CN106299196A - The cooling roller device of three kinds of microcellular structure lithium ion battery separators of preparation - Google Patents

The cooling roller device of three kinds of microcellular structure lithium ion battery separators of preparation Download PDF

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Publication number
CN106299196A
CN106299196A CN201510346365.4A CN201510346365A CN106299196A CN 106299196 A CN106299196 A CN 106299196A CN 201510346365 A CN201510346365 A CN 201510346365A CN 106299196 A CN106299196 A CN 106299196A
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Prior art keywords
roller
slab
slab roller
cooling
present
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CN106299196B (en
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张汉鸿
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LIAOYUAN HONGTU LI-ION BATTERY DIAPHRAGM TECHNOLOGY Co Ltd
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LIAOYUAN HONGTU LI-ION BATTERY DIAPHRAGM TECHNOLOGY Co Ltd
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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
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/05—Accumulators with non-aqueous electrolyte
    • H01M10/052—Li-accumulators
    • H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
    • 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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  • Engineering & Computer Science (AREA)
  • Manufacturing & Machinery (AREA)
  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Electrochemistry (AREA)
  • General Chemical & Material Sciences (AREA)
  • Cell Separators (AREA)

Abstract

The invention provides a kind of cooling roller device preparing three kinds of microcellular structure lithium ion battery separators, this cooling roller device includes the first slab roller, second slab roller and the 3rd slab roller, casting films through extrusion die outflow is fallen the second slab roller surface and is cooled down, and between the first slab roller and the second slab roller, pile up formation storage film, first slab roller and the second slab roller cooperate, two surfaces of storage film are cooled down simultaneously, the first slab roller and the second slab roller spacing is regulated by the adjusting means on the first slab roller, form slab in uniform thickness, further slab is cooled down through the 3rd slab roller again, so that subsequent technique is carried out；The lithium battery diaphragm that the present invention provides produce in chiller have cooling quickly, stable temperature control can control on prepared lithium ion battery separator the features such as pore structure.

Description

The cooling roller device of three kinds of microcellular structure lithium ion battery separators of preparation
Technical field
The present invention relates to battery diaphragm manufacturing technology field, particularly relate to a kind of lithium battery diaphragm Cooling roller device in production.
Background technology
Lithium ion battery is widely used in the fields such as telecommunications, energy storage and electrical source of power, main To be made up of positive pole, negative pole, electrolyte and battery diaphragm, lithium ion battery separator be lithium from A key component in sub-battery, it is the thin-film material of a kind of porous, and its Main Function is The positive and negative electrode making battery is separated, prevent the two poles of the earth contact and short-circuit, additionally there is energy Making the function that electrolyte ion passes through, the performance of barrier film determines the interfacial structure of battery, interior Resistances etc., directly affect the characteristics such as the capacity of battery, circulation and security performance, excellent performance Barrier film to improve battery combination property there is important effect.
The performance of battery diaphragm mainly characterizes by following index: the property cut off requires battery diaphragm There is partition property and electronic isolation, it is ensured that effective mechanical isolation of both positive and negative polarity；Porosity is wanted Barrier film is asked to have certain aperture and porosity, it is ensured that low resistance and high ion migration Rate, has good permeability to lithium ion；Chemical stability and electrical stability require barrier film tool Standby moisture-proof and electrolyte resistance corrosivity；Wellability requires the barrier film wellability to electrolyte Good, and there is preferable imbibition moisture-retaining capacity and ion permeability；Mechanical strength requires barrier film Enough mechanical properties and shock resistance is ensured, including puncturing while thickness is the least Intensity and hot strength；Security requirement barrier film heat stability to be had and automatically shut down protection Performance, including closed pore temperature and broken film temperature.
Especially wet processing (TIPS) in existing polyalkene diaphragm preparation technology, also known as phase Partition method or thermally induced phase separation, add little for high boiling point molecule to polyolefin as porogen In, heating is melt into homogeneous system, and then cooling occurs to be separated, and uses after biaxial tension Organic solvent extracts little molecule, can prepare the microporous membrane material being mutually communicated, and squeezes melted Generally using single chill roll in pressure drawing process, pore former is closed not exclusively, is easily flowed out, lead Cause micropore skewness, and the cooling degree on two surfaces of high-temperature fusant is differed Cause, thus cause the architectural difference on two surfaces of basement membrane；Simultaneously as to ensure certain Line speed, unavoidably to the cooling of film not in time.
Due to the existence of the problems referred to above, during existing lithium battery diaphragm is produced by the present inventor Slab cooling technology is studied and is improved, to design a kind of cooling quickly, uniformly, The cooling roller device that energy control hole structure is formed.
Summary of the invention
In order to solve above-mentioned technical problem, present inventor has performed and study with keen determination, use as follows Technical scheme: this cooling roller device includes the first slab roller, the second slab roller and the 3rd slab Roller, has a preset space length between described first slab roller and described second slab roller, and relatively Rotating, the film forming raw material of molten condition flowed out through extrusion die is at described first slab roller And pile up between described second slab roller and form storage film, described first slab roller and described second Slab roller cooperates, and cools down two surfaces of described storage film simultaneously, utilizes first Regulation parts on slab roller regulate the spacing between the first slab roller and the second slab roller, energy Enough sheets forming different-thickness according to different production requirements, then enter one through the 3rd slab roller Sheet is cooled down by step, in order to subsequent technique is carried out, thus completes the present invention.
Present invention aim at provide following aspect:
First aspect, the present invention provides one to prepare three kinds of microcellular structure lithium ion battery separators Cooling roller device, it is characterised in that: this cooling roller device include the first slab roller 1, Two slab roller 2 and the 3rd slab rollers 3, wherein,
Described second slab roller 2 be positioned at described first slab roller 1 and described 3rd slab roller 3 it Between；
Between described first slab roller 1 and the second slab roller 2, there is preset space length,
Preferably,
The axis of described first slab roller 1 and described second slab roller 2 is positioned at same level On.
Second aspect, the present invention also provides for above-mentioned cooling roller device, it is characterised in that in institute State and on the first slab roller 1, be provided with described first slab roller 1 of regulation and described second slab roller 2 The regulation parts of spacing.
The third aspect, the present invention also provides for above-mentioned cooling roller device, it is characterised in that described First slab roller 1 and the second slab roller 2 spacing are 180-580 μm, preferably 230-530 μ M, more preferably 280-480 μm.
Fourth aspect, the present invention also provides for above-mentioned cooling roller device, it is characterised in that described The diameter of the first slab roller 1 and the second slab roller 2 is than for 1:1～6, preferably 1:2～5, more It is preferably 1:3～4.
5th aspect, the present invention also provides for above-mentioned cooling roller device, it is characterised in that in institute State first slab roller the 1, second slab roller 2 and the 3rd slab roller 3 inside is provided with for dropping Low first slab roller the 1, second slab roller 2 and the chiller of the 3rd slab roller 3 surface temperature, Preferably, spiral-shaped groove is offered at described chiller outer surface.
6th aspect, the present invention also provides for above-mentioned cooling roller device, it is characterised in that described The surface temperature of first slab roller the 1, second slab roller 2 and the 3rd slab roller 3 is respectively 5～40 DEG C, preferably 10～35 DEG C, more preferably 12～33 DEG C.
7th aspect, the present invention also provides for above-mentioned cooling roller device, it is characterised in that described First slab roller 1 and described second slab roller 2 rotate in opposite directions, it is preferable that described first slab The roller linear velocity of roller 1 and the roller linear velocity numerical value of described second slab roller 2 are equal.
Eighth aspect, the present invention also provides for above-mentioned cooling roller device, it is characterised in that described The surface of first slab roller the 1, second slab roller 2 and the 3rd slab roller 3 is smooth or has Lines.
9th aspect, the present invention also provides for above-mentioned cooling roller device, it is characterised in that described Battery diaphragm is prepared according to the method comprised the steps:
1), by melted to polyethylene or a combination thereof thing, pore former and other optional additive mixed Close, extrude casting films；
2), step 1) casting films extruded flow through the first slab roller 1 and the second slab roller 2 it Between space, cast sheet；
3), step 2) the most preheated roller of sheet, draw roll and the chill roll that obtain carry out Longitudinal stretching；
4), step 3) the thin film both sides that obtain fix, successively through the first preheating zone, first Drawing zone and the first cooling zone carry out cross directional stretch；
5), step 4) thin film that obtains processes through extractant, is then dried；Preferably, Described drying device includes the transfer roller that multiple one-tenth broken line is arranged, and connects with transfer roller at thin film Touch position be provided with for dry air gun, the jet direction of the most described air gun preferably with The plane tangent of described transfer roller or parallel with the direction of transfer of thin film；
6), step 5) the thin film both sides that obtain fix, successively through the second preheating zone, second Drawing zone and the second cooling zone carry out second time cross directional stretch, obtain having three kinds of microcellular structures Lithium ion battery separator.
Tenth aspect, the present invention also provides for above-mentioned cooling roller device for three kinds of micropore knots of preparation The purposes of structure lithium ion battery separator, it is characterised in that described battery diaphragm includes outside first Layer the 9, second outer layer 10 and be clipped in internal layer 11 therebetween, described first outer layer 9, second Outer layer 10 and internal layer 11 have different microcellular structures, the aperture of the most described first outer layer 9 Being 20～100nm, the aperture of the second outer layer 10 is 30～140nm, and the aperture of internal layer 11 is 50～180nm.
Another object of the present invention also resides in offer and a kind of implements what above-mentioned preparation method was used Device, it includes extrusion device, cooling roller device and drying device, wherein,
Described extrusion device includes machine barrel, is disposed in parallel in two poly-second of described machine barrel one end Ene compositions charging aperture and be respectively arranged on described machine barrel to enter away from described polyethylene composition Material mouth is two pore former charging apertures at 1/3 and 2/3 barrel length, and/or
Described cooling roller device includes the first slab roller and second that spacing is 180～580 μm Slab roller, the diameter of described first slab roller and the second slab roller is than for 1:(1～6), described First slab roller and the second slab roller rotate in opposite directions, it is preferable that the roller of described first slab roller The roller linear velocity numerical value of cylinder linear velocity and described second slab roller is equal, and/or
Described drying device includes the transfer roller that multiple one-tenth broken line is arranged, at thin film and transfer roller The position contacted is provided with for dry air gun, the jet direction of the most described air gun with The plane tangent of described transfer roller.
The present invention described below.
To be mutually related between the multinomial performance index of battery diaphragm, such as: thickness less every Film tends to stretch out intensity and puncture strength is relatively low, the most damaged in battery installation process；Machine The general fusing point of polyolefine material that the barrier film that tool intensity is higher uses is higher, therefore closed pore temperature Higher, poor stability.Although can be come by the raw materials for production or working condition that change barrier film Significantly improve some performance indications, but want to take into account multinomial performance, to obtain indices equal Preferably battery diaphragm still has great difficulty.
In the present invention, slab process refers to that the film forming raw material of molten condition leaves extruder die After Tou, it is attached to rapidly on the slab roller surface of low temperature, due to the film forming raw material of molten condition Can quickly carry out heat exchange with slab roller, film forming raw material is rapidly cooled, when it departs from casting The process of solid sheet is formed behind sheet roller surface.
The state of appearance such as the shape of the sheet that slab process obtains, size determine lithium battery every The apparent quality of film.
In the present invention, material refers to the film forming raw material of molten condition, the film forming of described molten condition Raw material refer to through extruder die head be cast out by polyethylene or a combination thereof thing, pore former Mixture with the molten condition of optional additive composition.
According to the present invention first～nine aspects, it is provided that one prepare three kinds of microcellular structure lithiums from The cooling roller device of sub-battery diaphragm, it is characterised in that described cooling roller device includes first Slab roller, the second slab roller and the 3rd slab roller.
In the present invention, described first slab roller, the second slab roller and the structure of the 3rd slab roller Essentially identical with operation principle, it is referred to as slab roller, in the total skill describing three slab rollers During art feature, the present invention uses " slab roller " replacement " the first slab roller, the second slab roller With the 3rd slab roller ".
Described slab roller includes the cylindrical roller of inner hollow, is respectively arranged at roller two The end face of end, the roll shaft being arranged on described end face and be arranged at cooling roller within and fill Put.
In the present invention, described roller is made up of the metal material that thermal conductivity is high, it is preferable that Being made up of carbon steel, the intensity of carbon steel is big, hardness is higher, and wearability is good, extends slab roller Service life, more preferably, it is also possible to roller surface arrange have anticorrosive, anti-stick Property and the protective layer of the property such as wearability, such as ceramic layer etc., thus strengthen the anti-of roller The properties such as corrosivity, resistance to bond and wearability.
In the present invention, the surface of described slab roller is smooth or textured, preferably Ground, when the surface of slab roller is textured, its surface roughness is 0.005～0.2.
When slab roller surface is textured, prepared lithium ion battery separator surface also phase Should have certain roughness in ground, thus add the absorbency of lithium ion battery separator.
In the present invention, the end face being respectively arranged at roller two ends described in is fixing with roller even Connect, on the end surface, offer one or more through hole around described roll shaft respectively, make Roller is internally formed the cavity being in communication with the outside.
In the present invention, described roll shaft is coaxial with roller.
In the present invention, it is arranged at the chiller within roller and there is cylindrical outer shape, and Coaxial with roller, it is preferable that offer spiral-shaped recessed at described chiller outer surface Groove, the initiating terminal of described spiral-shaped groove is with the through hole of setting on the end face of roller one end even Logical, the end of groove connects with the through hole arranged on roller other end end face, it is highly preferred that Described spiral-shaped groove is one or more, described one or more spiral-shaped recessed Groove can make slab roller surface temperature uniform, i.e. the temperature of roller surface each point axially Degree keeps consistent, thus ensure that the uniformity of the film forming raw material cooling of molten condition.
It is further preferred that described chiller also includes for monitoring cooling Jie in slab roller Temperature data is also sent to the temperature sensor of cold by matter temperature.
One of the present invention preferred embodiment in, cooling medium pass through roller one end end face On through hole flow into inside roller, and along chiller outer surface offer spiral-shaped recessed Groove pair roller barrel surface cools down, and then carries out the coldest to the film forming raw material of molten condition But, then flowing out roller by the through hole on roller other end end face, circulation flows in cold.
In one embodiment being more highly preferred to of the present invention, on two end faces of slab roller Be respectively arranged with that the number of recesses spiral-shaped with chiller outer surface match is multiple Through hole, i.e. multiple inlets and liquid outlet, thus add cooling medium inside roller Circulating load, it is possible to the film forming raw material of molten state is quickly cooled down.
In a kind of embodiment being more highly preferred to of the present invention, described cooling medium is followed by outside Ring cooling device provides, it is preferable that described outer loop cooling device includes circulating pump and cold Machine.
In the present invention, described circulating pump for for cooling medium by inside roller to cold it Between circulation provide power.
Circulating pump by the cooling medium within roller from liquid outlet sucking-off, and can deliver to cold The heat exchanger of refrigeration system cools down again, is returned in roller by inlet the most again Portion, makes cooling medium constantly circulate, it is achieved thereby that the inner-outer circulation of cooling medium, Ensure that the slab roller continuous coo1ing effect to melted film forming raw material.
In the present invention, described cold will be for will implement the cooling of cooling effect in roller Medium cools down again, and it is connected with slab roller by the parts such as swivel joint, flexible pipe.
In the present invention, described swivel joint be one can 360 ° of rotations, and cooling can be made The airtight rotary connector that medium passes through.
In the present invention, described cold can be ammonia compressor, freon compressor or bromination Lithium refrigeration unit, can select suitable cold according to concrete preparation technology.
In the present invention, cold the temperature of the cooling medium exported is 15-23 DEG C, preferably For 18-22 DEG C, more preferably 19-21 DEG C, the temperature on slab roller surface is slightly above defeated by cold The temperature of the cooling medium gone out.
In the present invention, the operation of described circulating pump and cold and stopping are to control slab roller table The key of surface temperature, the two data returned according to temperature sensor transmission in chiller is No reach design temperature and automatically start or stop.
In the present invention, described slab roller is additionally provided with drive system, it is preferable that described Drive system includes that displacement drive subsystem and revolution drive subsystem.
In the present invention, described displacement drive subsystem is for regulating the position of slab roller roll shaft Put, it is possible to carry out the regular job work in workshop easily, if convenient, the most clear Except the waste material flowed out by extruder die head being deposited between slab roller, it is preferable that slab Roller is movable and oscilaltion is controlled by limit switch, thus ensures what slab roller moved Accuracy.
In the present invention, described revolution drives subsystem to be used for regulating the rotating speed of slab roller, excellent Selection of land, described revolution drives subsystem to include converter, makes slab roller reach the rotating speed set, Ensure that it can be stablized to operate evenly.
One of the present invention preferred embodiment in, all subsystems in described drive system System is all arranged at the same side of slab roller, and they can move together along with slab roller or Revolution.
In one preferred embodiment of the invention, the surface temperature of described slab roller is 5 DEG C～40 DEG C, preferably 10 DEG C～35 DEG C, more preferably 12 DEG C～33 DEG C, when slab roller surface Temperature less than 5 DEG C time, roller surface may dew, affect the normal of lithium battery diaphragm Produce；When slab roller surface temperature is higher than 40 DEG C, then can not play the effect of quickly cooling.
In the present invention, described first slab roller, described second slab roller and described 3rd casting The surface temperature of sheet roller can be identical, it is also possible to different, when described first slab roller, second When the surface temperature of slab roller and the 3rd slab roller is variant, the micropore of casting films both side surface The pore size of structure is different, and pore-size distribution is the most different.
In the present invention, described second slab roller be positioned at the first slab roller and the 3rd slab roller it Between, it is preferable that described second slab roller is near described first slab roller, it is highly preferred that institute State, between the first slab roller and the second slab roller, there is preset space length.
Described first slab roller and the second slab roller spacing are preferably 180-580 μm, are preferably 230-530 μm, more preferably 280-480 μm.
The axis of described first slab roller and described second slab roller is positioned in same level.
In the present invention, described first slab roller is additionally provided with for regulating described first casting The regulation parts of spacing between sheet roller 1 and described second slab roller, the present invention is to regulation used Parts are not specially limited, to be capable of spacing between the first slab roller and the second slab roller Minor adjustments be preferably, such as hydraulic jack and oil cylinder etc..
When described regulation parts are hydraulic jack, the micro-displacement of described first slab roller is Performed by hydraulic jack by a hydraulic system closed, can manually regulate liquid The crank of compressing cylinder realizes the regulation of the first slab roller displacement.
The regulative mode of described regulation parts is preferably and front and back regulates, thus the one-tenth of molten condition Film raw material gap between the first slab roller and the second slab roller, it is to avoid slab prepares Slab thicknesses uneven, also can avoid because of the mechanical oscillation of equipment various in technique simultaneously The adverse effect that sheet is produced, so that the lithium battery diaphragm thickness finally obtained is uniform, And the thickness making lithium ion battery separator can preferably coordinate different operating parameter request Lithium battery.
One of the present invention preferred embodiment in, described first slab roller and the second casting The diameter of sheet roller is than for 1:(1～6), preferably 1:(2～5), more preferably 1:(3～4)； The diameter of described first slab roller 1 and the 3rd slab roller 3 is than for 1:(1～4), preferably 1: (2～3).
In a preferred embodiment of the present invention, the diameter of described first slab roller For 300-600mm, a diameter of 500-900mm of the second slab roller, the 3rd slab roller straight Footpath is 400-600mm.
The roller peak of described 3rd slab roller is higher than the roller peak of the second slab roller, Be conducive to the sheet prepared regular array of lattice in stretching cooling procedure, and can make Obtain sheet sufficiently cool in transmitting procedure.
In the present invention, described first slab roller and the second slab roller rotate in opposite directions, it is preferable that The roller linear velocity of described first slab roller and the roller linear speed number of degrees of described second slab roller It is worth equal, it may be assumed that described first slab roller and the second slab roller synchronous axial system in opposite directions.
In the present invention, the 3rd slab roller and the second slab roller turn on the contrary, so that thick Sheet extends to follow-up process orientation.
The rotating speed of described 3rd slab roller is slightly larger than described first slab roller or described second casting The rotating speed of sheet roller, thus produce between the 3rd slab roller and the first slab roller or the second slab roller Raw draw ratio, it is achieved the first time of sheet is stretched.
Preferably, the rotating speed of described first slab roller is 1-6m/min, preferably 2-5m/min, More preferably 3-4m/min；The rotating speed of the second slab roller is 1-6m/min, is preferably 2-5m/min, more preferably 3-4m/min；The rotating speed of the 3rd slab roller is 2-7m/min, excellent Elect 3-6m/min as, more preferably 4-8m/min.
The rotating speed of described second slab roller constrain lithium ion battery separator speed of production and Product quality, by control the rotating speed of the second slab roller coordinate follow-up stretching, extraction and The techniques such as rolling, thus control the quality of lithium battery diaphragm.
In the present invention, described first slab roller and described second slab roller can be to casting films Two surfaces cool down simultaneously, and the 3rd slab roller carries out one side cooling to casting films.
In the present invention, the film forming raw material of molten condition is at the first slab roller, the second slab roller It is made as sheet under effect with the 3rd slab roller, and quickly cools down work at described slab roller Degree of crystallinity with lower prepared sheet is low, it is to avoid geode formation, beneficially subsequent machining technology In stretch orientation, polyethylene or a combination thereof thing also can be made thermotropic with pore former generation simultaneously Being separated, the quick cooling on sheet surface then makes to have produced separated most of pore former It is locked in inside sheet, makes pore former be not easy to flow away and ooze out, thus ensure that micropore is tied The good sizing of structure.
Through the film forming raw material of the molten condition that extruder die head flows out, its temperature is 220-240 DEG C, attach to the most rapidly on the second slab roller surface, and at the second slab roller And the space between the first slab roller is piled up and is formed storage film such that it is able to enter uninterruptedly Row slab, thus ensure that slab prepares the stable and uniform of slab thicknesses.
The inventors discovered that, quiet at high pressure from the film forming raw material of the molten condition of extruder outflow Electric field brings electrostatic charge because of electrostatic induction.
In one preferred embodiment, at described second slab roller surface and extruder Arranging opposite polarity microelectrode between extrusion die, on the one hand microelectrode can neutralize from squeezing Go out the electrostatic that the film forming raw material of the molten condition that machine flows out is carried, it is to avoid in sheet, carry sky secretly Gas, on the other hand, microelectrode also makes the second slab roller surface former with the film forming of molten condition The electric charge that material strip polarized is contrary, under the effect that the charges of different polarity attract each other, molten condition Film forming raw material can adsorb more rapidly on the second slab roller surface, thus cool down rapidly Shape.
In the present invention, the first slab roller and the second slab roller can be regulated according to product needed Between spacing, thus control the thickness of sheet prepared.
In the present invention, described spacing specifically refers to the first slab roller roller and the second slab roller Distance minimum between roller；Described first slab roller and the second slab roller spacing are preferably 180-580 μm, preferably 230-530 μm, more preferably 280-480 μm.
The thickness of heretofore described sheet is 200～600 μm, preferably 250-550 μm, More preferably 300-500 μm, the lithium battery diaphragm thickness finally given is 5～25 μm, preferably It is 8～22 μm, more preferably 10～18 μm.
In the present invention, slab is controlled by the internal chiller arranged of described slab roller The temperature on roller surface thus realize the film forming raw material to molten condition and casting films the most all Even cooling.
From the temperature of the film forming raw material of the molten condition of extruder die head extrusion it is 220-240 DEG C, after the first slab roller and the second slab roller, it becomes casting films, institute The temperature stating casting films reduces to 120-180 DEG C, preferably 100-160 DEG C, more preferably 90-140℃；After the 3rd slab roller, the temperature of casting films reduces to 70-80 DEG C further, excellent Elect 50-60 DEG C as, more preferably 30-40 DEG C.
In the present invention, on the bearing of trend of casting films, in slab roller and longitudinal stretching work Skill is additionally provided with carry-over pinch rolls between region.
The sheet traction cooled and solidified through slab roller is used by described carry-over pinch rolls to stretch zones It is one or more for coordinating follow-up production technology, the quantity of described carry-over pinch rolls, is preferably Three.
One of the present invention preferred embodiment in, described first slab roller and carry-over pinch rolls Diameter is than 4:(1～3), preferably 3:(1～2), it is preferable that described carry-over pinch rolls a diameter of 160-220mm。
In another preferred embodiment of the present invention, can be according to concrete technique bar Part, suitably controls the rotating speed of each roller, thus produces the high-quality lithium accorded with the demands of the market in a large number Battery diaphragm product, it is preferable that the rotating speed of described carry-over pinch rolls is the second slab roller rotating speed 110～130%, preferably 110%, 120% or 130%, more preferably 120%.
The chill roll dress of three kinds of microcellular structure lithium ion battery separators of preparation that the present invention provides Putting, use according to the preparation technology of following lithium ion battery separator, described preparation technology includes Following steps:
Step 1), extrusion: by above-mentioned polyethylene or a combination thereof thing, pore former and optional adding Add agent melting mixing, extrude casting films.
In a preferred embodiment in accordance with the present invention, the preferred high score of described polyethylene composition Sub-polyethylene and ultra high molecular polyethylene are by weight (88～92): (8～12), are preferably (89～91): (9～11), the compositions of more preferably 90:10 composition, described polyphosphazene polymer The number-average molecular weight of ethylene is 100,000～600,000, preferably 200,000～500,000, more preferably 30 Ten thousand～400,000, the number-average molecular weight of described ultra high molecular polyethylene is 1,200,000～1,500,000, preferably It is 1,300,000～1,400,000.
In a preferred embodiment in accordance with the present invention, described pore former includes organic pore former And Inorganic pore forming agents, wherein, described organic pore former is high boiling point small organic molecule, excellent Selection of land, described high boiling point small organic molecule is that boiling point is higher than 200 DEG C, and number-average molecular weight Liquid state organics less than 500, preferably mineral oil, C6-15 alkane, C8-15 aliphatic series carboxylic One or more in acid, C1-4 alkyl ester, C2-6 halogenated alkane, wherein,
Described mineral oil is preferably white oil, and described C6-15 alkane is selected from heptane, naphthalane, the last of the ten Heavenly stems Alkane, hendecane and dodecane, described C8-15 aliphatic carboxylic acid selected from capric acid, hendecoic acid and Lauric acid, described C1-4 alkyl ester is selected from methyl caprate, ethyl caprate, capric acid propyl ester, the last of the ten Heavenly stems Acid N-butyl, hendecoic acid methyl ester, hendecoic acid ethyl ester, hendecoic acid propyl ester, 11 carbon Acid N-butyl, lauric acid methyl ester, dodecanoate, lauric acid propyl ester, 12 carbon Acid N-butyl, described C2-6 halogenated alkane is selected from dichloroethanes, dichloropropane, chlorofluoroethane With fluorine chloropropane,
Described organic pore former more preferably mineral oil, more preferably white oil.
Described Inorganic pore forming agents is water-soluble inorganic nano-particle, it is preferable that described water solublity Inorganic nanoparticles be particle diameter be 1～200nm, preferably 3～100nm, more preferably The water-soluble nano sulfate of 5～20nm, water-soluble nano nitrate, water-soluble nano salt One or more in hydrochlorate, wherein,
Described water-soluble nano sulfate is selected from nanometer sodium sulfate, nanometer potassium sulfate and nano-sulfur Acid ammoniums etc., described water-soluble nano nitrate is selected from nanometer sodium nitrate, nanometer potassium nitrate, receives Rice ammonium nitrate, nanometer magnesium nitrate and nanometer copper nitrate etc., described water-soluble nano hydrochlorate selects From nanometer sodium chloride, nanometer potassium chloride, nanometer ammonium chloride, nanometer magnesium chloride, nanometer chlorination Calcium and nanometer copper chloride etc..
Compared to organic pore former, the Inorganic pore forming agents of described solid granular has bigger Particle diameter and fixing form, thus there is higher occupy-place effect, can in battery diaphragm shape Become the microcellular structure that aperture is bigger, the formation size of micropore, shape can be better controled over and divide Cloth, and be conducive to improving porosity and the air permeability of battery diaphragm, such as: can be by selecting not The battery diaphragm that micropore size is different is prepared with the Inorganic pore forming agents of particle diameter.
It is 100 weight portions with the weight sum of high-molecular polythene and ultra high molecular polyethylene Meter, the addition of described pore former is 20～70 weight portions, preferably 30～60 weight portions, more It is preferably 50 weight portions, wherein, described organic pore former and the weight of described Inorganic pore forming agents Than being (30～60): (1～10), it is preferably (35～55): (2～8), more preferably (40～50): (4～6).
In a preferred embodiment in accordance with the present invention, described melting mixing the process extruded Extruder or extrusion device are carried out, described extruder or extrusion device include machine barrel and Row are arranged on two polyethylene composition charging apertures of described machine barrel one end and are respectively arranged at On described machine barrel away from described polyethylene composition charging aperture be at 1/3 and 2/3 barrel length two Individual pore former charging aperture.
Polyethylene or a combination thereof thing, Inorganic pore forming agents and optional additive are pre-mixed all Put into extruder through polyethylene or a combination thereof thing charging aperture after even, preferably by Inorganic pore forming agents with High-molecular polythene is pre-mixed uniformly, and optional additive is pre-with ultra high molecular polyethylene First mix homogeneously, puts into extruder through two different polyethylene or a combination thereof thing charging aperture, Then heat fusing is added, in polyethylene or the extrusion direction of a combination thereof thing of extruder inner molten Upper addition organic pore former, described organic pore former is the most in batches from two different pore formers Charging aperture is separately added into extruder, extrudes casting films, use above-mentioned after melted also mix homogeneously Preferably mode adds described Inorganic pore forming agents and organic pore former, can avoid polyethylene or its Being separated and causing mixing inequality and with pressure in extruder occur in compositions and pore former Fluctuation so that polyethylene or a combination thereof thing are sufficiently mixed uniformly with pore former, and pore former is uniform It is distributed in polyethylene or a combination thereof thing, subsequent step beneficially prepares the hole of micropore Footpath and the battery diaphragm being more evenly distributed.
In a preferred embodiment in accordance with the present invention, it is optionally added into following weight proportion Additive,
In a preferred embodiment in accordance with the present invention, described polyethylene or a combination thereof thing, one-tenth Hole agent and optional additive can first mix, and are again heated to molten condition, it is also possible to first divide Not adding heat fusing, then mixed by melted above-mentioned substance, the present invention is the most first by institute State polyethylene or a combination thereof thing, pore former and optional additive mix homogeneously respectively, then add Enter extruder is heated to molten condition and stir mixing, mix homogeneously, and easy and simple to handle, Energy consumption is low.
In a preferred embodiment in accordance with the present invention, extrusion temperature and the direct shadow of rate of extrusion Ring step 2) in prepare the character of sheet and thickness, and determine finally to prepare each of barrier film Item physicochemical property.Extrusion temperature is the highest, and the mobility of casting films is the best, molecule confusion degree The highest, the crystallinity preparing barrier film is the poorest；Extrusion temperature is the lowest, and the mobility of casting films is more Difference, molecule confusion degree is the lowest, and degree of molecular orientation is the highest, and the crystallinity preparing barrier film is the best, In the present invention, extrusion temperature is 150～250 DEG C, preferably 170～240 DEG C.Rate of extrusion is too fast, Casting films is piled up too much between the first slab roller 3 and the second slab roller 4, is likely to result in local Cool down hardening and affect slab and carry out；Rate of extrusion is the slowest, is likely to result in prepared sheet thick Spending uneven or the thinnest, in the present invention, rate of extrusion is 800～2000g/min, is preferably 1000～1500g/min.
Wherein, described melting mixing the process extruded are carried out in an extruder, use in batches Described pore former is added to polyolefin and optional additive agent mixture by mode, can avoid Being separated and causing mixing inequality and with pressure in extruder occur in polyolefin and pore former Fluctuation so that polyolefin and pore former are sufficiently mixed uniformly, and pore former is uniformly distributed in polyene In hydrocarbon mixture, subsequent step beneficially prepares the aperture of micropore and is more evenly distributed Lithium battery diaphragm.
Step 2), slab: step 1) casting films extruded flows through the first slab roller and second Space between slab roller, casts sheet.
Described cooling roller device includes the first slab roller and second that spacing is 180～580 μm Slab roller, the diameter of described first slab roller and the second slab roller is than for 1:(1～6), described First slab roller and the second slab roller rotate in opposite directions, it is preferable that the roller of described first slab roller The roller linear velocity numerical value of cylinder linear velocity and described second slab roller is equal.
In a preferred embodiment in accordance with the present invention, as it is shown in figure 1, described first slab Roller and the second slab roller opposite direction rotating, from the casting films of extruder die head extrusion in the first slab Formed between roller and the second slab roller and pile up, be then passed through gap therebetween and squeeze Pressure, cooling, cast sheet, reduce that rate of extrusion is uneven and extruder machinery concussion etc. because of The element impact on sheet character, thus prepare the sheet that thickness is uniform, character is stable.
In a preferred embodiment in accordance with the present invention, described first slab roller 3 and the second casting The surface temperature of sheet roller 4 is 5～40 DEG C, preferably 10～35 DEG C, more preferably 12～33 DEG C, The casting films of extrusion flows through during the gap between the first slab roller and the second slab roller two-sided cold But molding, casts sheet, meanwhile, be uniformly distributed pore former therein and polyethylene or There is thermotropic being separated in a combination thereof thing, pore former is closed within it by the sheet of two-sided cooling Portion, compared with the sheet of one side cooling in traditional handicraft, pore former is less susceptible to ooze out, favorably In the aperture of prepared micropore, it is distributed more uniform battery diaphragm.
In a preferred embodiment in accordance with the present invention, optionally by described first slab roller or the The surface of two slab rollers is processed into rough plane, can prepare the electricity that single or double is coarse Pond barrier film, improves the membrane surface bonding to other material (such as: coating, film etc.) Ability, lays a good foundation for research and development novel battery barrier film.
In a preferred embodiment in accordance with the present invention, the thickness of described sheet directly affects Preparing the thickness of barrier film eventually, in general, sheet is the thickest, and the barrier film prepared is the thickest, can lead to Overregulate the gap length between the first slab roller and the second slab roller to regulate the thickness of sheet Degree, the thickness of heretofore described sheet is 200～600 μm, preferably 250～550 μm, More preferably 300～500 μm.
Step 3), longitudinal stretching: step 2) obtain the most preheated roller of sheet, stretching Roller and chill roll carry out longitudinal stretching.
In a preferred embodiment in accordance with the present invention, the most preheated roller of described sheet is with relatively Low temperature preheats, and softens sheet, prepares for stretching, prevents sheet because of unexpected high-temperature heating And cause character cataclysm；Then, the draw roll that described sheet gradually rises through multiple rotating speeds exists Longitudinal stretching is carried out under high temperature；Finally, cooled roller sub-cooled is shaped, and obtains character solid Fixed thin film.After longitudinal stretching, thin film elongates compared with sheet in the vertical, and thickness becomes Thin, and longitudinal mechanical strength is improved, meanwhile, the micropore of its internal pore former occupy-place is indulged To being elongated to elongate.
In a preferred embodiment in accordance with the present invention, the temperature of described pre-hot-rolling is 40～130 DEG C, preferably 50～120 DEG C, more preferably 60～110 DEG C, preheat sheet, for drawing Stretch and prepare；
The temperature of described draw roll is 70～150 DEG C, preferably 80～140 DEG C, more preferably 90～130 DEG C, while ensureing the good tensile property of sheet, make the micropore of pore former occupy-place Reach suitable aperture；
The temperature of described chill roll is 3～50 DEG C, preferably 5～45 DEG C, more preferably 8～40 DEG C, Make the rapid cooling and shaping of the thin film after drawing by high temperature, keep the length after longitudinal stretching, thickness Degree and aperture.
In a preferred embodiment in accordance with the present invention, the rotating speed of the plurality of draw roll exists In the range of 2～40m/min, gradient raises so that stretching is uniform, by turning of regulation draw roll Speed regulates the longitudinal stretching degree of thin film, obtains different ratios of elongation.
The ratio of elongation of described longitudinal stretching is 3～10, preferably 3.5～9.5, more preferably 4～9, Obtain that there is suitable thickness, aperture and the thin film of longitudinal mechanical strength.
Step 4), cross directional stretch for the first time: step 3) the thin film both sides that obtain fix, depend on Secondary carry out cross directional stretch through the first preheating zone, the first drawing zone and the first cooling zone.
In a preferred embodiment in accordance with the present invention, described thin film both sides are used fixture respectively Fixing, first pass around the first preheating zone and preheat, soften thin film, prepare for stretching； Then, at high temperature carry out cross directional stretch through the first drawing zone, symmetrical spacing jig from by Cumulative greatly；Finally, through the first cooling zone sub-cooled sizing, the thin film that character is fixing is obtained. After first time cross directional stretch, thin film elongates in the horizontal, lower thickness, and laterally machinery Intensity is improved, and meanwhile, the micropore horizontal elongation of its internal pore former occupy-place becomes similar circle Shape.
In a preferred embodiment in accordance with the present invention, the temperature of described first preheating zone is 60～150 DEG C, preferably 70～140 DEG C, more preferably 75～135 DEG C, preheated film, for drawing Stretch and prepare；
The temperature of described first drawing zone is 80～150 DEG C, preferably 85～145 DEG C, more preferably It is 90～140 DEG C, while ensureing the good tensile property of thin film, makes the micro-of pore former occupy-place Hole reaches suitable aperture；
The temperature of described first cooling zone is 60～150 DEG C, preferably 70～140 DEG C, more preferably It is 75～135 DEG C so that the rapid cooling and shaping of thin film after drawing by high temperature, keeps the most horizontal Length, thickness and aperture after stretching.
In a preferred embodiment in accordance with the present invention, described thin film the most at the uniform velocity moves Dynamic, regulate the cross directional stretch degree of thin film by regulating the distance between horizontal fixture, obtain Different ratios of elongation.
The ratio of elongation of described first time cross directional stretch is 3～11, and preferably 3.5～10.5 are more excellent Elect 4～10 as, obtain that there is suitable thickness, aperture and the thin film of horizontal mechanical strength.
Step 5), extraction: step 4) thin film that obtains processes through extractant, then successively It is dried.
In a preferred embodiment in accordance with the present invention, described extractant preferably includes the first extraction Taking agent and the second extractant, step 4) thin film that obtains is successively through the first extractant and second Extractant immersion treatment.
In a preferred embodiment in accordance with the present invention, the most at twice pore former is extracted Take, first extract the organic pore former component in pore former with the first extractant, then extract with water Take out the Inorganic pore forming agents component in pore former.Soak with the first extractant and the second extractant During thin film, be evenly distributed on the pore former within thin film be dissolved extract, originally by pore-forming Position that agent occupies forms microcellular structure, the distribution of micropore and aperture the most uniformly and pore creating material It is distributed the most dispersed directly related in thin film；Described first extractant is to pore former In organic pore former component dissolubility good, and the polyethylene in insoluble thin film or a combination thereof Thing and the reagent of additive, the present invention preferably selects the mixed of dichloromethane and phosphate ester composition Compound, described phosphate ester is preferably the one in trimethyl phosphate and triethyl phosphate or several Kind, wherein, dichloromethane is 10:1～40:1 with the weight ratio of phosphate ester, is preferably 15:1～30:1, described organic extractant is better than simple dichloro to organic pore former effect of extracting Methane, extraction is more complete, and pore former residual is few；Described second extractant is in pore former Inorganic pore forming agents component dissolubility good, and the polyethylene in insoluble thin film or a combination thereof thing With the reagent of additive, the present invention preferably selects water, more preferably high purity water.
Drying device is dried.Described drying device includes what multiple one-tenth broken line was arranged Transfer roller.In a preferred embodiment in accordance with the present invention, contact with transfer roller at thin film Position be provided with for dry air gun, the jet direction of the most described air gun and described biography Send the plane tangent of roller.
Use air gun that the thin film after extraction is dried, to remove the extraction of film surface residual Taking agent, prevent stain mark, described air gun drying effect is good, and effectively prevent thin film The generation of surface water wave stricture of vagina, meanwhile, by the position of Reasonable adjustment air gun Yu thin film so that The vertical impact forces of thin film is obviously reduced by air gun, significantly improves final prepared battery diaphragm The bad phenomenon such as outward appearance fold, scollop, scallop.
Step 6), cross directional stretch for the second time: step 5) the thin film both sides that obtain fix, depend on Secondary through the second preheating zone, the second drawing zone and the second cooling zone carry out second time cross directional stretch, Obtain the battery diaphragm with three kinds of microcellular structures.
In a preferred embodiment in accordance with the present invention, the both sides fixture of described thin film is solid Fixed, first pass around the second preheating zone and preheat, soften thin film, prepare for stretching；So After, at high temperature carry out small size cross directional stretch through the second drawing zone, symmetrical spacing jig from It is gradually increased；Finally, through the second cooling zone sub-cooled sizing, obtain that character is fixing three Plant the battery diaphragm of microcellular structure.Cross directional stretch is compared with first time cross directional stretch for the second time, Level of stretch substantially reduces, and after second time cross directional stretch, the thin film with microcellular structure exists The most slightly elongate or keep constant, by heating-cooling process make its mechanical strength, Air permeability, thermal contraction performance improve further, meanwhile, and its internal micropore horizontal elongation, Aperture increases, and obtains the battery diaphragm with three kinds of microcellular structures of good character.
In a preferred embodiment in accordance with the present invention, the temperature of described second preheating zone is 70～160 DEG C, preferably 80～150 DEG C, more preferably 90～140 DEG C, preheated film, for drawing Stretch and prepare；
The temperature of described second drawing zone is 100～155 DEG C, preferably 105～150 DEG C, more excellent Elect 110～145 DEG C as, make micropore reach to close while ensureing the good tensile property of thin film Suitable aperture；
The temperature of described second cooling zone is 60～130 DEG C, preferably 65～135 DEG C, more preferably It is 70～130 DEG C so that the rapid cooling and shaping of thin film after drawing by high temperature, keeps second time horizontal Length, thickness and aperture after stretching.
In a preferred embodiment in accordance with the present invention, described thin film the most at the uniform velocity moves Dynamic, regulate the cross directional stretch degree of thin film by regulating the distance between horizontal fixture, obtain Different ratios of elongation.
The ratio of elongation of described second time cross directional stretch is 0.5～5, preferably 0.7～4, more preferably It is 0.8～3, obtains that there is the three of suitable thickness, aperture, mechanical strength and thermal contraction performance Plant the battery diaphragm of microcellular structure.
According to the present invention, it is provided that the battery of three kinds of microcellular structures prepared by employing such as said method Barrier film, it is characterised in that as shown in Figure 4, this barrier film includes the first outer layer, the second outer layer With the internal layer being clipped in therebetween, described first outer layer, the second outer layer and internal layer have difference Microcellular structure.
In a preferred embodiment in accordance with the present invention, the aperture of described first outer layer is 20～100nm, the aperture of the second outer layer is 30～140nm, and the aperture of internal layer is 50～180 nm。
In a preferred embodiment in accordance with the present invention, the performance of described barrier film is as follows:
Thickness is 5～25 μm, preferably 8～22 μm, more preferably 10～18 μm；
Porosity is 40～90%, preferably 42～80%, more preferably 44～75%；
Venting quality is 200～400sec, preferably 220～380sec, more preferably 250～350 sec；
Longitudinal tensile strength is 1800～2200kgf/cm2, preferably 1850～2150 Kgf/cm2, more preferably 1900～2100kgf/cm2；
Transverse tensile strength is 1800～2500kgf/cm2, preferably 1900～2450 Kgf/cm2, more preferably 2000～2400kgf/cm2；
Puncture strength is 600～1000gf, preferably 640～950gf, more preferably 660～900 gf；
Longitudinal extension rate is 160～220%, preferably 170～210%, more preferably 180～200%；
Horizontal expansion rate is 150～210%, preferably 160～200%, more preferably 170～195%；
Longitudinal percent thermal shrinkage is not more than 3%, and preferably no greater than 2.8%, more preferably no more than 2.5%；
Laterally percent thermal shrinkage is not more than 1%, and preferably no greater than 0.5%, more preferably no more than 0.1%；
Closed pore temperature is 120～150 DEG C, preferably 130～148 DEG C, more preferably 138～142 DEG C；
Broken film temperature is 160～180 DEG C, preferably 163～175 DEG C, more preferably 166～172 DEG C.
The battery diaphragm that the method using the present invention to provide prepares has while thickness is relatively low There are higher hot strength and puncture strength, can be used for preparing the battery that volume is less, and Battery assembling process can bear higher mechanical force, not cracky；It addition, porosity and Venting quality is high, and low with its internal resistance of cell prepared, capacitance improves relatively；And percent thermal shrinkage Low, reduce during the use of battery, cause battery open circuit etc. because of barrier film heat shrinkable Problem；Meanwhile, having relatively low closed pore temperature and higher broken film temperature, safety is high.
According to a further aspect in the invention, it is provided that above-mentioned cooling roller device is for preparation three kinds The purposes of microcellular structure battery diaphragm, it is characterised in that described battery diaphragm includes outside first Layer, the second outer layer and be clipped in internal layer therebetween, described first outer layer, the second outer layer and Internal layer has different microcellular structures, and the aperture of the most described first outer layer is 20～100nm, The aperture of the second outer layer is 30～140nm, and the aperture of internal layer is 50～180nm.
According to the present invention, the preparation method of three kinds of microcellular structure battery diaphragms described above is made Device include extrusion device, cooling roller device and drying device.
Described extrusion device includes machine barrel, is disposed in parallel in two poly-second of described machine barrel one end Ene compositions charging aperture and be respectively arranged on described machine barrel to enter away from described polyethylene composition Material mouth is two pore former charging apertures at 1/3 and 2/3 barrel length.
Described cooling roller device includes the first slab roller and second that spacing is 180～580 μm Slab roller, the diameter of described first slab roller and the second slab roller is than for 1:(1～6), described First slab roller and the second slab roller rotate in opposite directions, it is preferable that the roller of described first slab roller The roller linear velocity numerical value of cylinder linear velocity and described second slab roller 4 is equal.
Described drying device includes the transfer roller that multiple one-tenth broken line is arranged, at thin film and transfer roller The position contacted is provided with for dry air gun, the jet direction of the most described air gun with The plane tangent of described transfer roller.
As fully visible, the cooling roller device that provides according to the present invention and with its three kinds prepared Microcellular structure battery diaphragm includes following beneficial effect:
(1) cooling roller device during the lithium battery diaphragm that the present invention provides produces is through first Slab roller and the second slab roller can carry out two-sided cooling to casting films, to ensure the most quickly Cooling effect；
(2) the slab cooling roller device during the lithium battery diaphragm that the present invention provides produces passes through Regulate the spacing between the first slab roller and the second slab roller and can control the thickness of casting films Thus prepare sheet in uniform thickness；
(3) the first slab roller, the second slab roller and the surface of the 3rd slab roller in the present invention Temperature is essentially identical so that casting films can cool down uniformly, without due to the bigger temperature difference And affect the Surface structure and property of barrier film；
(4) cooling roller device during the lithium battery diaphragm that the present invention provides produces is by the 3rd Casting films can be cooled down and can be enclosed in by stable for pore former by slab roller further Inside sheet, the beneficially sizing of microcellular structure；
(5) cooling roller device during the lithium battery diaphragm using the present invention to provide produces produces Lithium battery diaphragm there is three-decker, and the micro-pore shape of every layer, aperture are the most different, micro- Pore size distribution is uniform, and porosity is high；And take into account multinomial physicochemical property, good combination property, Possess high puncture strength and hot strength while reaching relatively low thickness, can be applicable to less Battery and in installation process not cracky；There is good air permeability and porosity simultaneously, Internal resistance is little, improves capacity and the cycle performance of battery；It addition, also have relatively low closed pore temperature Degree and broken film temperature, safety is high.
Accompanying drawing explanation
Fig. 1 illustrates the extrusion device schematic diagram according to one embodiment of the present invention；
During Fig. 2 illustrates that the lithium battery diaphragm according to a kind of preferred implementation of the present invention produces The schematic diagram of cooling roller device；
Fig. 3 illustrates the end view drawing of the slab roller according to a kind of preferred implementation of the present invention；
Fig. 4 illustrates chiller in the slab roller according to a kind of preferred implementation of the present invention Structural representation；
Fig. 5 illustrates the drying device schematic diagram according to one embodiment of the present invention；
Fig. 6 illustrates the drying mode schematic diagram in traditional processing technology；
Fig. 7 illustrates the battery diaphragm of three kinds of microcellular structures according to one embodiment of the present invention Representative side section view.
Drawing reference numeral illustrates:
1-the first slab roller
2-the second slab roller
3-the 3rd slab roller
4-inlet or liquid outlet
5-extruder die head
6-transfer roller
7-air gun
8-hydraulic giant
9-the first outer layer
10-the second outer layer
11-internal layer
12-carry-over pinch rolls
The groove that 13-is spiral-shaped
14-polyethylene composition charging aperture
15-pore former charging aperture
Detailed description of the invention
Below by the present invention is described in detail, the features and advantages of the invention will be along with These illustrate and become more apparent from, clearly.
The most special word " exemplary " means " as example, embodiment or illustrative ". The here as any embodiment illustrated by " exemplary " should not necessarily be construed as preferred or advantageous over it Its embodiment.Although the various aspects of embodiment shown in the drawings, but unless especially Point out, it is not necessary to accompanying drawing drawn to scale.
According to the present invention, the preparation method of three kinds of microcellular structure battery diaphragms of preparation uses specific Device, this device includes extrusion device, cooling roller device and drying device, specific as follows:
Extrusion device
As it is shown in figure 1, described extrusion device includes polyethylene composition charging aperture 14 and pore-forming Agent charging aperture 15.
In a preferred embodiment in accordance with the present invention, described extrusion device preferably includes two Polyethylene composition charging aperture 14 and two pore former charging apertures 15.
Described extrusion device also includes machine barrel, said two polyethylene composition charging aperture 14 Being juxtaposed on one end of described machine barrel, said two pore former charging aperture 15 is respectively arranged at On described machine barrel away from described polyethylene composition charging aperture 1 be at 1/3 and 2/3 barrel length.
In a preferred embodiment in accordance with the present invention, polyethylene or a combination thereof thing, inorganic one-tenth Hole agent and optional additive enter through said two polyethylene composition after being pre-mixed uniformly Material mouth 14 adds described extrusion device, preferably by Inorganic pore forming agents with high-molecular polythene in advance Mix homogeneously, is pre-mixed uniformly by optional additive and ultra high molecular polyethylene, above-mentioned Two kinds of mixture add described extrusion through said two polyethylene composition charging aperture 14 respectively Device, is more easy to mix homogeneously.
Said mixture is heated to molten condition and along described machine barrel in described extrusion device Extrusion, adds organic pore former through said two pore former charging aperture 15 in extrusion direction, Extrude casting films after melted also mix homogeneously, polyethylene composition and pore former can be avoided to occur It is separated and causes mixing inequality and with pressure oscillation in extruder so that polyethylene composition Thing and pore former are sufficiently mixed uniformly, and pore former is uniformly distributed in polyethylene composition mixture In, the aperture beneficially preparing micropore in subsequent step and the battery that is more evenly distributed every Film.
Cooling roller device
As in figure 2 it is shown, described cooling roller device includes that axis is positioned in same level One slab roller 1 and the second slab roller 2, between described first slab roller 1 and the second slab roller 2 Spacing is 180-580 μm, preferably 230-530 μm, more preferably 280-480 μm.
In a kind of detailed description of the invention of the present invention, as in figure 2 it is shown, the second slab roller 2 Between the first slab roller 1 and the 3rd slab roller 3, the 3rd slab roller the first slab roller 1 with Second slab roller 2 is close to each other, and forms space, and the axis of two described slab rollers In same level, the highest point of the 3rd slab roller 3 roller is higher than the second slab roller 2 roller Highest point, wherein, the diameter of the second slab roller 2 is more than the diameter of the first slab roller 1.
First the film forming raw material of the molten condition of extrusion is adsorbed in the surface of the second slab roller 2, And the space accumulation between the first slab roller 1 and the second slab roller 2 forms storage film, described storage Film both sides are cooled down rapidly by the first slab roller 1 and the second slab roller 2 respectively, and first Casting films is formed under slab roller 1 and the second slab roller 2 squeezing action in relative rotation, i.e. thick Sheet, reduces the factor shadows to sheet character such as rate of extrusion inequality, extruder machinery concussion Ringing, thus prepare the sheet that thickness is uniform, character is stable, prepared sheet is through the 3rd Slab roller 3 is cooled down by stretching and one side first.
Sheet through the 3rd slab roller 3 is drawn to subsequent technique by carry-over pinch rolls 12 again, excellent Selection of land, described carry-over pinch rolls 12 are multiple, more preferably 3.
According in another embodiment of the invention, as it is shown on figure 3, described slab roller Offer through hole on the end face at two ends, as inlet or liquid outlet 4, described inlet or Go out the internal chiller arranged of liquid 4 and slab roller to connect, it is preferable that described inlet or Go out the spiral-shaped groove 13 that liquid 4 offers with described chiller outer surface to connect, thus Realize the control to slab roller surface temperature.
According in another embodiment of the present invention, as shown in Figure 4, in slab roller Portion is provided with chiller, offers spiral-shaped groove at described chiller outer surface 13, it is preferable that offer a plurality of spiral-shaped groove, for cooling medium in slab roller The circulation in portion.
In a preferred embodiment in accordance with the present invention, described first slab roller 3 and the second casting Sheet roller 4 opposite direction rotating, from the casting films of extruder die head 5 extrusion at the first slab roller 3 and the Formed between two slab rollers 4 and pile up, be then passed through space extruding therebetween, cooling, Casting sheet, the factors such as rate of extrusion inequality, extruder machinery concussion that reduce are to sheet The impact of shape, thus prepare the sheet that thickness is uniform, character is stable.
In a preferred embodiment in accordance with the present invention, described first slab roller 3 and the second casting The diameter of sheet roller 4 is than for 1:(1～6), preferably 1:(2～5), more preferably 1:(3～4), A diameter of 300-600mm of the most described first slab roller 3, the second slab roller 4 a diameter of 500-900mm。
At the chiller that is internally provided with of described first slab roller 3 and the second slab roller 4, use In controlling the first slab roller 3 and temperature on the second slab roller 4 surface, thus the curtain coating to extrusion Film cools down, and the temperature of the most described first slab roller 3 and the second slab roller 4 is 5～40 DEG C, preferably 10～35 DEG C, more preferably 12～33 DEG C, the casting films of extrusion flows through Two-sided cooling molding during space between one slab roller 3 and the second slab roller 4, casts sheet, Meanwhile, being uniformly distributed pore former therein occurs thermotropic phase to divide with polyethylene composition From, pore former is closed therein by the sheet of two-sided cooling, cold with one side in traditional handicraft But sheet is compared, and pore former is less susceptible to ooze out, and is conducive to preparing the aperture of micropore, distribution More uniform battery diaphragm.
In a preferred embodiment in accordance with the present invention, optionally by described first slab roller 3 or The surface of the second slab roller 4 is processed into rough plane, can prepare single or double coarse Battery diaphragm, improve membrane surface to other material (such as coating, film etc.) Adhesive power, lays a good foundation for research and development novel battery barrier film.
Drying device
As it is shown in figure 5, described drying device includes the transfer roller 6 that multiple one-tenth broken line is arranged, The position that thin film contacts with transfer roller 6 is provided with for dry air gun 7.
In a preferred embodiment in accordance with the present invention, the jet direction of described air gun 7 and institute State the plane tangent of transfer roller 6.
In a preferred embodiment in accordance with the present invention, the thin film after extraction is through multiple transfer rollers 6 advance along broken line, and the position contacted with each transfer roller 6 at thin film is provided with for being dried Air gun 7, with remove film surface residual extractant, prevent stain mark, described gas The jet direction of rifle 7 and the plane tangent of transfer roller, i.e. parallel with the direction of transfer of thin film, Drying effect is good, and effectively prevent the generation of film surface water ripples, meanwhile, air gun The vertical impact forces of 7 pairs of thin film is obviously reduced, and significantly improves final preparing outside battery diaphragm See the bad phenomenon such as fold, scollop, scallop.
Different from foregoing of the present invention, and in traditional processing technology, as shown in Figure 6, Thin film after extraction linearly transmits, and uses hydraulic giant 8 and air gun 7 mixing to be dried, system Easily there are water ripples in the film surface obtained, causes the final battery diaphragm uneven thickness prepared Or uneven, and hydraulic giant 8 and air gun 7 inject directly on the surface of thin film the most at a certain angle, punching Power of hitting is big, and the phenomenon such as battery diaphragm outward appearance fold, scollop, scallop is serious, affects battery diaphragm Use and rolling.
According in another embodiment of the present invention, as it is shown in fig. 7, described three kinds micro- The battery diaphragm of pore structure includes first outer layer the 9, second outer layer 10 and is clipped in therebetween Internal layer 11, described first outer layer the 9, second outer layer 10 and internal layer 11 have different micropore knots Structure.
The aperture of described first outer layer 9 is 20～100nm, and the aperture of the second outer layer 10 is 30～140nm, the aperture of internal layer 11 is 50～180nm.
Embodiment
Embodiment 1
There is the polyethylene composition of the lithium ion battery separator of three kinds of microcellular structures for preparation Thing includes the component of following weight proportion:
Wherein,
The number-average molecular weight of high-molecular polythene is 500,000,
The number-average molecular weight of ultra high molecular polyethylene is 1,400,000,
The mean molecule quantity of white oil is 200,
The particle diameter of described nanometer magnesium chloride is 50～70nm.
Above-mentioned composition is made in accordance with the following methods lithium ion battery separator:
Step 1), extrusion: by high-molecular polythene and nanometer magnesium chloride melting mixing, by the One charging aperture add extruder, by ultra high molecular polyethylene, 4,4-thiobis is (between the 6-tert-butyl group Cresol), 2,4-DihydroxyBenzophenone, octadecyl quaternary ammonium sodium and Tween 80 enter by second Material mouth adds extruder, by white oil by the first pore former charging aperture and the second pore former charging aperture Adding extruder, be 210～240 DEG C at extrusion temperature, rate of extrusion is the bar of 1200g/min Under part, above-mentioned composition is extruded, form casting films；
Step 2), slab: step 1) casting films that is extruded into flows through the first slab roller (table Face is smooth, and surface temperature is 20 DEG C) and the second slab roller (smooth surface, surface temperature is 20 DEG C) between gap, cast the sheet that thickness is 400 μm；
Step 3), longitudinal stretching: step 2) the most preheated roller of the sheet (surface that obtains Temperature is 80 DEG C), draw roll (ratio of elongation of every grade is 6, and surface temperature is 110 DEG C) and Chill roll (surface temperature is 20 DEG C) carries out longitudinal stretching；
Step 4), cross directional stretch for the first time: step 3) thin film that obtains is in the direction of the width Both sides be individually fixed on clamping device, through the first preheating zone, (surface temperature is successively 100 DEG C), the first drawing zone (ratio of elongation of every grade is 7, and surface temperature is 115 DEG C) and During one cooling zone (surface temperature is 95 DEG C), under the effect of described clamping device, carry out horizontal stroke To stretching；
Step 5), extraction: step 4) thin film that obtains is through the first extractant (dichloromethane The mixture formed by weight 22:1 with trimethyl phosphate) and the second extractant (high purity water) Soak 6h, be then dried with air gun, obtain thin film；
Step 6), cross directional stretch for the second time: step 5) thin film that obtains is in the direction of the width Both sides be individually fixed on clamping device, through the second preheating zone, (surface temperature is successively 115 DEG C), the second drawing zone (ratio of elongation of every grade is 1.2, and surface temperature is 125 DEG C) and Second cooling zone (surface temperature is 95 DEG C) carries out second time cross directional stretch, and obtaining thickness is 16.2 μm have the battery diaphragm of three kinds of microcellular structures.
Embodiment 2
The component of following weight proportion is included for preparing the compositions of lithium ion battery separator:
Wherein,
The number-average molecular weight of high-molecular polythene is 300,000.
The number-average molecular weight that ultra high molecular polyethylene is is 1,300,000.
The mean molecule quantity of white oil is 180；
The particle diameter of nanometer magnesium chloride is 60～90nm.
Above-mentioned composition is prepared in accordance with the following methods lithium ion battery separator:
Step 1), extrusion: by high-molecular polythene and nanometer magnesium chloride melting mixing, by the One charging aperture add extruder, by ultra high molecular polyethylene, 3,5-di-t-butyl-4-hydroxyl first Benzene, 4 benzoyloxy 2,2,6,6 tetramethyl piperidine, octadecyl quaternary ammonium sodium and lauric acid Extruder is added, by white oil by the first pore former charging aperture and the second pore-forming by the second charging aperture Agent charging aperture is separately added into extruder, is 210～240 DEG C at extrusion temperature, and rate of extrusion is Under conditions of 1200g/min, above-mentioned composition is extruded, form casting films；
Step 2), slab: step 1) casting films that is extruded into flows through the first slab roller (table Surface roughness is 0.1, and surface temperature is 20 DEG C) and the second slab roller (surface roughness is 0.2, surface temperature is 20 DEG C) between gap, cast the sheet that thickness is 400 μm；
Step 3), longitudinal stretching: step 2) the most preheated roller of the sheet (surface that obtains Temperature is 80 DEG C), draw roll (ratio of elongation of every grade is 6, and surface temperature is 110 DEG C) and Chill roll (surface temperature is 20 DEG C) carries out longitudinal stretching；
Step 4), cross directional stretch for the first time: step 3) thin film that obtains is in the direction of the width Both sides be individually fixed on clamping device, through the first preheating zone, (surface temperature is successively 100 DEG C), the first drawing zone (ratio of elongation of every grade is 7, and surface temperature is 115 DEG C) and During one cooling zone (surface temperature is 95 DEG C), under the effect of described clamping device, carry out horizontal stroke To stretching, obtain thin film；
Step 5), extraction: step 4) thin film that obtains is through the first extractant (dichloromethane The mixture formed by weight 22:1 with trimethyl phosphate) and the second extractant (high purity water) Soak 6h, be then dried with air gun, obtain thin film；
Step 6), cross directional stretch for the second time: step 5) thin film that obtains is in the direction of the width Both sides be individually fixed on clamping device, through the second preheating zone, (surface temperature is successively 115 DEG C), the second drawing zone (ratio of elongation of every grade is 1.2, and surface temperature is 125 DEG C) and Second cooling zone (surface temperature is 95 DEG C) carries out second time cross directional stretch, and obtaining thickness is 16.2 μm have the battery diaphragm of three kinds of microcellular structures.
Comparative example
Comparative example 1
Use the preparation of battery diaphragm described in embodiment 6 in patent CN201210454073.9 Method, it may be assumed that the polyethylene that number-average molecular weight is 800,000 g/mol is heated to 180 DEG C and melts, Add in double screw extruder with 54kg/h feed rate.White oil is heated to 95 DEG C, with 2,6- Di-tert-butyl-4-methy phenol mix and blend 3h, injects mixture twin screw at twice and squeezes Go out in machine.Temperature within extruder is 200 DEG C, and extrusion temperature is 190 DEG C, extruded material The sheet that thickness is 1.4mm is cast in space extruding between 15 DEG C of chill rolls and adjustable roller. Polyethylene is 1:2.4 with the mass ratio of white oil, and the quality of 2,6-di-tert-butyl-4-methy phenols is The 1.0% of white oil quality.
Sheet obtained above is carried out successively longitudinal stretching and first time cross directional stretch, longitudinally The temperature of stretching is 100 DEG C, and stretching ratio is 5.78, and the temperature of cross directional stretch is for the first time 120 DEG C, stretching ratio is 4.41, after dichloromethane extracts, obtains medial septum.
Medial septum obtained above is carried out second time cross directional stretch, for the second time cross directional stretch Temperature be 132 DEG C, stretching ratio is 1.6, and rolling is cut, 50 DEG C of Ageing Treatment 18h, To battery diaphragm.
Experimental example
The battery diaphragm preparing embodiment and comparative example is tested as follows, and test result is shown in Table 1:
(1) thickness of battery diaphragm is measured；
(2) use electronic scanner microscope to observe the microcellular structure of battery diaphragm, and measure Aperture；
(3) press pump instrument is used to measure the porosity of battery diaphragm；
(4) venting quality tester is used to measure the venting quality of battery diaphragm；
(5) tension tester is used to measure the longitudinal tensile strength of battery diaphragm and laterally draw Stretch intensity；
(6) electronic tensile machine is used to measure the puncture strength of battery diaphragm, longitudinal extension rate With horizontal expansion rate；
(7) the longitudinally heat using battery diaphragm percent thermal shrinkage tester to measure battery diaphragm is received Shrinkage and horizontal percent thermal shrinkage；
(8) battery septum closed pore temperature and broken film temperature tester is used to measure battery diaphragm Closed pore temperature and broken film temperature.
Table 1. battery diaphragm test result
Being learnt by above example, comparative example and experimental example, utilize that the present invention provides is cold But roller arrangement can prepare the battery diaphragm with three kinds of microcellular structures of function admirable.
In describing the invention, it should be noted that term " interior ", " outward " etc. instruction Orientation or position relationship are based on the orientation under duty of the present invention or position relationship, are only For the ease of describe the present invention and simplify describe rather than instruction or hint indication device or Element must have specific orientation, with specific azimuth configuration and operation, therefore can not manage Solve as limitation of the present invention.Additionally, term " first ", " second " are only used for describing purpose, And it is not intended that indicate or hint relative importance.
Above in association with detailed description of the invention and exemplary example, the present invention is carried out specifically Bright, but these explanations can not be interpreted as limitation of the present invention.Those skilled in the art Understand, without departing from the spirit and scope of the invention, can be to the technology of the present invention side Case and embodiment thereof carry out multiple equivalencing, modify or improve, and these each fall within this In bright scope.Protection scope of the present invention is as the criterion with claims.

Claims (10)

1. prepare a cooling roller device for three kinds of microcellular structure lithium ion battery separators, It is characterized in that: this cooling roller device includes the first slab roller (1), the second slab roller (2) and the 3rd slab roller (3), wherein,
Described second slab roller (2) is positioned at described first slab roller (1) and described Between three slab rollers (3)；
Have between described first slab roller (1) and the second slab roller (2) between making a reservation for Away from,
Preferably, described first slab roller (1) and described second slab roller (2) Axis is positioned in same level.
Cooling roller device the most according to claim 1, it is characterised in that in institute State and be provided with described first slab roller (1) of regulation on the first slab roller (1) with described The regulation parts of the second slab roller (2) spacing.
Cooling roller device the most according to claim 1 and 2, it is characterised in that institute Stating the first slab roller (1) with the second slab roller (2) spacing is 180-580 μm, excellent Elect 230-530 μm, more preferably 280-480 μm as.
4., according to the cooling roller device one of claims 1 to 3 Suo Shu, its feature exists In the diameter ratio of, described first slab roller (1) and the second slab roller (2) for 1:(1～6), It is preferably 1:(2～5), more preferably 1:(3～4).
5., according to the cooling roller device one of Claims 1-4 Suo Shu, its feature exists In, at described first slab roller (1), the second slab roller (2) and the 3rd slab roller (3) Inside is provided with for reducing the first slab roller (1), the second slab roller (2) and The chiller of three slab rollers (3) surface temperature, it is preferable that at described chiller Outer surface offers spiral-shaped groove.
6., according to the cooling roller device one of claim 1 to 5 Suo Shu, its feature exists In, described first slab roller (1), the second slab roller (2) and the 3rd slab roller (3) Surface temperature be respectively 5～40 DEG C, preferably 10～35 DEG C, more preferably 12～33 DEG C.
7., according to the cooling roller device one of claim 1 to 6 Suo Shu, its feature exists In, described first slab roller (1) and described second slab roller (2) rotate in opposite directions, Preferably, the roller linear velocity of described first slab roller (1) and described second slab roller (2) roller linear velocity numerical value is equal.
8., according to the cooling roller device one of claim 1 to 7 Suo Shu, its feature exists In, described first slab roller (1), the second slab roller (2) and the 3rd slab roller (3) Surface be smooth or textured.
9., according to the cooling roller device one of claim 1 to 8 Suo Shu, its feature exists In, described battery diaphragm is prepared according to the method comprised the steps:
1), polyethylene or a combination thereof thing, pore former and other optional additive are melted Melt mixing, extrude casting films；
2), step 1) casting films extruded flows through the first slab roller (1) and the second casting Space between sheet roller (2), casts sheet；
3), step 2) the most preheated roller of sheet, draw roll and the chill roll that obtain enter Row longitudinal stretching；
4), step 3) the thin film both sides that obtain fix, successively through the first preheating zone, One drawing zone and the first cooling zone carry out cross directional stretch；
5), step 4) thin film that obtains processes through extractant, is then dried；Preferably, Described drying device includes the transfer roller that multiple one-tenth broken line is arranged, at thin film and transfer roller The position contacted is provided with for dry air gun, the jet side of the most described air gun To preferably with the plane tangent of described transfer roller or parallel with the direction of transfer of thin film；
6), step 5) the thin film both sides that obtain fix, successively through the second preheating zone, Two drawing zones and the second cooling zone carry out second time cross directional stretch, obtain having three kinds micro- The lithium ion battery separator of pore structure.
10. according to the cooling roller device one of claim 1 to 9 Suo Shu for preparation three The purposes of kind of microcellular structure lithium ion battery separator, it is characterised in that described battery every Film includes the first outer layer (9), the second outer layer (10) and is clipped in internal layer therebetween (11), described first outer layer (9), the second outer layer (10) and internal layer (11) have Different microcellular structures, the aperture of the most described first outer layer (9) is 20～100nm, The aperture of the second outer layer (10) is 30～140nm, and the aperture of internal layer (11) is 50～180 nm。
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CN108466415A (en) * 2018-05-04 2018-08-31 湖南烁普新材料有限公司 Wet method diaphragm membrane preparation facilities and preparation method
CN109192907A (en) * 2018-09-30 2019-01-11 湖南润沅新材料有限公司 Quickly cooling device is used in a kind of manufacture of lithium ion battery separator
CN110571389A (en) * 2019-08-02 2019-12-13 河北金力新能源科技股份有限公司 Forming device and forming method for lithium battery diaphragm casting sheet
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CN111463417A (en) * 2020-04-17 2020-07-28 贵州梅岭电源有限公司 Method for doping conductive agent into positive electrode material
CN112497713A (en) * 2020-06-14 2021-03-16 湖南安福环保科技股份有限公司 Quick wire drawing forming device of heat-seal cloth
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CN107808943A (en) * 2017-09-28 2018-03-16 广东工业大学 A kind of multi-layer polyolefin micro-pore septum and preparation method thereof
CN108466415A (en) * 2018-05-04 2018-08-31 湖南烁普新材料有限公司 Wet method diaphragm membrane preparation facilities and preparation method
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CN110877448A (en) * 2018-09-05 2020-03-13 李鑫 Cast sheet system of polyethylene microporous membrane with three-dimensional restraint
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CN109192907A (en) * 2018-09-30 2019-01-11 湖南润沅新材料有限公司 Quickly cooling device is used in a kind of manufacture of lithium ion battery separator
CN110571389A (en) * 2019-08-02 2019-12-13 河北金力新能源科技股份有限公司 Forming device and forming method for lithium battery diaphragm casting sheet
CN110571389B (en) * 2019-08-02 2022-03-11 河北金力新能源科技股份有限公司 Forming device and forming method for lithium battery diaphragm casting sheet
CN110828751A (en) * 2019-11-06 2020-02-21 江苏厚生新能源科技有限公司 Preparation method of polyethylene diaphragm with multilayer microporous structure
WO2021175277A1 (en) * 2020-03-04 2021-09-10 华为技术有限公司 Battery separator and preparation method therefor, battery, and terminal
CN111463417A (en) * 2020-04-17 2020-07-28 贵州梅岭电源有限公司 Method for doping conductive agent into positive electrode material
CN112497713A (en) * 2020-06-14 2021-03-16 湖南安福环保科技股份有限公司 Quick wire drawing forming device of heat-seal cloth
CN112582750A (en) * 2020-12-07 2021-03-30 界首市天鸿新材料股份有限公司 Process for preparing high-performance lithium battery diaphragm by using polyethylene graft copolymer
CN116638698A (en) * 2023-05-31 2023-08-25 镇江越升智能装备制造有限公司 Wet diaphragm wire casting piece casting equipment for lithium battery and application method of wet diaphragm wire casting piece casting equipment

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