CN109638206A - It is used to prepare the device and method for preparing polyolefin microporous membrane of MIcroporous polyolefin film - Google Patents
It is used to prepare the device and method for preparing polyolefin microporous membrane of MIcroporous polyolefin film Download PDFInfo
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- 229920000098 polyolefin Polymers 0.000 title claims abstract description 129
- 238000000034 method Methods 0.000 title claims abstract description 49
- 239000012982 microporous membrane Substances 0.000 title abstract description 8
- 239000002052 molecular layer Substances 0.000 claims abstract description 83
- 238000001125 extrusion Methods 0.000 claims abstract description 46
- 238000002360 preparation method Methods 0.000 claims abstract description 36
- 239000002131 composite material Substances 0.000 claims abstract description 23
- 238000001816 cooling Methods 0.000 claims abstract description 18
- 230000008569 process Effects 0.000 claims abstract description 12
- 238000012545 processing Methods 0.000 claims abstract description 7
- 239000000463 material Substances 0.000 claims description 41
- 238000000137 annealing Methods 0.000 claims description 21
- 238000002844 melting Methods 0.000 claims description 12
- 230000008018 melting Effects 0.000 claims description 12
- 238000000465 moulding Methods 0.000 claims description 4
- 230000007704 transition Effects 0.000 claims description 4
- 150000001336 alkenes Chemical class 0.000 claims description 2
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 claims 1
- 210000001787 dendrite Anatomy 0.000 abstract description 5
- 230000015572 biosynthetic process Effects 0.000 abstract description 2
- 210000004027 cell Anatomy 0.000 abstract description 2
- 238000012360 testing method Methods 0.000 description 27
- -1 polyenes Hydrocarbon Chemical class 0.000 description 15
- 239000012528 membrane Substances 0.000 description 13
- 239000004215 Carbon black (E152) Substances 0.000 description 10
- 229930195733 hydrocarbon Natural products 0.000 description 10
- 239000004743 Polypropylene Substances 0.000 description 8
- 229920001155 polypropylene Polymers 0.000 description 8
- 230000004888 barrier function Effects 0.000 description 5
- 238000005516 engineering process Methods 0.000 description 5
- 150000002430 hydrocarbons Chemical class 0.000 description 5
- 150000004291 polyenes Chemical class 0.000 description 5
- 238000005266 casting Methods 0.000 description 4
- 230000004927 fusion Effects 0.000 description 4
- 238000003475 lamination Methods 0.000 description 4
- 239000004698 Polyethylene Substances 0.000 description 3
- 239000013078 crystal Substances 0.000 description 3
- 238000007766 curtain coating Methods 0.000 description 3
- 239000000306 component Substances 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 238000002425 crystallisation Methods 0.000 description 2
- 230000008025 crystallization Effects 0.000 description 2
- 238000013461 design Methods 0.000 description 2
- 238000003912 environmental pollution Methods 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 238000005259 measurement Methods 0.000 description 2
- 229920000573 polyethylene Polymers 0.000 description 2
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000000919 ceramic Substances 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 230000008602 contraction Effects 0.000 description 1
- 239000008358 core component Substances 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 239000003085 diluting agent Substances 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000004146 energy storage Methods 0.000 description 1
- 238000009778 extrusion testing Methods 0.000 description 1
- 230000003993 interaction Effects 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 229910001416 lithium ion Inorganic materials 0.000 description 1
- 239000000155 melt Substances 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 238000013517 stratification Methods 0.000 description 1
- 238000004781 supercooling Methods 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
Classifications
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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
-
- 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
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
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- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Manufacturing & Machinery (AREA)
- Cell Separators (AREA)
- Manufacture Of Porous Articles, And Recovery And Treatment Of Waste Products (AREA)
- Laminated Bodies (AREA)
Abstract
This application discloses a kind of devices and method for preparing polyolefin microporous membrane for being used to prepare MIcroporous polyolefin film.The device of the application includes extruder, micro-nano layer multiplier, extrusion die and cooling traction module；If micro-nano layer multiplier is used to the fused polyolefin that extruder squeezes out being divided into carried interest, one layer of per share formation forms the composite multi-layer melt of several layer stackups, and squeezed out by extrusion die, is then cast and is drawn to subsequent processing by cooling traction module.The device of the application can produce the MIcroporous polyolefin film with several layers structure, improve its mechanical strength, lay a good foundation for preparation high-quality battery.The MIcroporous polyolefin film of the application, MD tensile strength, MD elongation at break, puncture strength all greatly improve, especially TD tensile strength improves, diaphragm mechanical performance is set integrally to reach high-strength and high ductility performance, avoid diaphragm tearable in assembly cell process, it effectively improves MIcroporous polyolefin film and resists Li dendrite ability, improve battery security.
Description
Technical field
This application involves battery diaphragm Preparation equipment fields, more particularly to a kind of dress for being used to prepare MIcroporous polyolefin film
It sets and method for preparing polyolefin microporous membrane.
Background technique
As New-energy electric vehicle and energy storage industry are fast-developing, power ion battery due to its own particularity,
Need higher voltage, bigger power, higher energy and stronger high security.MIcroporous polyolefin film is as lithium ion battery
One of core component, the performances such as balanced mechanical property, aperture height consistency, high porosity directly affect battery safety,
Internal resistance, battery capacity, the current density of cycle performance and charge and discharge.But high porosity often sacrifices MIcroporous polyolefin film
Mechanical strength promotes battery micro-short circuit risk, and then influences the safety of battery.
There are three types of techniques for method for preparing polyolefin microporous membrane at present: dry method simple tension, dry method biaxial tension and wet process.It is wet
Although method biaxial stretching film and the product mechanical performance of dry method biaxial tension technology preparation are balanced, each there is obvious lack
It falls into.For example, wet process is due to using a large amount of organic diluents, the device is complicated, at high cost, easily causes environmental pollution, while PE
Material thermal contraction is big, thermal stability is poor, and application security is lower in the battery；Although can be effectively improved using ceramic coated,
But cost also increases many.Dry method biaxial tension changes using beta crystal to alpha-crystal form, and crystal volume, which is shunk, generates micropore,
This technique prepares the problems such as pore-size distribution is wider, and the thickness uniformity is poor, and stable product quality is lower, can only largely answer
For low side field.Dry method simple tension is since equipment is simple, at low cost, non-environmental-pollution problem, and it is consistent to prepare aperture
Property is good, thickness is uniform, becomes current dry method tension prevailing technology.But dry method list is drawn due to simple tension technique, prepares product
Anisotropy, i.e. MD and TD mechanical property difference are larger, and longitudinal elongation at break rate is low, transverse tensile strength is poor, puncture process is held
Easily occur tearing phenomenon the problems such as, eventually result in its resists in the battery Li dendrite puncture ability it is weaker.
Therefore, the lateral mechanical strength for how improving MIcroporous polyolefin film is always the emphasis of diaphragm area research.
Summary of the invention
The purpose of the application is to provide a kind of improved device for being used to prepare MIcroporous polyolefin film, and is based on the device
Method for preparing polyolefin microporous membrane.
To achieve the goals above, the application uses following technical scheme:
The one side of the application discloses a kind of device for being used to prepare MIcroporous polyolefin film, including extruder, micro-nano layer
Multiplier, extrusion die and cooling traction module；Extruder is used to squeeze out the polyolefine material of melting；Micro-nano layer multiplier is whole
For a kind of shunting tiered container, technique accepts extruder, if for the polyolefine material of melting to be divided into carried interest, then per one
A layer is formed, the composite multi-layer melt of several layer stackups is ultimately formed；Extrusion die technique accepts micro-nano layer multiplier, is used for
Squeeze out the composite multi-layer melt of several layer stackups；Cooling traction module technique accepts extrusion die, for by micro-nano layer double
Polyolefin composite multi-layer melt it is cooling, be cast and draw to subsequent processing.
It should be noted that the application's it is critical that introduce micro-nano in existing polyolefin micropore membrane preparation device
Layer multiplier, the MIcroporous polyolefin film of multilayered structure, remaining module or component is prepared using micro-nano layer multiplier, such as squeeze out
Machine, extrusion die and cooling traction module etc., can refer to existing MIcroporous polyolefin film dry method tension preparation facilities.Micro-nano
The basic principle of layer multiplier is, if the polyolefine material of melting is divided into carried interest, independently forms one layer per one, therefore, former
If being segmented into carried interest on then, formation several layers, the MIcroporous polyolefin film of such multilayered structure, either mechanical strength, still
Porosity is better than the MIcroporous polyolefin film of individually stratification.In the application, technique accepts the movement referred to according to polyolefine material
For the module passed through, the two is in the relationship of front and back station；The module or component that technique is accepted, can be connected together
, it is also possible to that front and back station connects together using pipeline acquisition traction device.
Preferably, micro-nano layer multiplier include technique accept entrance, shunting section, layering section, interflow section, changeover portion and
Outlet section；The outlet of entrance and extruder connects, for receiving the polyolefine material of the melting squeezed out by extruder；Shunting section
Including several shunt conduits, if for the polyolefine material of melting to be divided into carried interest；It is layered section and accepts shunting section, for quilt
If the fused polyolefin material for being divided into carried interest is pre-chilled, it is allowed to still maintain layering after collaborating again, without merging one
It rises；Collaborate section and accept layering section, if for being gradually close together the fused polyolefin material of carried interest；Changeover portion accepts interflow
Section, if for carried interest fused polyolefin material gradually to be suppressed layered, and it is final stacked together；Outlet section accepts transition
Section obtains the polyolefin composite multi-layer melt of micro-nano layer multiplication if the composite multi-layer melt for exporting a layer stackup；Extrusion die
Head is connect with outlet section, for squeezing out the polyolefin composite multi-layer melt of micro-nano layer multiplication.
It should be noted that entrance, shunting section, layering section, interflow section, the specific constructive form of changeover portion and outlet section
Only in a kind of implementation of the application, the micro-nano layer doubler structures that specifically use, however not excluded that other classes can also be used
As structure, with realize shunt, layer functions, be not specifically limited herein.
Preferably, the device of the application further includes co-extrusion module, and co-extrusion module is set to extruder and micro-nano layer multiplier
Entrance between, the polyolefine material for squeezing out multiple extruders converges extrusion, be then conveyed to again micro-nano layer multiplication
Device carries out the multiplication of micro-nano layer.
It should be noted that in the preparation process of MIcroporous polyolefin film, it usually can be by of the same race or different materials polyenes
Hydrocarbon coextrusion, to form multilayer complex films, for example, by using identical trade mark polypropylene or polyethylene, different trade mark polypropylene or poly- second
Alkene coextrusion or different materials, as polypropylene and two kinds of polyethylene it is polyolefin coextruded；Therefore, it is necessary to use co-extrusion module
The polyolefin for the similar and different material that multiple extruders squeeze out is converged into extrusion, then carries out micro-nano layer multiplication.
Preferably, the device of the application includes that several micro-nano layer multipliers are connected, and is used between micro-nano layer multiplier
Extrusion die transition connection, the last one micro-nano layer multiplier are accepted after connecting extrusion die with cooling traction module technique.
It should be noted that the number of share of stock that each micro-nano layer multiplier can distribute is limited, therefore, if only with
The micro-nano layer that one micro-nano layer multiplier is capable of forming also is limited.In order to obtain the micro-nano layer of more numbers of plies, the application
Multiple micro-nano layer multipliers are used in series in preferred scheme, are obtained with more numbers of plies in this way.In principle, it is assumed that polyene
Hydrocarbon material is to be expressed into micro-nano layer multiplier by co-extrusion module by converging after two kinds of polyolefin plastifying fusions of A and B, if each micro-
Layer multiplier of receiving can distribute 2 strands, and the number of plies that can be obtained if n micro-nano layer multiplier is connected is 2 × 2nLayer；Also
It is to say, the number of plies that the series connection of several micro-nano layer multipliers can obtain is x × ynLayer, wherein x is the polyene that co-extrusion module squeezes out
Hydrocarbon number, the i.e. quantity of extruder, y are that each micro-nano layer multiplier can distribute number of share of stock, and n is the series connection of micro-nano layer multiplier
Number.In general, the quantity of extruder is 1,2 or 3, and therefore, the value of x is usually 1-3, certainly, if do not considered
Machine cost or some special producing demands can also use more extruders.Usual each micro-nano layer multiplier can
2 strands or 4 strands are distributed, therefore, the value of y can be 2 or 4, certainly, also be not excluded for other special designs.The multiplication of micro-nano layer
The stock that the number of device depends on the number of plies of required MIcroporous polyolefin film and each micro-nano layer multiplier can distribute
Number；For example, in the case where distributing 4 strands for two extruders, each micro-nano layer multiplier, 3 micro-nano layer multiplier series connection
128 layers of MIcroporous polyolefin film can have been prepared；Although number of plies increase has increase to the mechanical performance of MIcroporous polyolefin film,
But if the number of plies is too many, the tortuosity ratio in hole increases, and will affect ventilative value；Therefore, usual for 4 strands of micro-nano layer multiplier
Using 1-3, and for 2 strands of micro-nano layer multiplier using 1-5, certainly, according to different product demands,
It can be connected, be not specifically limited herein using more micro-nano layer multipliers.
The another side of the application discloses a kind of preparation method of MIcroporous polyolefin film, the device including using the application,
Prepare the multilayer polyolefine microporous film with micro-nano layer multiplication structure.
It should be noted that the polyolefin micropore membrane preparation device of the application, due to use micro-nano layer multiplier, or even is adopted
It is connected with multiple micro-nano layer multipliers, x × y can be preparednThe multilayered microporous polyolefin film of layer, multilayered structure interaction,
The mechanical performance of MIcroporous polyolefin film can effectively be improved.
Preferably, the preparation method of the application, further include extrusion die is squeezed out using cooling traction module it is compound more
Layer melt forms Multi-layer cast film by the molding of chill roll slab, traction film forming.
Preferably, the temperature of chill roll is 30 DEG C~120 DEG C.
Preferably, the preparation method of the application further includes making annealing treatment to Multi-layer cast film.
Preferably, the condition of annealing is that 1h~20h is toasted at 100~160 DEG C.
Preferably, the preparation method of the application further includes that stretching pore-forming is carried out to the product of annealing, obtains polyolefin
Microporous barrier.
Preferably, the condition for stretching pore-forming is to carry out stretching the longitudinal stretching that speed ratio is 1~3 to the product of annealing,
Draft temperature is 110~160 DEG C, 1~10m/min of tensile speed.Preferably, tensile speed 4m/min.
It should be noted that chill roll slab molding, traction film forming, annealing and stretch pore-forming can refer to it is existing
Dry method simple tension；But in order to prepare the better MIcroporous polyolefin film of performance, the application is to chill-roll temperature, annealing
Treatment conditions, stretching pore-forming condition are particularly limited to.
The application's discloses the polyene of a kind of device using the application or the preparation method preparation of the application on one side again
Hydrocarbon microporous barrier.
Due to using the technology described above, the beneficial effects of the present application are as follows:
The application is used to prepare the device of MIcroporous polyolefin film, on the basis of existing MIcroporous polyolefin film dry process device
Upper increase micro-nano layer multiplier, can prepare the MIcroporous polyolefin film with several layers structure, effectively increasing has
The mechanical strength of the MIcroporous polyolefin film of micro-nano layer structure, especially greatly improves transverse tensile strength；Cross directional stretch is strong
The raising of degree makes the mechanical performance of MIcroporous polyolefin film integrally reach high-strength and high ductility performance, can not only avoid or reduce polyene
Hydrocarbon microporous barrier diaphragm is torn in battery assembling process, moreover, can effectively improve MIcroporous polyolefin film resists Li dendrite
The ability of puncture, provides battery security, lays a good foundation to prepare the battery of high-quality.
The MIcroporous polyolefin film of device or the preparation method preparation of the application, has high-strength and high ductility performance, compared to not having
The MIcroporous polyolefin film prepared using micro-nano layer multiplier, the MIcroporous polyolefin film MD tensile strength of the application preparation, MD fracture
Elongation, TD tensile strength and puncture strength all greatly improve, and effectively improve MIcroporous polyolefin film and resist Li dendrite ability,
Improve battery security.
Detailed description of the invention
Fig. 1 is the organigram that the device of MIcroporous polyolefin film is used to prepare in the embodiment of the present application；
Fig. 2 is the structural schematic diagram of micro-nano layer multiplier in the embodiment of the present application.
Specific embodiment
Plurality of raw materials is usually coextruded, or flow respectively by existing MIcroporous polyolefin film in order to reach multilayered structure
Prolong film forming after stacked together again or diaphragm be prepared separately after it is stacked together again, no matter which kind of mode, it is contemplated that polyene
The integral thickness of hydrocarbon microporous barrier and existing production technology all can only simply accomplish 3 layers or so.The application it is creative will be micro-
Layer technology of receiving introduces the preparation of MIcroporous polyolefin film, and has developed a kind of new micro-nano layer multiplier for being suitable for diaphragm preparation,
The polyolefin micropore membrane preparation device of the application is allowed to produce x × ynThe multilayer polyolefine microporous film of layer, x are coextrusion
Polyolefin number, i.e. the quantity of extruder, y is the shunting number of share of stock of each micro-nano layer multiplier, and n is concatenated micro-nano layer multiplier
Number.
The preparation facilities of the MIcroporous polyolefin film of the application and preparation method based on the device utilize micro-nano that skill is laminated
Art is transformed on existing co-extrusion equipment, increases micro-nano layer multiplier, enables the device that can only prepare 1~3 layer of microporous barrier originally
Enough prepare x × ynThe multilayer microporous film of layer, to improve the mechanical performance of multilayer polyolefine microporous film.The application improves multilayer
The basic principle of MIcroporous polyolefin film mechanical performance is that effect is laminated using the stretching that it is special to polymer melt that the number of plies doubles,
Keep strand height-oriented, so that special alternating multilayered structure be prepared, the meeting of this alternating multilayered structure makes product machine
Tool performance greatly improves, while the layering and sliding phenomenon that occur at bed boundary and the crystallite dimension of refinement can be further improved
Toughness.
Melt is shunted using micro-nano layer multiplier, is layered, repeatedly in lamination process, is narrowed by melt width and is become again
Width is occurred similar biaxial tension and is acted on by thick thinning lamination process again, improve MIcroporous polyolefin film laterally, longitudinal tensile strength,
Simultaneously it is also that MIcroporous polyolefin film elongation at break is got higher, improves MIcroporous polyolefin film puncture resistant ability, keep multi-layer polyolefin micro-
Pore membrane becomes high-strength and high ductility product.
The application is described in further detail below by specific embodiments and the drawings.Following embodiment is only to the application
It is further described, should not be construed as the limitation to the application.
Embodiment
This example squeezes out A material and B material using two extruders respectively, is then coextruded again and carries out the multiplication of micro-nano layer, because
This, the preparation facilities of the MIcroporous polyolefin film of this example, as shown in Figure 1, including two extruders 1, co-extrusion module 5, micro-nano layer times
Increase device 2, extrusion die 3 and cooling traction module 4；Wherein, two extruders 1 are respectively used to squeeze out the polyolefin material A of melting
With polyene hydrocarbon material B；Co-extrusion module 5 is set to the delivery outlet of two extruders, the polyolefin for squeezing out two extruders
Materials A and B converge extrusion, are then conveyed to micro-nano layer multiplier 2 again；The generally a kind of shunting layering of micro-nano layer multiplier 2 is held
Then device forms a layer per one, finally if the polyene hydrocarbon material of the melting for squeezing out co-extrusion module 5 is divided into carried interest
Form the composite multi-layer melt of several layer stackups；3 technique of extrusion die accept micro-nano layer multiplier 2, for squeeze out it is several layer by layer
Folded composite multi-layer melt；Cooling 4 technique of traction module accepts extrusion die 3, the polyene of the micro-nano layer multiplication for that will squeeze out
Hydrocarbon composite multi-layer melt is cooling, is cast and draws to subsequent processing.
The micro-nano layer multiplier 2 of this example, as shown in Fig. 2, including entrance 21, shunting section 22, layering section that technique is accepted
23, collaborate section 24, changeover portion 25 and outlet section 26；Entrance 21 is connect with the outlet of co-extrusion module 5, for receiving by coextruding die
The polyolefine material for the melting that block squeezes out；Shunting section 22 includes several shunt conduits, the polyolefine material point for that will melt
If may be generally divided into two strands or four strands at carried interest, Fig. 2, which is shown, is divided into four strands of micro-nano layer multiplier, and still, this example considers
The number of plies to MIcroporous polyolefin film easily causes ventilative value too much and is significantly increased, and this example is specifically using can be divided into two strands
Micro-nano layer multiplier, i.e. shunting section 22 include two shunt conduits, and the polyolefine material of melting is divided into two strands；Layering section 23 is held
Shunting section 22 is connect, for the fused polyolefin material for being divided into two strands to be pre-chilled, is allowed to still maintain after collaborating again point
Layer, without being fused together；Collaborate section 24 and accept layering section 23, for two strands of fused polyolefin materials to be gradually close in one
It rises；Changeover portion 25 accepts interflow section 24, for two strands of fused polyolefin materials gradually to be suppressed layered, and is finally layered in one
It rises, forms the structure of 2 × 2 total four layer stackups；Outlet section 26 accepts changeover portion 25, for exporting the composite multi-layer of four layer stackups
Melt obtains the polyolefin composite multi-layer melt of micro-nano layer multiplication；Extrusion die 3 is connect with outlet section 26, for squeezing out micro-nano
The polyolefin composite multi-layer melt of layer multiplication.
It is appreciated that this example is only that two strands of micro-nano layer multipliers is used illustratively to illustrate that the polyolefin of this example is micro-
Hole membrane preparation device can be connected, specifically, micro-nano if it is desired to obtaining the structure with multilayer using multiple micro-nano layer multipliers
It is connected between layer multiplier using extrusion die transition, the last one micro-nano layer multiplier is drawn after connecting extrusion die with cooling
Module process is accepted.For example, 2 × 2 can be obtained if connected using n micro-nano layer multipliernThe polyolefin of layer is compound more
Layer melt.Depending on production requirement, it is not specifically limited herein.
Polyolefin micropore membrane preparation device based on this example, the method for preparing polyolefin microporous membrane of this example include following step
It is rapid:
1, curtain coating squeezes out: two extruders squeeze out two kinds of materials of A, B respectively, and A, B material can be the polyene of same model
Hydrocarbon is also possible to different model polyolefin；Converged after plastifying fusion by co-extrusion module and be expressed into micro-nano layer multiplier, such as Fig. 1
It is shown.
2, multilayer double: A, B material is laminated together converge after, flow into the entrance of a micro-nano layer multiplier, then exist
Two stock streams are divided by a stock stream in shunting section, have respectively entered layering section, by spatial alternation, such as are rotated by 90 °, respectively
It enters in the runner of interflow section, then is summarized by changeover portion and be shaped to 8 layers of stream, squeezed out from outlet section.If the n that connects is a micro-
It receives a layer multiplier, then can prepare 2 × 2nLayer composite membrane.It is this by shunting, layering, repeatedly in lamination process, by the wide change of melt
It is narrow to broaden again, by thick thinning lamination process again, similar biaxial tension occurs and acts on, keeps macromolecular chain height-oriented.
3, slab forms: composite multi-layer melt being squeezed out from extrusion die, the chill roll slab through supercooling traction module
Molding, traction film forming, 30~120 DEG C of chill-roll temperature.
Then, according to conventional annealing and stretching forming hole method, multilayer polyolefine microporous film is prepared.Specific packet
It includes, Multi-layer cast film is put into baking 1h~20h at 100~160 DEG C of baking oven, that is, is made annealing treatment；Then, it will make annealing treatment
Casting films afterwards carry out longitudinal stretching, stretch speed ratio 1~3, and draft temperature is 110~160 DEG C, 1~10m/min of tensile speed,
Prepare multilayer polyolefine microporous film.
Polyolefin micropore membrane preparation device and method for preparing polyolefin microporous membrane based on this example, this example are prepared for not respectively
The MIcroporous polyolefin film that overall thickness with the number of plies is 16 μm, specific A material and B material all use polypropylene；Also, in order to obtain
Different layers of MIcroporous polyolefin films are obtained, following tests is to the micro-nano layer multiplier in this example polyolefin micropore membrane preparation device
Number has carried out appropriate adjustment, as follows in detail:
Test 1:
(1) curtain coating squeezes out: two extruders squeeze out trade mark polypropylene of the same race respectively, converge co-extrusion module after plastifying fusion,
Processing temperature is all 230 DEG C.
(2) multilayer doubles: after the polypropylene that two extruders squeeze out is laminated converges together, this test could be used without micro-nano layer
The polyolefin micropore membrane preparation device of multiplier, is directly squeezed out two layers of melt by co-extrusion module, and extrusion die temperature is 220
℃。
(3) slab forms: two layers of the melt that will be squeezed out from die head is formed by chill roll slab, traction film forming, chill roll
90 DEG C of temperature.
(4) annealing crystallization: being put into baking oven for two layers of casting films and be heat-treated, and 140 DEG C of annealing temperature, annealing time 14h；
(5) it stretches pore-forming: the above-mentioned casting films after annealing being stretched, speed ratio 2.5, draft temperature are stretched
It is 150 DEG C, tensile speed 4m/min, prepares two layers of co-extrusion MIcroporous polyolefin film.
Test 2:
(1) curtain coating squeezes out: two extruders distinguish the identical polypropylene of extrusion test 1, converge after plastifying fusion and are expressed into
Layer multiplier, processing temperature is all 230 DEG C.
(2) multilayer doubles: after the polypropylene that two extruders squeeze out be laminated converge together, this test use is micro- with 2
Receive the polyolefin micropore membrane preparation device of layer multiplier, melt flow enters in micro-nano layer multiplier, and by shunting, being layered, overlapping is again
Summarized by changeover portion and be shaped to 8 layers of stream, be expressed into die head, temperature is 220 DEG C.
(3) slab forms: composite multi-layer melt being squeezed out from die head, is formed by chill roll slab, traction film forming is cooling
90 DEG C of roll temperature.
(4) annealing crystallization: being put into baking oven for Multi-layer cast film and be heat-treated, and 140 DEG C of annealing temperature, annealing time 14h；
(5) it stretches pore-forming: the above-mentioned casting films after annealing being stretched, speed ratio 2.5, draft temperature are stretched
It is 150 DEG C, tensile speed 4m/min, prepares 8 layers of co-extrusion MIcroporous polyolefin film.
Test 3:
This test is similar with test 2, except that this test is using with 3 concatenated polyolefin of micro-nano layer multiplier
Micropore membrane preparation device prepares MIcroporous polyolefin film, remaining step and condition are all identical as test 2, finally prepares 16 layers altogether
Squeeze MIcroporous polyolefin film.
Test 4:
This test is similar with test 2, except that this test is using with 4 concatenated polyolefin of micro-nano layer multiplier
Micropore membrane preparation device prepares MIcroporous polyolefin film, remaining step and condition are all identical as test 2, finally prepares 32 layers altogether
Squeeze MIcroporous polyolefin film.
Thickness, MD tensile strength, MD elongation at break, TD is carried out to four MIcroporous polyolefin films of test 1 to test 4 to draw
Intensity and puncture strength test are stretched, the specific test method is as follows:
Following parameter attribute test is carried out to the multilayer polyolefine microporous film of embodiment 1 to 3:
(1) thickness is tested
It carries out, is measured using hand-held calibrator, the direction TD along film takes 5 every 5cm with reference to GB/T 6672-2001
Point measurement, the average value of measurement are its thickness, and thickness unit is μm.
(2) MD, TD tensile strength, elongation at break test
It is carried out with reference to GB/T 1040.3-2006, the sample that specification is 100mm × 20mm is taken to measure in electronic tensile machine.
(3) puncture strength is tested
It is carried out with reference to GB/T 21302-2007, takes specimen holder of the diameter greater than 60mm in the puncture fixture of electronic tensile machine
In, sample is pierced through downwards with 100mm/s speed with the tack needle that diameter is 1mm and is measured.
Every test result is as shown in table 1.
1 MIcroporous polyolefin film the performance test results of table
| Test number | Test 1 | Test 2 | Test 3 | Test 4 |
| The MIcroporous polyolefin film number of plies | 2 | 8 | 16 | 32 |
| Thickness (μm) | 16 | 16 | 16 | 16 |
| MD tensile strength (Kgf/cm2) | 1830 | 2000 | 2280 | 2550 |
| MD elongation at break (Kgf/cm2) | 82 | 142 | 191 | 275 |
| TD tensile strength (Kgf/cm2) | 160 | 195 | 243 | 315 |
| Puncture strength (g) | 350 | 403 | 440 | 492 |
Table 1 the results show that compared to test 1, as the micro-nano layer multiplier used increases, the layer of MIcroporous polyolefin film
Number is presented index and increases；Also, in the case where identical material and same overall thickness, the number of plies is more, corresponding MIcroporous polyolefin film
MD tensile strength, MD elongation at break, puncture strength all gradually increase, especially TD tensile strength improves, and keeps diaphragm mechanical
Performance integrally reaches high-strength and high ductility performance, avoids diaphragm tearable situation in assembly cell process, while also improving diaphragm and existing
Li dendrite ability is resisted in battery.
The foregoing is a further detailed description of the present application in conjunction with specific implementation manners, and it cannot be said that this Shen
Specific implementation please is only limited to these instructions.For those of ordinary skill in the art to which this application belongs, it is not taking off
Under the premise of from the application design, a number of simple deductions or replacements can also be made.
Claims (10)
1. a kind of device for being used to prepare MIcroporous polyolefin film, it is characterised in that: including extruder (1), micro-nano layer multiplier
(2), extrusion die (3) and cooling traction module (4)；
The extruder (1) is used to squeeze out the polyolefine material of melting；
Generally a kind of shunting tiered container of micro-nano layer multiplier (2), technique accepts the extruder (1), for that will melt
If the polyolefine material melted is divided into carried interest, a layer then is formed per one, the composite multi-layer for ultimately forming several layer stackups is molten
Body；
Extrusion die (3) technique accepts the micro-nano layer multiplier (2), and the composite multi-layer for squeezing out several layer stackups is molten
Body；
Cooling traction module (4) technique accepts the extrusion die (3), the polyolefin of the micro-nano layer multiplication for that will squeeze out
Composite multi-layer melt is cooling, is cast and draws to subsequent processing.
2. the apparatus according to claim 1, it is characterised in that: the micro-nano layer multiplier (2) includes entering for technique undertaking
Mouth section (21), shunting section (22), layering section (23), interflow section (24), changeover portion (25) and outlet section (26)；
The entrance (21) connect with the outlet of extruder (1), for receiving the polyolefin of the melting squeezed out by extruder (1)
Material；
The shunting section (22) includes several shunt conduits, if for the polyolefine material of melting to be divided into carried interest；
The layering section (23) accepts shunting section (22), if for the fused polyolefin material for being divided into carried interest to be pre-chilled,
It is allowed to still maintain layering after collaborating again, without being fused together；
The interflow section (24) accepts layering section (23), if for being gradually close together the fused polyolefin material of carried interest；
The changeover portion (25) accepts interflow section (24), if for carried interest fused polyolefin material gradually to be suppressed layered, and
It is final stacked together；
The outlet section (26) accepts changeover portion (25), if the composite multi-layer melt for exporting a layer stackup, obtains micro-nano layer
The polyolefin composite multi-layer melt of multiplication；
The extrusion die (3) connect with the outlet section (26), and the polyolefin composite multi-layer for squeezing out the multiplication of micro-nano layer is molten
Body.
3. device according to claim 1 or 2, it is characterised in that: it further include co-extrusion module (5), the co-extrusion module (5)
It is set between extruder (1) and the entrance (21) of the micro-nano layer multiplier (2), it is poly- for squeezing out multiple extruders
Olefin material converges extrusion, is then conveyed to micro-nano layer multiplier (2) again and carries out the multiplication of micro-nano layer.
4. device according to claim 1 or 2, it is characterised in that: including several concatenated micro-nano layer multipliers, micro-nano
It is connected between layer multiplier using extrusion die transition, the last one micro-nano layer multiplier is drawn after connecting extrusion die with cooling
Module process is accepted.
5. a kind of preparation method of MIcroporous polyolefin film, it is characterised in that: including using the described in any item dresses of claim 1-3
It sets, prepares the multilayer polyolefine microporous film with micro-nano layer multiplication structure.
6. preparation method according to claim 5, it is characterised in that: further including will using the cooling traction module (4)
The composite multi-layer melt that the extrusion die (3) squeezes out forms Multi-layer cast film by the molding of chill roll slab, traction film forming；
Preferably, the temperature of the chill roll is 30 DEG C~120 DEG C.
7. preparation method according to claim 6, it is characterised in that: further include being carried out at annealing to the Multi-layer cast film
Reason；Preferably, the condition of the annealing is that 1h~20h is toasted at 100~160 DEG C.
8. preparation method according to claim 7, it is characterised in that: further include drawing the product of the annealing
It is stretched into hole, obtains the MIcroporous polyolefin film.
9. preparation method according to claim 8, it is characterised in that: the condition for stretching pore-forming is, to the annealing
The product of processing carries out stretching the longitudinal stretching that speed ratio is 1~3, and draft temperature is 110~160 DEG C, 1~10m/ of tensile speed
min。
10. a kind of using the described in any item devices of claim 1-4 or the described in any item preparation method systems of claim 5-9
Standby MIcroporous polyolefin film.
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|---|---|---|---|
| CN201811637480.7A CN109638206A (en) | 2018-12-29 | 2018-12-29 | It is used to prepare the device and method for preparing polyolefin microporous membrane of MIcroporous polyolefin film |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109980165A (en) * | 2019-04-22 | 2019-07-05 | 深圳中兴新材技术股份有限公司 | A kind of strong mechanical performance laminated film of low temperature closed pore and its preparation method and application |
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Citations (11)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1522201A (en) * | 2001-05-02 | 2004-08-18 | 美国杜邦泰津胶片合伙人有限公司 | Multilayer polymeric films |
| CN1687626A (en) * | 2005-03-18 | 2005-10-26 | 四川大学 | Multiplayer composite tube made from polymer possessing texture in nano layer and making method |
| CN1693149A (en) * | 2005-05-25 | 2005-11-09 | 四川大学 | Multilayer polymer compound packaging material with with nano layer texture and its processing method |
| CN201800215U (en) * | 2010-08-25 | 2011-04-20 | 翁文桂 | Layer multiplication device for preparing multi-layer material |
| CN103302835A (en) * | 2012-03-14 | 2013-09-18 | 宏腾光电股份有限公司 | Shunting and multiplying device, shunting system, shunting method and multi-layer membrane structure |
| CN104979513A (en) * | 2015-05-25 | 2015-10-14 | 武汉惠强新能源材料科技有限公司 | Three-layer co-extruded lithium-ion battery separation membrane and production method thereof |
| CN105220259A (en) * | 2015-10-16 | 2016-01-06 | 同济大学 | A kind of polymer nanocomposite conductive fiber and preparation method thereof |
| CN105489916A (en) * | 2015-11-26 | 2016-04-13 | 同济大学 | Porous polymer film for lithium-ion battery and preparation method and application of porous polymer film |
| CN106738793A (en) * | 2016-12-27 | 2017-05-31 | 深圳市星源材质科技股份有限公司 | Novel dry-method biaxially-oriented lithium battery diaphragm, preparation method and application |
| CN108470873A (en) * | 2018-03-09 | 2018-08-31 | 同济大学 | ABAB type multilayer lithium ion battery membranes with Thermal shutdown function and preparation method thereof |
| CN209401716U (en) * | 2018-12-29 | 2019-09-17 | 武汉中兴创新材料技术有限公司 | It is used to prepare the device of MIcroporous polyolefin film |
-
2018
- 2018-12-29 CN CN201811637480.7A patent/CN109638206A/en active Pending
Patent Citations (11)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1522201A (en) * | 2001-05-02 | 2004-08-18 | 美国杜邦泰津胶片合伙人有限公司 | Multilayer polymeric films |
| CN1687626A (en) * | 2005-03-18 | 2005-10-26 | 四川大学 | Multiplayer composite tube made from polymer possessing texture in nano layer and making method |
| CN1693149A (en) * | 2005-05-25 | 2005-11-09 | 四川大学 | Multilayer polymer compound packaging material with with nano layer texture and its processing method |
| CN201800215U (en) * | 2010-08-25 | 2011-04-20 | 翁文桂 | Layer multiplication device for preparing multi-layer material |
| CN103302835A (en) * | 2012-03-14 | 2013-09-18 | 宏腾光电股份有限公司 | Shunting and multiplying device, shunting system, shunting method and multi-layer membrane structure |
| CN104979513A (en) * | 2015-05-25 | 2015-10-14 | 武汉惠强新能源材料科技有限公司 | Three-layer co-extruded lithium-ion battery separation membrane and production method thereof |
| CN105220259A (en) * | 2015-10-16 | 2016-01-06 | 同济大学 | A kind of polymer nanocomposite conductive fiber and preparation method thereof |
| CN105489916A (en) * | 2015-11-26 | 2016-04-13 | 同济大学 | Porous polymer film for lithium-ion battery and preparation method and application of porous polymer film |
| CN106738793A (en) * | 2016-12-27 | 2017-05-31 | 深圳市星源材质科技股份有限公司 | Novel dry-method biaxially-oriented lithium battery diaphragm, preparation method and application |
| CN108470873A (en) * | 2018-03-09 | 2018-08-31 | 同济大学 | ABAB type multilayer lithium ion battery membranes with Thermal shutdown function and preparation method thereof |
| CN209401716U (en) * | 2018-12-29 | 2019-09-17 | 武汉中兴创新材料技术有限公司 | It is used to prepare the device of MIcroporous polyolefin film |
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109980165A (en) * | 2019-04-22 | 2019-07-05 | 深圳中兴新材技术股份有限公司 | A kind of strong mechanical performance laminated film of low temperature closed pore and its preparation method and application |
| CN110014711A (en) * | 2019-04-22 | 2019-07-16 | 深圳中兴新材技术股份有限公司 | A kind of MIcroporous polyolefin film and its preparation method and application that adhesive property improves |
| CN110021729A (en) * | 2019-04-22 | 2019-07-16 | 深圳中兴新材技术股份有限公司 | A kind of composite diaphragm and preparation method thereof of gradient low temperature closed pore |
| CN110048061A (en) * | 2019-04-22 | 2019-07-23 | 深圳中兴新材技术股份有限公司 | A kind of MULTILAYER COMPOSITE microporous barrier and its preparation method and application |
| CN110071247A (en) * | 2019-04-22 | 2019-07-30 | 深圳中兴新材技术股份有限公司 | A kind of gradient low temperature closed pore composite diaphragm and preparation method thereof that adhesive property improves |
| CN115609977A (en) * | 2022-10-25 | 2023-01-17 | 北京化工大学 | Preparation device and method of high-strength waterproof breathable film |
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