indication or suggestion relative importance.
Embodiment 1
Melt index for the homopolypropylene resin of 2.5g/10min and is accounted for into the poly- of homopolypropylene resin 0.03wt%
Propylene β crystalline substance nucleant agent N, N- dicyclohexyl -2,6 naphthalene diamides are uniformly mixed, and are added to single screw extrusion machine 2 by feeder 1
In, after temperature is 160-230 DEG C of melting, is measured by metering pump 3, enter T through the second melt pipe 5 after filter 4
Pattern head 6 squeezes out, cooling on slab roller 7, obtains the polypropylene diaphragm of the nucleating agent of crystalline substance containing β.Poly- the third of the nucleating agent of crystalline substance containing β
Alkene diaphragm with a thickness of 140 microns.
The diaphragm enters longitudinal stretching system 10 by diaphragm calibrator 9, and 4.5 times of longitudinal stretchings are carried out at 100 DEG C and are obtained
To longitudinal stretching diaphragm.
The polymethyl methacrylate that longitudinal stretching diaphragm is 25wt% in two sides coating solid content through the second coating system
Aqueous dispersion, coating layer thickness is 6 microns after drying.Coated longitudinal stretching diaphragm enters cross directional stretch system at 135 DEG C
3.0 times of cross directional stretch are carried out, compound poly- the third of the double spread of polymethyl methacrylate of the surface with porous structure is obtained
Alkene microporous barrier.
The coat with a thickness of 2 microns；The composite polypropylene microporous barrier with a thickness of 20 microns.
When the above-mentioned composite polypropylene microporous barrier being prepared is used as lithium ion battery separator, the diaphragm is to lithium ion
The wellability and imbibition rate of battery electrolyte are significantly improved compared with single-layer polypropylene seperation film.
Embodiment 2
With embodiment 1, difference is only that embodiment 2, and the coated system of longitudinal stretching diaphragm (II) is coated in a side surface
Nafion solution (is bought from E.I.Du Pont Company), and coating layer thickness is 3 microns after drying, and it is non-porous for obtaining a side surface through cross directional stretch
The composite polypropylene microporous barrier of the one side coating of the Nafion of compact structure.
The coat with a thickness of 1.0 microns；The composite polypropylene microporous barrier with a thickness of 19 microns.
When the above-mentioned composite polypropylene microporous barrier being prepared is used as lithium-sulfur cell diaphragm, due to the Nafion layer on surface
For non-porous compact structure, the polysulfide being dissolved in electrolyte can not pass through diaphragm and be transmitted, and lithium ion can be with
Sulfonate radical in Nafion in conjunction with and transmitted, therefore composite polypropylene microporous barrier can slow down polysulfide in lithium-sulfur cell
" shuttle effect " and improve the cycle performance of lithium-sulfur cell.
Embodiment 3
With embodiment 1, difference is only that embodiment 3, and longitudinal stretching diaphragm is coated with through the second coating system in a side surface
The xylene solution of dimethyl silicone polymer, coating layer thickness is 6 microns after drying, and it is non-porous for obtaining a side surface through cross directional stretch
The composite polypropylene microporous barrier of the one side coating of the dimethyl silicone polymer of compact structure.
The coat with a thickness of 2 microns；The composite polypropylene microporous barrier with a thickness of 20 microns.
The above-mentioned composite polypropylene microporous barrier being prepared is used as gas separation membrane, infiltration evaporation separating alcohol/water-soluble
Liquid achieves good separating effect.
Embodiment 4
A kind of device preparing composite polypropylene microporous barrier described in embodiment 1-3, described device include that feeding squeezes out
System, curtain coating chill roll system, longitudinal stretching system, the second coating system and cross directional stretch system；
The feeding extrusion system is connected by being cast chill roll system with longitudinal stretching system, and the longitudinal stretching system is logical
The second coating system is crossed to connect with cross directional stretch system.
In a preferred embodiment of the present invention, the feeding extrusion system include feeder 1, screw extruder 2,
First melt pipe, filter 4 and the second melt pipe 5；
Second melt pipe 5 is connected with curtain coating chill roll system；The feeder 1 is located at the screw extruder 2
The top of feed inlet；The screw extruder 2 is connected by the first melt pipe with filter 4；The filter 4 passes through second
Melt pipe 5 is connected with curtain coating chill roll system；Metering pump 3 is additionally provided in first melt pipe；
In a preferred embodiment of the present invention, the curtain coating chill roll system includes die head 6 and slab roller 7；It is described
Die head 6 is selected from that thickness is self-adjustable gets to know；The slab roller 7 is selected from the slab roller that temperature accurately controls.
In a preferred embodiment of the present invention, described device further includes the first coating system；First coating
System is set between curtain coating chill roll system and longitudinal stretching system；First coating system includes coated member 8；Described
Two coating systems include the second coated member 11；
In a preferred embodiment of the present invention, the longitudinal stretching system 10 accurately controls pre- including temperature
Heat, stretching and thermal finalization roller group；The cross directional stretch system 12 includes track, chain pincers, baking oven and transmission mechanism.
In a preferred embodiment of the present invention, described device further includes traction winding system 14.
In a preferred embodiment of the present invention, described device further includes thickness measuring feedback control system；The thickness measuring
Feedback control system includes calibrator and control system；The calibrator carries out on-line measurement to the thickness of film, and passes through control
System control can automatically adjust die head, realize the automatic control to polypropylene microporous film thickness.
In a preferred embodiment of the present invention, the thickness measuring feedback control system includes the first thickness measuring feedback control
System and the second thickness measuring feedback control system；
The first thickness measuring feedback control system is set between curtain coating chill roll system and longitudinal stretching system；Described first
Thickness measuring feedback control system is set between the first coating system and longitudinal stretching system；The second thickness measuring feedback control system
It is set to after cross directional stretch system；The second thickness measuring feedback control system is set to cross directional stretch system and traction winding system
Between system 14.
The first thickness measuring feedback control system includes diaphragm calibrator 9；The second thickness measuring feedback control system includes
THICKNESS GAUGE FOR THE MEASUREMENT OF THIN FOILS 13 is measured and is controlled the purpose is to the thickness to stretched film.
In a preferred embodiment of the present invention, described device further includes automatic control system 15；The automatic control
System 15 processed includes pressure and temperature control module, PLC, frequency converter, sensor.
More than, embodiments of the present invention are illustrated.But the present invention is not limited to above embodiment.It is all
Within the spirit and principles in the present invention, any modification, equivalent substitution, improvement and etc. done should be included in guarantor of the invention
Within the scope of shield.
Claims (10)
1. a kind of preparation method of composite polypropylene microporous barrier, which is characterized in that the preparation method comprises the following steps:
(S1) nucleating agent that beta crystal can be promoted to be formed is added into polypropylene；
(S2) by the polypropylene for being mixed with nucleating agent of step (S1) through melting extrusion, molding obtains high β epitaxial piece；
(S3) high β epitaxial piece is obtained into longitudinal stretching film through longitudinal stretching, coating liquid is applied to the one of the longitudinal stretching film
Side or both side surface；
(S4) the longitudinal stretching film for being coated with coating liquid obtains the composite polypropylene microporous barrier through cross directional stretch.
2. preparation method according to claim 1, which is characterized in that (S2) and step (S3) the step of the preparation method
Between further include following steps:
Coating liquid is applied to the one or both sides surface of the resulting high β epitaxial piece of step (S2) by (S2 '), obtains being coated with coating
The high β epitaxial piece of liquid.
Preferably, in step S1, it is described can promote beta crystal formed nucleating agent be selected from nucleation efficiencies with higher, and
Nucleating agent of the beta crystal content 50% or more under conditions of stationary crystallization.
Preferably, the nucleating agent either one pack system small organic molecule such as N, N- dicyclohexyl terephthalamide, N,
N- dicyclohexyl -2,6 naphthalene diamides or γ-Kui bifurcation pyridine etc. are also possible to double/multi-component inorganic salts such as adipic acid and/or pungent
The hydrazine salt of diacid, the calcium salt of pimelic acid and/or suberic acid, the calcium salt of tetrahydrophthalic anhydride or barium salt, hexahydrophthalic anhydride calcium salt or barium
Salt etc..
Preferably, in step S1, the nucleating agent that beta crystal can be promoted to be formed and polyacrylic amount ratio are 0.001-
0.1wt%.
Preferably, in step S2, the content of β crystalline substance is higher than 80% in the high β epitaxial piece, it is preferable that β in the high β epitaxial piece
Brilliant content is higher than 85%；
Preferably, in step S3, the temperature of the longitudinal stretching is 60-120 DEG C, it is preferable that the temperature of the longitudinal stretching is
80-110℃；The multiplying power of the longitudinal stretching is 2.5-5.5 times, it is preferable that the multiplying power of the longitudinal stretching is 3-5 times.
3. preparation method according to claim 1 or 2, which is characterized in that in step S3 and step S2 ', the coating liquid
Including using organic solvent as the solution of medium or using water as the solution of medium or dispersion liquid；
Preferably, described using organic solvent as the solution of medium includes being dissolved polymer or polymer composition with organic solvent
The solution of formation；Described using water as the solution of medium includes being dissolved water-soluble polymer or water-soluble polymer composition with water
The solution of formation；Described by the dispersion liquid of medium of water includes by polymer not soluble in water or combination of polymers not soluble in water
Object obtains the lotion of polymer or polymer composition by the method for emulsion polymerization, or by polymer not soluble in water or insoluble
In the aqueous dispersion containing polymer or polymer composition that the polymer composition of water is obtained by the method ground or crushed.
Preferably, described using organic solvent as the solution of medium or by the solution of medium or dispersion liquid of water can also include inorganic
Filler.
Preferably, the inorganic filler includes silica, titanium dioxide, lanthana, zirconium dioxide, aluminum oxide, sulfuric acid
One of barium, calcium carbonate, carbonitride, boehmite, silicon carbide, molecular sieve, talcum powder, montmorillonite are a variety of.
Preferably, described using organic solvent as in the solution of medium, the polymer or polymer composition include gathering inclined fluorine
Ethylene, vinylidene fluoride-hexafluoropropylene copolymer, polyacrylonitrile, polyvinylidene chloride, polymethacrylates, polyethylene, poly- second
Alkene wax, the polyethylene of chlorination, the polypropylene of chlorination, polyvinyl alcohol, polyurethane, methacrylate and acrylonitrile copolymer,
Polyoxyethylene ether, sodium alginate, cellulose derivative, dimethyl silicone polymer, polyimides, polyurethane, polystyrolsulfon acid
Sodium, sulfonated polyether-ether-ketone, polyvinyl alcohol vinyl sulfonic acid graft copolymer, sulfonated polysulfone, sulfonate polybenzimidazole, sulfonated polyphenyl
One or more of base quinoline, perfluorinated sulfonic acid polymer (such as Nafion).
Preferably, described using organic solvent as in the solution of medium, the organic solvent can be selected from ketone solvent such as acetone,
Butanone etc. can also can also be selected from halogenated hydrocarbon solvent such as monochloro methane, dichloro selected from alcohols solvent such as methanol, ethyl alcohol etc.
Methane, chloroform, carbon tetrachloride etc. can also be selected from amide solvent such as n,N-Dimethylformamide, n,N-dimethylacetamide
Deng can also be sub- selected from benzene kind solvent such as benzene,toluene,xylene etc. and tetrahydrofuran, N-Methyl pyrrolidone, dimethyl
Sulfone, ether etc..
Preferably, described using water as in the solution of medium, the water-soluble polymer or water-soluble polymer composition include
In polyvinyl alcohol, polyoxyethylene ether, sodium alginate, sodium carboxymethylcellulose, polyacrylamide, chitosan, Amorphophallus rivieri glucomannan sugar etc.
One or more.
Preferably, described using water as in the dispersion liquid of medium, the polymer not soluble in water or polymer not soluble in water
Composition includes Kynoar, polyvinylidene chloride, polytetrafluoroethylene (PTFE), vinylidene fluoride-hexafluoropropylene copolymer, polyphenyl second
One or more of alkene, polymethyl methacrylate, polyurethane, perfluorinated sulfonic acid polymer (such as Nafion).
Preferably, in step S3, the coating layer thickness obtained after the coating liquid is dry is 0.3-10 microns；Preferably, the painting
The coating layer thickness obtained after covering liquid is dry is 2-10 microns, preferably 3-5 microns.
Preferably, in step S4, the temperature stretching in the transverse direction is 120-150 DEG C；Preferably, the temperature stretching in the transverse direction is
130-140℃；The multiplying power stretching in the transverse direction is 2-5 times；Preferably, the multiplying power stretching in the transverse direction is 2.5-4.5 times.
Preferably, in step S4, the composite polypropylene microporous barrier with a thickness of 10-60 microns, preferably 15-30 microns.
Preferably, in step S4, surface covering with a thickness of 0.1-4 microns, preferably 1-2 in the composite polypropylene microporous barrier
Micron.
4. a kind of composite polypropylene microporous barrier, the composite polypropylene microporous barrier includes the polypropylene microporous basal layer of biaxial tension
With the simple tension coat for being located at the basal layer at least one side.
Preferably, the composite polypropylene microporous barrier further includes the biaxial tension coat positioned at the basal layer at least one side.
Preferably, the composite polypropylene microporous barrier further includes at least one between the basal layer and simple tension coat
The biaxial tension coat in face.
Preferably, the simple tension coat positioned at the basal layer at least one side can be porous coat, can also
To be non-porous closely knit coat.
Preferably, the biaxial tension coat positioned at the basal layer at least one side can be porous coat, can also
To be non-porous closely knit coat.
Preferably, when the coating liquid of coat is using organic solvent as the solution of medium, the coating that is formed after coating liquid is dry
Layer forms non-porous closely knit coat during stretching.The non-porous compact structure is formed by the polymer in coating liquid
's.
Preferably, when the coating liquid of coat is using organic solvent as the solution of medium and the composite coated liquid of inorganic filler,
The coat formed after coating liquid is dry forms porous coat during stretching.The porous structure is due to coating liquid
In polymer and inorganic filler interface tension rupture caused by.
Preferably, it when the coating liquid of coat is using water as the dispersion liquid, that is, polymer lotion or aqueous dispersion of medium, applies
The coat formed after covering liquid is dry forms porous coat during stretching.The porous structure is due to polymer particles
Grain accumulation generates caused by gap.
Preferably, when the coating liquid of coat be using water as dispersion liquid, that is, polymer lotion of medium or aqueous dispersion with it is inorganic
When the composite coated liquid of filler, the coat formed after coating liquid is dry forms porous coat during stretching.It is described
Porous structure is to be accumulated as polymer beads caused by generating gap and polymer and the rupture of inorganic filler interface tension.
Preferably, it when the coating liquid of coat is using water as the water-soluble polymer solution of medium, is formed after coating liquid is dry
Coat form non-porous closely knit coat during stretching.The non-porous compact structure is by the polymer in coating liquid
It is formed.
Preferably, when the coating liquid of coat is using water as the composite coated of the water-soluble polymer solution of medium and inorganic filler
When liquid, the coat formed after coating liquid is dry forms porous coat during stretching.The porous structure be due to
Caused by the interface tension rupture of polymer and inorganic filler in coating liquid.
Preferably, the polypropylene microporous basal layer is biaxial stretching film；
Preferably, the porosity of the polypropylene microporous basal layer is 25-60%；Gurley gas permeability value is 100-400s.
Preferably, the longitudinal tensile strength of the composite polypropylene microporous barrier is 60-130MPa；Longitudinal elongation at break rate is 5-
70%；Transverse tensile strength is 15-60MPa；Transverse breakage elongation is 10-100%.
Preferably, the composite polypropylene microporous barrier is prepared using any one of claim 1-3 the method.
5. the purposes of composite polypropylene microporous barrier as claimed in claim 4, can be used for preparing lithium ion battery separator or gas
Body seperation film.
6. a kind of lithium battery diaphragm, the diaphragm includes composite polypropylene microporous barrier as claimed in claim 4.
Preferably, the composite polypropylene microporous barrier include biaxial tension polypropylene microporous basal layer and be located at the basal layer
The simple tension coat of at least one side.
Preferably, the composite polypropylene microporous barrier further includes the biaxial tension coat positioned at the basal layer at least one side.
Preferably, the composite polypropylene microporous barrier further includes at least one between the basal layer and simple tension coat
The biaxial tension coat in face.
Preferably, the polymer in the coat of the diaphragm at least one side can with the electrolyte of lithium ion battery formed gel or
With lithium ion conduction performance.
Preferably, the simple tension coat of at least one side can be porous coat, be also possible to non-porous closely knit
Coat.
Preferably, the biaxial tension coat of at least one side can be porous coat, be also possible to non-porous closely knit
Coat.
7. a kind of gas separation membrane, the gas separation membrane includes composite polypropylene microporous barrier as claimed in claim 4.
Preferably, the composite polypropylene microporous barrier include biaxial tension polypropylene microporous basal layer and be located at the basal layer
The simple tension coat of at least one side.
Preferably, the composite polypropylene microporous barrier further includes the biaxial tension coat positioned at the basal layer at least one side.
Preferably, the composite polypropylene microporous barrier further includes at least one between the basal layer and simple tension coat
The biaxial tension coat in face.
Preferably, the main component for preparing the coating liquid of the coat is the material for having different diffusion coefficients to gas.
Preferably, the material to gas with different diffusion coefficients includes silicon rubber, polyimides, polysulfones, polyphenylene oxide, vinegar
The macromolecules such as acid cellulose.
Preferably, the gas separation membrane can be used for preparing the gas separation membrane with gas separating. functional layer.
8. a kind of device for preparing above-mentioned composite polypropylene microporous barrier, described device includes feeding extrusion system, curtain coating slab system
System, longitudinal stretching system, the second coating system and cross directional stretch system；
The feeding extrusion system is connected by being cast chill roll system with longitudinal stretching system, and the longitudinal stretching system passes through the
Two coating systems are connect with cross directional stretch system.
9. device according to claim 8, which is characterized in that the feeding extrusion system includes feeder, Screw Extrusion
Machine, the first melt pipe, filter and melt pipe；
Preferably, second melt pipe is connected with curtain coating chill roll system；
Preferably, the feeder is located at the top of the feed inlet of the screw extruder；The screw extruder passes through first
Melt pipe is connected with filter；The filter is connected by the second melt pipe with curtain coating chill roll system；
Preferably, metering pump is additionally provided in first melt pipe；
According to the present invention, the curtain coating chill roll system includes die head and slab roller；
Preferably, the die head is selected from that thickness is self-adjustable gets to know；The slab roller is selected from the slab that temperature accurately controls
Roller；
Preferably, described device further includes the first coating system.
Preferably, first coating system is set between curtain coating chill roll system and longitudinal stretching system.
Preferably, first coating system includes the first coated member；
Preferably, second coating system includes the second coated member；
Preferably, the longitudinal stretching system includes preheating, stretching and the thermal finalization roller group that temperature accurately controls.
Preferably, the cross directional stretch system includes track, chain pincers, baking oven and transmission mechanism.
Preferably, described device further includes traction winding system.
Preferably, described device further includes thickness measuring feedback control system.The thickness measuring feedback control system includes calibrator and control
System processed；The calibrator carries out on-line measurement to the thickness of film, and can automatically adjust die head by control system control, realizes
Automatic control to polypropylene microporous film thickness.
Preferably, the thickness measuring feedback control system includes the first thickness measuring feedback control system and the second thickness measuring feedback control system
System.
Preferably, the first thickness measuring feedback control system is set between curtain coating chill roll system and longitudinal stretching system.
Preferably, the second thickness measuring feedback control system is set between the first coating system and longitudinal stretching system.
Preferably, the second thickness measuring feedback control system is set to after cross directional stretch system.
Preferably, the second thickness measuring feedback control system is set between cross directional stretch system and traction winding system.
Preferably, the first thickness measuring feedback control system includes diaphragm calibrator.
Preferably, the second thickness measuring feedback control system includes THICKNESS GAUGE FOR THE MEASUREMENT OF THIN FOILS.
Preferably, described device further includes automatic control system；
Preferably, the automatic control system includes pressure and temperature control module, PLC, frequency converter, sensor.
10. a kind of preparation method of composite polypropylene microporous barrier is prepared using device described in claim 8 or 9
's.
Preferably, the preparation method includes the following steps:
A) polypropylene containing the nucleating agent that beta crystal can be promoted to be formed is entered into screw extruder melting, melt warp through feeder
First melt pipe flows through metering pump, and after accurate metering, the second melt pipe is entered after being filtered；
B) melt through die of step a) is cast to the diaphragm that crystallization on slab roller forms high β crystalline substance；
C) diaphragm of the high β crystalline substance of step b) is removed from slab roller；
Optionally, coating liquid is applied to the one or both sides surface of diaphragm through the first coating system；
Optionally, the diaphragm of high β crystalline substance is monitored through diaphragm calibrator, the thickness or at least one side for measuring unstretched diaphragm apply
It is furnished with the thickness of the unstretched diaphragm of coating liquid；
D) the unstretched diaphragm that the unstretched diaphragm of step c) or one or both sides surface are coated with coating liquid is passed through
It crosses longitudinal stretching system and obtains the diaphragm of longitudinal stretching；
E) coating liquid is applied to the one or both sides surface of the diaphragm of the longitudinal stretching of step d) through the second coating system；
F) diaphragm of step e) is obtained into diaphragm stretching in the transverse direction by cross directional stretch system, the composite polypropylene is prepared
Microporous barrier.
Preferably, the preparation method further includes following steps:
G) the composite polypropylene microporous barrier of step f) is obtained into coiled composite polypropylene microporous barrier by traction winding system；
Optionally, before through traction winding system, the thickness through THICKNESS GAUGE FOR THE MEASUREMENT OF THIN FOILS monitoring composite polypropylene microporous barrier.
Priority Applications (6)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201710744074.XA CN109422890A (en) | 2017-08-25 | 2017-08-25 | A kind of composite polypropylene microporous barrier and its preparation method and application |
| KR1020197035820A KR20200047451A (en) | 2017-08-25 | 2018-08-24 | Composite porous membrane and manufacturing method and use thereof |
| EP18847905.9A EP3674354A4 (en) | 2017-08-25 | 2018-08-24 | Composite porous membrane and preparation method therefor and use thereof |
| JP2020511525A JP7273415B2 (en) | 2017-08-25 | 2018-08-24 | Composite porous membrane and its manufacturing method and use |
| US16/640,391 US11603443B2 (en) | 2017-08-25 | 2018-08-24 | Composite porous membrane and preparation method therefor and use thereof |
| PCT/CN2018/102316 WO2019037785A1 (en) | 2017-08-25 | 2018-08-24 | Composite porous membrane and preparation method therefor and use thereof |
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| CN114784460A (en) * | 2022-06-17 | 2022-07-22 | 宁波长阳科技股份有限公司 | Low-temperature-resistant lithium battery microporous membrane and preparation method thereof |
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