CN103273654A - Preparation method for ultrathin polyolefin microporous membrane, and polyolefin microporous membrane prepared by same - Google Patents
Preparation method for ultrathin polyolefin microporous membrane, and polyolefin microporous membrane prepared by same Download PDFInfo
- Publication number
- CN103273654A CN103273654A CN201310144948XA CN201310144948A CN103273654A CN 103273654 A CN103273654 A CN 103273654A CN 201310144948X A CN201310144948X A CN 201310144948XA CN 201310144948 A CN201310144948 A CN 201310144948A CN 103273654 A CN103273654 A CN 103273654A
- Authority
- CN
- China
- Prior art keywords
- stretching
- preparation
- annealing
- basement membrane
- microporous membrane
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
Images
Abstract
The invention discloses a preparation method for an ultrathin polyolefin microporous membrane, and a polyolefin microporous membrane prepared by the same. The preparation method comprises the steps of tape casting a polyolefin melt into a substrate, annealing the substrate, stretching at a drawing ratio of 1.0-2.5, and performing thermosetting treatment to prepare the polyolefin microporous membrane. The stretching step includes cold stretching and stepwise hot stretching, wherein the conditions for the stepwise hot drawing stretching are as follows: a number of stretching points is 10-30; a stretching rate per stretching point is smaller than or equal to 200%/min; and a stretching temperature at each stretching point is from Tm-90 DEG C to Tm-15 DEGC, wherein Tm represents a melting point of the polyolefin. The method is characterized in that the prepared polyolefin microporous membrane has the characteristic of very uniform pore structure by stepwise hot stretching at relatively low stretching rate through a plurality of stretching points. Besides, the method is very suitable for making the ultrathin polyolefin microporous membrane with the thickness of 6-14 [mu]m. The polyolefin microporous membrane can meet applications having relatively high requirements for pore-forming homogeneity of the microporous membrane and the thickness of the membrane, and is particularly suitable for the fields of battery diaphragms.
Description
Technical field
The application relates to the battery diaphragm field, particularly relates to a kind of preparation method of ultra-thin MIcroporous polyolefin film and the MIcroporous polyolefin film of preparation thereof.
Background technology
MIcroporous polyolefin film is widely used in fields such as battery diaphragm, filter membrane, medical film.At present, the manufacture method of MIcroporous polyolefin film has two kinds of wet method and dry method: Asahi-Kasai, the MitsuiChemical of Japan and relevant patent JP2004323820 (2004), the U.S.Patent6245272 (2001) of Tonen company have reported wet processing, wet process need be used a large amount of organic diluents, the equipment complexity, the cost height, easily cause environmental pollution, advantage is to make 8～20 microns ultrathin membrane, and is also very difficult less than the film of 14 μ m but this method is produced thickness; United States Patent (USP) U.S.Patent3558764 (1971), 5385777(1995) reported dry process, the relative equipment of dry method is simple, cost is low, the non-environmental-pollution problem, but the most thickness of present commercial barrier film is more than 20 μ m, and having only minute quantity thickness is the product of 16 μ m, and than wet method, dry method is higher to the control accuracy requirement of technology, and the barrier film of production often uniformity is relatively poor.
Constantly popularizing and continuous advancement in technology of lithium battery applications had higher requirement to uniformity and the thickness of barrier film.On the one hand, the uniformity of battery diaphragm influences the uniformity between each battery cell, also influences the uniformity that discharges and recharges between each inside battery both positive and negative polarity; These all can cause harmful effect to qualification rate, security and the life-span of battery, and prior art does not still have good solution.On the other hand, guaranteeing under the prerequisite of membrane properties that each battery manufacturer wishes that barrier film gets over Bao Yuehao, thin barrier film is conducive to improve energy density and the capacity of battery.But prior art is even, the stay-in-grade ultra-thin barrier film of production structure well.
Summary of the invention
The preparation method that the application's purpose is to provide a kind of new MIcroporous polyolefin film can prepare the uniform ultra-thin polyalkene diaphragm of microcellular structure according to this method.
To achieve these goals, the technical scheme that adopts of the application is as follows:
The application's one side discloses a kind of preparation method of MIcroporous polyolefin film, comprise the polyolefin melt curtain coating is become basement membrane, respectively basement membrane is annealed then, stretch, thermal finalization is handled, make MIcroporous polyolefin film, wherein, the whole draw ratio that stretches is 1.0～2.5, stretching comprises cold drawn and hot-drawn, hot-drawn is the substep hot-drawn, and the hot drawn actual conditions of substep is 10～50 of drawing points, the rate of extension of each drawing point is 50～200%/min, draw ratio is 1.0～2.5, and the draft temperature of each drawing point is Tm-90 ℃～Tm-15 ℃, and wherein Tm is polyolefinic fusing point.Wherein, Tm-90 ℃～Tm-15 ℃ expression deducts 90 ℃ temperature at polyolefinic melting temperature, deducts to polyolefinic melting temperature in 15 ℃ the scope of temperature to stretch.
Further, the polyolefin melt curtain coating is become basement membrane, specifically comprise, polyolefin melt is melt extruded under 180 ℃～280 ℃, curtain coating becomes basement membrane, draw ratio 100～200.
Further, annealing specifically comprises, controls Tm-70 ℃ of annealing temperature～Tm-10 ℃, annealing time 10min～24h, and the elastic recovery rate of annealing back basement membrane is 80%～98%.Preferably, the elastic recovery rate of annealing back basement membrane is 85%～93%.Wherein, Tm-70 ℃～Tm-10 ℃ expression deducts 70 ℃ temperature at polyolefinic melting temperature, deducts to polyolefinic melting temperature in 10 ℃ the scope of temperature to carry out annealing in process.
Further, cold drawnly specifically comprise, at 10 ℃～80 ℃, under hauling speed 0.1m/min～20m/min, stretch draw ratio 0.15～0.85 with the rate of extension of 200%/min～2000%/min.
Further, thermal finalization comprises that with the microporous barrier negative stretch 1%～30% after the stretch processing, heat treatment 2s～10min under Tm-50 ℃～Tm-5 ℃ temperature namely makes MIcroporous polyolefin film simultaneously.Wherein, Tm-50 ℃～Tm-5 ℃ expression deducts 50 ℃ temperature at polyolefinic melting temperature, deducts to polyolefinic melting temperature in 15 ℃ the scope of temperature to heat-treat.
Different characteristics at the application and common dry technique special needs to be pointed out is, the great difference of the more known dry technique of the present invention is employing multiple spot stretching technique, and the more known dry technique of the rate of extension of each drawing point is little by 20～200%.It is high 5～10 ℃ that another difference of the more known dry technique of the present invention is that the more known dry technique of casting films curtain coating temperature is wanted, and draw ratio is more about 20～100%, and annealing temperature, hot-drawn temperature and the more known dry technique of heat setting temperature will hang down about 5～20 ℃.
The polyolefin that adopts among the application is polyethylene and/or polypropylene.The material that is appreciated that the application can be polyethylene or polypropylene, also can be two kinds mixing.
The application's another side discloses a kind of MIcroporous polyolefin film that is prepared by the application's preparation method.
Disclosed herein as well is the application's the application of MIcroporous polyolefin film in battery diaphragm.
The application's one side again discloses a kind of battery diaphragm, includes the application's MIcroporous polyolefin film in this battery diaphragm.Need to prove that the disclosed battery diaphragm of the application can be single or multiple lift, when battery diaphragm was individual layer, then this layer namely adopted the MIcroporous polyolefin film of preparation method's preparation of the application; When battery diaphragm was multilayer, wherein one deck was the application's MIcroporous polyolefin film at least.
Because adopt above technical scheme, the application's beneficial effect is:
The application's preparation method improves on the basis of dry process, adopts substep hot-drawn method, and specifically controls 10～50 of drawing points, stretches under slower stretching ratio, makes that the MIcroporous polyolefin film pore-forming of preparing is even; Solve the homogeneity question of MIcroporous polyolefin film from the even aspect of pore-forming, further improved the serviceability of MIcroporous polyolefin film.Another beneficial effect of the present invention is, adopts the technology of the present invention can produce high-quality ultra-thin barrier film.The MIcroporous polyolefin film of the application's preparation method preparation can satisfy the application that microporous barrier uniformity and thickness are had higher requirements, and is particularly suitable for the battery diaphragm field.
Description of drawings
Fig. 1 is the surface scan Electronic Speculum figure as a result of the MIcroporous polyolefin film of the application's Comparative Examples 1 preparation;
Fig. 2 is the surface scan Electronic Speculum figure as a result of the MIcroporous polyolefin film of the embodiment of the present application 1 preparation;
Fig. 3 is the profile scanning Electronic Speculum figure as a result of the MIcroporous polyolefin film of the embodiment of the present application 1 preparation.
The specific embodiment
The application is at the not enough problem of existing MIcroporous polyolefin film pore-forming uniformity, on the basis of existing technology, existing dry technique is optimized, thereby has proposed a kind of improved method for preparing polyolefin microporous membrane.This preparation method is divided into cold drawn it and hot-drawn in stretching step, and adopt the substep hot-drawn, 10～50 of drawing points, the rate of extension of each drawing point is less than or equal to 50～200%/min, draw ratio is 1.0～2.5, the draft temperature of each drawing point is Tm-90 ℃～Tm-15 ℃, and wherein Tm is polyolefinic fusing point.By a plurality of drawing points, under relatively low rate of extension, carry out the substep hot-drawn, make the MIcroporous polyolefin film of preparation have pore-forming uniformity preferably.
Need to prove, wherein rate of extension 200%/min represents that per minute stretches 200%, this rate of extension is the application's a critical value, remain on to be less than or equal under this rate of extension and stretch, can be at the platelet orientations uniform MIcroporous polyolefin film of stretched pore-forming under the situation preferably.Draft temperature is adjusted according to polyolefinic concrete fusing point, and among the application, preferred hot drawn draft temperature deducts 90 ℃ at the polyolefin melting temperature and deducts to the polyolefin melting temperature in 15 ℃ the scope, but more known dry technique will hang down about 5～20 ℃.
In addition, among the application, in order to obtain platelet orientations preferably, also become the condition of basement membrane to optimize to the polyolefin melt curtain coating, concrete, polyolefin melt is melt extruded under 180 ℃～280 ℃, curtain coating becomes basement membrane, control draw ratio 100～200.Further, in order to ensure the platelet orientations, also the annealing conditions of basement membrane is optimized, concrete, control Tm-70 ℃ of annealing temperature～Tm-10 ℃, annealing time 10min～24h, the elastic recovery rate of annealing back basement membrane is 80%～98%; Preferably, elastic recovery rate is 85%～93%.Wherein annealing temperature is adjusted according to polyolefinic fusing point equally, and the application's annealing temperature deducts 70 ℃ at the polyolefin melting temperature and deducts to the polyolefin melting temperature in 10 ℃ the scope.It is high 5～10 ℃ that the casting films curtain coating temperature of more known dry technique is wanted, and draw ratio is more about 20～100%, and annealing temperature and heat setting temperature will hang down about 5～20 ℃.
Adopt the application's preparation method can prepare the uniform ultra-thin MIcroporous polyolefin film of pore-forming, this MIcroporous polyolefin film is particularly suitable for battery diaphragm, thereby problem such as reduce that the battery qualification rate that the micropore lack of homogeneity because of battery diaphragm causes is low, poor stability and service life are short is conducive to promote battery capacity simultaneously.Be appreciated that the application's MIcroporous polyolefin film except being used for battery diaphragm, other pore-forming uniformity to MIcroporous polyolefin film has the field of specific (special) requirements can use equally.
Among the application, Tm represents polyolefinic fusing point, can adopt the DSC method to measure.Draw ratio is the ratio that curtain coating becomes sharp cooling roll draught line speed and die head discharging speed in the process of basement membrane.Draw ratio=(stretched film length-former length)/former length.Hauling speed refers to roller to the draught line speed of film, is roll surface speed under the normal condition.Rate of extension=draw ratio/stretching time.
Also by reference to the accompanying drawings the application is described in further detail below by specific embodiment.Following examples only further specify the application, should not be construed as the restriction to the application.
Comparative Examples 1
Be raw material with the polypropylene, polyacrylic index is mean molecule quantity 300000, density 0.902g/cm
3, 165 ℃ of fusing points, melt index 3.0 grams/10 minutes.Produce barrier film according to conventional barrier film production technology, its concrete operation is:
(1) curtain coating prepares basement membrane, under 240 ℃ condition, adopts T type curtain coating head to melt extrude the raw material polypropylene, and draw ratio is 80, makes basement membrane;
(2) annealing in process goes into the basement membrane of preparation in the step (1) to carry out annealing in process in the baking oven, and oven temperature is 145 ℃, and the time of annealing in process is 2 hours, and after annealing was finished, the basement membrane elastic recovery rate was 80%;
(3) basement membrane after the annealing in process in the step (2) is carried out earlier cold drawn formation crazing defective under 25 ℃ and 1000%/minutes stretching ratio, and then 80～150 ℃ temperature and 300%/minute stretching ratio under the formation microcellular structure that stretches;
(4) thermal finalization is handled, and the film that the back that stretches in the step (3) is formed micropore carries out negative stretch earlier, and ratio is 15%, microporous polypropylene membrane thermal finalization under 145 ℃ of conditions is handled 1 minute again, namely becomes the microporous polypropylene membrane product.
Comparative Examples 2
Be raw material with the polyethylene, poly index is mean molecule quantity 200000, density 0.965g/cm
3, 125 ℃ of fusing points, melt index 0.4 gram/10 minutes.Produce barrier film according to common process, concrete operation is:
(1) curtain coating prepares basement membrane, under 210 ℃ condition, adopts T type curtain coating head to melt extrude material polyethylene, and draw ratio is 80, makes basement membrane;
(2) annealing in process goes into the basement membrane of preparation in the step (1) to carry out annealing in process in the baking oven, and oven temperature is 110 ℃, and the time of annealing in process is 2 hours, and after annealing was finished, the basement membrane elastic recovery rate was 83%;
(3) basement membrane after the annealing in process in the step (2) is carried out earlier cold drawn formation crazing defective under 25 ℃ and 1000%/minutes stretching ratio, and then 70～105 ℃ temperature and 300%/minute stretching ratio under the formation microcellular structure that stretches;
(4) thermal finalization is handled, and the film that the back that stretches in the step (3) is formed micropore carries out negative stretch earlier, and ratio is 15%, microporous polypropylene membrane thermal finalization under 115 ℃ of conditions is handled 1 minute again, namely becomes the polyethene microporous membrane product.
Embodiment 1
Be raw material with the polypropylene, its index is mean molecule quantity 300000, density 0.902g/cm
3, 165 ℃ of fusing points, melt index 3.0 grams/10 minutes.Concrete operation is:
(1) curtain coating prepares basement membrane, under 240 ℃ condition, adopts T type curtain coating head to melt extrude the raw material polypropylene, and draw ratio is 50, makes basement membrane;
(2) annealing in process goes into the basement membrane of preparation in the step (1) to carry out annealing in process in the baking oven, and oven temperature is 145 ℃, and the time of annealing in process is 2 hours, and after annealing was finished, the basement membrane elastic recovery rate was 80%;
(3) hole forming by multipoint stretching, basement membrane after the annealing in process in the step (2) is carried out earlier cold drawn formation crazing defective under 10 ℃ and 2000%/minutes stretching ratio, and then 80～150 ℃ temperature and 400%/minute stretching ratio under carry out multiple spot and stretch and form microcellular structure, the drawing point that multiple spot stretches is 5;
(4) thermal finalization is handled, and the film that the back that stretches in the step (3) is formed micropore carries out negative stretch earlier, and ratio is 15%, microporous polypropylene membrane thermal finalization under 150 ℃ of conditions is handled 1 minute again, namely becomes the microporous polypropylene membrane product.
Embodiment 2
Be raw material with the polypropylene, its index is mean molecule quantity 300000, density 0.902g/cm
3, fusing point is 165 ℃, melt index 3.0 grams/10 minutes.Concrete operation is:
(1) curtain coating prepares basement membrane, under 240 ℃ condition, adopts T type curtain coating head to melt extrude the raw material polypropylene, and draw ratio is 100, makes basement membrane;
(2) annealing in process goes into the basement membrane of preparation in the step (1) to carry out annealing in process in the baking oven, and oven temperature is 155 ℃, and the time of annealing in process is 20 minutes, and after annealing was finished, the basement membrane elastic recovery rate was 93%;
(3) hole forming by multipoint stretching, basement membrane after the annealing in process in the step (2) is carried out earlier cold drawn formation crazing defective under 10 ℃ and 2000%/minutes stretching ratio, and then 80～150 ℃ temperature and 300%/minute stretching ratio under carry out multiple spot and stretch and form microcellular structure, the drawing point that multiple spot stretches is 20;
(4) thermal finalization is handled, and the film that the back that stretches in the step (3) is formed micropore carries out negative stretch earlier, and ratio is 30%, microporous polypropylene membrane thermal finalization under 130 ℃ of conditions is handled 10 minutes again, namely becomes the microporous polypropylene membrane product.
Embodiment 3
Be raw material with the polypropylene, its index is mean molecule quantity 350000, density 0.905g/cm
3, fusing point is 166 ℃, melt index 2.1 grams/10 minutes.Concrete operation is:
(1) curtain coating prepares basement membrane, under 280 ℃ condition, adopts T type curtain coating head to melt extrude the raw material polypropylene, and draw ratio is 150, makes basement membrane;
(2) annealing in process goes into the basement membrane of preparation in the step (1) to carry out annealing in process in the baking oven, and oven temperature is 140 ℃, and the time of annealing in process is 5 hours, and after annealing was finished, the basement membrane elastic recovery rate was 91%;
(3) hole forming by multipoint stretching, basement membrane after the annealing in process in the step (2) is carried out earlier cold drawn formation crazing defective under 40 ℃ and 1000%/minutes stretching ratio, and then 90～145 ℃ temperature and 150%/minute stretching ratio under carry out multiple spot and stretch and form microcellular structure, the drawing point that multiple spot stretches is 15;
(4) thermal finalization is handled, and the film that the back that stretches in the step (3) is formed micropore carries out negative stretch earlier, and ratio is 20%, microporous polypropylene membrane thermal finalization under 135 ℃ of conditions is handled 5 minutes again, namely becomes the microporous polypropylene membrane product.
Embodiment 4
Be raw material with the polypropylene, its index is mean molecule quantity 250000, density 0.907g/cm
3, fusing point is 166 ℃, melt index 2.0 grams/10 minutes.Concrete operation is:
(1) curtain coating prepares basement membrane, under 210 ℃ condition, adopts T type curtain coating head to melt extrude the raw material polypropylene, and draw ratio is 100, makes basement membrane;
(2) annealing in process goes into the basement membrane of preparation in the step (1) to carry out annealing in process in the baking oven, and oven temperature is 100 ℃, and the time of annealing in process is 24 hours, and after annealing was finished, the basement membrane elastic recovery rate was 86%;
(3) hole forming by multipoint stretching, basement membrane after the annealing in process in the step (2) is carried out earlier cold drawn formation crazing defective under 80 ℃ and 800%/minutes stretching ratio, and then 90～150 ℃ temperature and 100%/minute stretching ratio under carry out multiple spot and stretch and form microcellular structure, the drawing point that multiple spot stretches is 30;
(4) thermal finalization is handled, and the film that the back that stretches in the step (3) is formed micropore carries out negative stretch earlier, and ratio is 1%, microporous polypropylene membrane thermal finalization under 160 ℃ of conditions is handled 2 seconds again, namely becomes the microporous polypropylene membrane product.
Embodiment 5
Be raw material with the polyethylene, its index is mean molecule quantity 200000, density 0.965g/cm
3, fusing point is 125 ℃, melt index 0.4 gram/10 minutes.Concrete operation is:
(1) curtain coating prepares basement membrane, under 210 ℃ condition, adopts T type curtain coating head to melt extrude material polyethylene, and draw ratio is 80, makes basement membrane;
(2) annealing in process goes into the basement membrane of preparation in the step (1) to carry out annealing in process in the baking oven, and oven temperature is 110 ℃, and the time of annealing in process is 2 hours, and after annealing was finished, the basement membrane elastic recovery rate was 83%;
(3) hole forming by multipoint stretching, basement membrane after the annealing in process in the step (2) is carried out earlier cold drawn formation crazing defective under 50 ℃ and 400%/minutes stretching ratio, and then 75～110 ℃ temperature and 50%/minute stretching ratio under carry out multiple spot and stretch and form microcellular structure, the drawing point that multiple spot stretches is 50;
(4) thermal finalization is handled, and the film that the back that stretches in the step (3) is formed micropore carries out negative stretch earlier, and ratio is 15%, microporous polypropylene membrane thermal finalization under 115 ℃ of conditions is handled 1 minute again, namely becomes the polyethene microporous membrane product.
Embodiment 6
Be raw material with the polyethylene, its index is mean molecule quantity 180000, density 0.964g/cm
3, fusing point is 125 ℃, melt index 0.5 gram/10 minutes.Concrete operation is:
(1) curtain coating prepares basement membrane, under 180 ℃ condition, adopts T type curtain coating head to melt extrude material polyethylene, and draw ratio is 140, makes basement membrane;
(2) annealing in process goes into the basement membrane of preparation in the step (1) to carry out annealing in process in the baking oven, and oven temperature is 95 ℃, and the time of annealing in process is 18 hours, and after annealing was finished, the basement membrane elastic recovery rate was 86%;
(3) hole forming by multipoint stretching, basement membrane after the annealing in process in the step (2) is carried out earlier cold drawn formation crazing defective under 40 ℃ and 200%/minutes stretching ratio, and then 70～105 ℃ temperature and 30%/minute stretching ratio under carry out multiple spot and stretch and form microcellular structure, the drawing point that multiple spot stretches is 30;
(4) thermal finalization is handled, and the film that the back that stretches in the step (3) is formed micropore carries out negative stretch earlier, and ratio is 1%, microporous polypropylene membrane thermal finalization under 110 ℃ of conditions is handled 1 minute again, namely becomes the polyethene microporous membrane product.
Embodiment 7
Be raw material with the polyethylene, its index is mean molecule quantity 250000, density 0.964g/cm
3, fusing point is 120 ℃, melt index 0.6 gram/10 minutes.Concrete operation is:
(1) curtain coating prepares basement membrane, under 200 ℃ condition, adopts T type curtain coating head to melt extrude material polyethylene, and draw ratio is 100, makes basement membrane;
(2) annealing in process goes into the basement membrane of preparation in the step (1) to carry out annealing in process in the baking oven, and oven temperature is 85 ℃, and the time of annealing in process is 20 hours, and after annealing was finished, the basement membrane elastic recovery rate was 85%;
(3) hole forming by multipoint stretching, basement membrane after the annealing in process in the step (2) is carried out earlier cold drawn formation crazing defective under 20 ℃ and 300%/minutes stretching ratio, and then 80～105 ℃ temperature and 50%/minute stretching ratio under carry out multiple spot and stretch and form microcellular structure, the drawing point that multiple spot stretches is 30;
(4) thermal finalization is handled, and the film that the back that stretches in the step (3) is formed micropore carries out negative stretch earlier, and ratio is 3%, microporous polypropylene membrane thermal finalization under 110 ℃ of conditions is handled 1 minute again, namely becomes the polyethene microporous membrane product.
Thickness and Gurley index to the battery diaphragm of all Comparative Examples and embodiment are measured, and concrete measuring method is as follows:
Membrane thicknesses adopts the CHY-C2 of Labthink Instruments Co., Ltd. calibrator to press ASTM D5947-2006 canonical measure.
The Gurley index, characterize the gas permeability of barrier film, adopt Gurley air permeability measuring instrument to measure, each sample is chosen 10 different point measurement Gurley indexes, record its mean value and standard deviation, wherein standard deviation has reflected the uniformity of barrier film pore-forming, and the more little pore-forming uniformity of standard deviation is more good.
Test result is as shown in table 1, the Gurley standard of index deviation of two Comparative Examples is all bigger, the pore-forming uniformity that its microporous barrier is described is relatively poor, and the Gurley standard of index deviation of all embodiment is all much smaller than Comparative Examples, as seen, the pore-forming uniformity of the MIcroporous polyolefin film prepared of the application's preparation method has greatly improved.Simultaneously, the application has also adopted the surface micropore structure of scanning electron microscopic observation MIcroporous polyolefin film; Show intuitively by scanning electron microscopic observation, the pore-forming uniformity of the MIcroporous polyolefin film of preparation method's preparation of the application is better than Comparative Examples.Part ESEM result as depicted in figs. 1 and 2, Fig. 1 is the ESEM figure as a result of the MIcroporous polyolefin film of Comparative Examples 1 preparation, Fig. 2 be the ESEM figure as a result of the MIcroporous polyolefin film for preparing of embodiment 1.
Table 1 MIcroporous polyolefin film The performance test results
Above content be in conjunction with concrete embodiment to further describing that the application does, can not assert that the application's concrete enforcement is confined to these explanations.For the application person of an ordinary skill in the technical field, under the prerequisite that does not break away from the application's design, can also make some simple deduction or replace, all should be considered as belonging to the application's protection domain.
Claims (10)
1. the preparation method of a MIcroporous polyolefin film, comprise the polyolefin melt curtain coating is become basement membrane, then respectively to basement membrane anneal, stretching, thermal finalization handle, make MIcroporous polyolefin film, it is characterized in that: the draw ratio of described stretching is 1.0～2.5, described stretching comprises cold drawn and hot-drawn, described hot-drawn is the substep hot-drawn, the hot drawn actual conditions of described substep is, 10～50 of drawing points, the rate of extension of each drawing point is 50～200%/min, and the draft temperature of each drawing point is Tm-90 ℃～Tm-15 ℃, and wherein Tm is polyolefinic fusing point.
2. preparation method according to claim 1 is characterized in that: described the polyolefin melt curtain coating is become basement membrane, comprise that specifically polyolefin melt is melt extruded, and curtain coating becomes basement membrane, draw ratio 100～200 under 180 ℃～280 ℃.
3. preparation method according to claim 1 is characterized in that: described annealing specifically comprises, Tm-70 ℃ of control annealing temperature～Tm-10 ℃, and annealing time 10min～24h, the elastic recovery rate of annealing back basement membrane is 80%～98%.
4. preparation method according to claim 3, it is characterized in that: described elastic recovery rate is 85%～93%.
5. according to each described preparation method of claim 1～4, it is characterized in that: described cold drawnly specifically comprise, at 10 ℃～80 ℃, under hauling speed 0.1m/min～20m/min, rate of extension with 200%/min～2000%/min stretches, draw ratio 0.15～0.85.
6. according to each described preparation method of claim 1～4, it is characterized in that: described thermal finalization comprises, with the microporous barrier negative stretch 1%～30% after the stretch processing, heat treatment 2s～10min under Tm-50 ℃～Tm-5 ℃ temperature namely makes MIcroporous polyolefin film simultaneously.
7. according to each described preparation method of claim 1～4, it is characterized in that: described polyolefin is polyethylene and/or polypropylene.
8. according to the MIcroporous polyolefin film of each described preparation method preparation of claim 1～7.
9. the thickness of MIcroporous polyolefin film according to claim 8 is 6～14 μ m.
10. battery diaphragm, it is characterized in that: described battery diaphragm comprises the described MIcroporous polyolefin film of claim 8.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201310144948.XA CN103273654B (en) | 2013-04-24 | 2013-04-24 | The MIcroporous polyolefin film of a kind of ultra-thin method for preparing polyolefin microporous membrane and preparation thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201310144948.XA CN103273654B (en) | 2013-04-24 | 2013-04-24 | The MIcroporous polyolefin film of a kind of ultra-thin method for preparing polyolefin microporous membrane and preparation thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN103273654A true CN103273654A (en) | 2013-09-04 |
| CN103273654B CN103273654B (en) | 2015-11-25 |
Family
ID=49056325
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201310144948.XA Active CN103273654B (en) | 2013-04-24 | 2013-04-24 | The MIcroporous polyolefin film of a kind of ultra-thin method for preparing polyolefin microporous membrane and preparation thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN103273654B (en) |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104835930A (en) * | 2015-03-24 | 2015-08-12 | 中国科学技术大学 | A preparing method of a polyolefin microporous separating membrane |
| CN107599435A (en) * | 2017-09-28 | 2018-01-19 | 中国科学技术大学 | A kind of MIcroporous polyolefin film and preparation method thereof |
| CN110943194A (en) * | 2019-12-02 | 2020-03-31 | 江苏厚生新能源科技有限公司 | Preparation method and coating application of lithium battery diaphragm with controllable surface structure |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4873034A (en) * | 1987-04-30 | 1989-10-10 | Toa Nenryo Kogyo Kabushiki Kaisha | Process for producing microporous ultra-high-molecular-weight polyolefin membrane |
| CN101695869A (en) * | 2009-10-30 | 2010-04-21 | 沧州明珠塑料股份有限公司 | Preparation method of polyolefin microporous film |
| CN101704308A (en) * | 2009-10-30 | 2010-05-12 | 沧州明珠塑料股份有限公司 | Polyolefin three-layer composite microporous membrane and preparation method thereof |
| CN102153771A (en) * | 2010-11-12 | 2011-08-17 | 深圳市星源材质科技股份有限公司 | Polyolefin microporous membrane preparation method and use |
-
2013
- 2013-04-24 CN CN201310144948.XA patent/CN103273654B/en active Active
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4873034A (en) * | 1987-04-30 | 1989-10-10 | Toa Nenryo Kogyo Kabushiki Kaisha | Process for producing microporous ultra-high-molecular-weight polyolefin membrane |
| CN101695869A (en) * | 2009-10-30 | 2010-04-21 | 沧州明珠塑料股份有限公司 | Preparation method of polyolefin microporous film |
| CN101704308A (en) * | 2009-10-30 | 2010-05-12 | 沧州明珠塑料股份有限公司 | Polyolefin three-layer composite microporous membrane and preparation method thereof |
| CN102153771A (en) * | 2010-11-12 | 2011-08-17 | 深圳市星源材质科技股份有限公司 | Polyolefin microporous membrane preparation method and use |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104835930A (en) * | 2015-03-24 | 2015-08-12 | 中国科学技术大学 | A preparing method of a polyolefin microporous separating membrane |
| CN104835930B (en) * | 2015-03-24 | 2017-01-25 | 中国科学技术大学 | A preparing method of a polyolefin microporous separating membrane |
| CN107599435A (en) * | 2017-09-28 | 2018-01-19 | 中国科学技术大学 | A kind of MIcroporous polyolefin film and preparation method thereof |
| CN110943194A (en) * | 2019-12-02 | 2020-03-31 | 江苏厚生新能源科技有限公司 | Preparation method and coating application of lithium battery diaphragm with controllable surface structure |
Also Published As
| Publication number | Publication date |
|---|---|
| CN103273654B (en) | 2015-11-25 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN104022249B (en) | A kind of three layers of lithium battery diaphragm and preparation method thereof | |
| CN109065817B (en) | Porous multilayer composite diaphragm and preparation method thereof | |
| CN103407140B (en) | Preparation method for PP/PE/PE three-layer compound microporous film | |
| CN1243784C (en) | Polyolefine multiple micoporous film and preparing process thereof | |
| CN102769115A (en) | Lithium ion battery membrane prepared by polypropylene mixture and preparing method thereof | |
| CN102248713B (en) | Polyene microporous multilayer diaphragm and manufacturing method thereof | |
| EP3098256A1 (en) | Polyolefin microporous membrane and method for producing same | |
| CN109449349A (en) | A kind of microporous polypropylene membrane and its preparation method and application | |
| CN104395382A (en) | Porous polypropylene film, separator for electricity storage devices, and electricity storage device | |
| KR20160016805A (en) | Multilayer, microporous polyolefin membrane, and production method thereof | |
| US10205149B2 (en) | Manufacturing method of porous multilayered polyolefin | |
| WO2017152731A1 (en) | Method for preparing lithium-ion battery separator | |
| CN109980157A (en) | A kind of preparation method, battery diaphragm and the battery of anti-fold battery diaphragm | |
| CN102241142A (en) | Method for producing lithium battery diaphragm and transverse stretcher | |
| WO2023045384A1 (en) | High-porosity, high-permeability lithium ion battery base film and preparation method therefor, and lithium ion battery | |
| JP2015120786A (en) | Microporous film and separator using the same | |
| CN103273654B (en) | The MIcroporous polyolefin film of a kind of ultra-thin method for preparing polyolefin microporous membrane and preparation thereof | |
| JP2001081221A (en) | Polyolefin microporous film | |
| CN109728234B (en) | Lithium battery diaphragm with uniform aperture and preparation method thereof | |
| JPH0247031A (en) | Manufacture of microporous film | |
| CN109742296B (en) | Three-layer co-extrusion lithium battery diaphragm and preparation method thereof | |
| CN114188663A (en) | Multilayer diaphragm and preparation method thereof | |
| CN106626457A (en) | Preparation method of polyolefin microporous membrane | |
| WO2023045312A1 (en) | Microporous membrane with high pore uniformity and preparation method therefor, and battery | |
| CN113809474B (en) | Polypropylene diaphragm, preparation method thereof and lithium ion battery |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant | ||
| CP03 | Change of name, title or address |
Address after: 518120 No. 8 Binhai Road, Dapeng street, Dapeng New District, Shenzhen, Guangdong, China. Patentee after: Shenzhen Zhongxing new material technology Limited by Share Ltd Address before: 518000 block D, office building, Hanhan Innovation Park, Langshan Road, Nanshan District, Shenzhen, Guangdong 503 Patentee before: Shenzhen ZTE Innovation Material Technology Co., Ltd. |
|
| CP03 | Change of name, title or address |