CN106459467A - Microporous polyolefin membrane - Google Patents
Microporous polyolefin membrane Download PDFInfo
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- CN106459467A CN106459467A CN201580023402.6A CN201580023402A CN106459467A CN 106459467 A CN106459467 A CN 106459467A CN 201580023402 A CN201580023402 A CN 201580023402A CN 106459467 A CN106459467 A CN 106459467A
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- polyolefin
- temperature
- micro
- polyolefin membrane
- micro porous
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
- C08J5/20—Manufacture of shaped structures of ion-exchange resins
- C08J5/22—Films, membranes or diaphragms
- C08J5/2206—Films, membranes or diaphragms based on organic and/or inorganic macromolecular compounds
- C08J5/2218—Synthetic macromolecular compounds
- C08J5/2231—Synthetic macromolecular compounds based on macromolecular compounds obtained by reactions involving unsaturated carbon-to-carbon bonds
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J9/00—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof
- C08J9/26—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof by elimination of a solid phase from a macromolecular composition or article, e.g. leaching out
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L23/00—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers
- C08L23/02—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers not modified by chemical after-treatment
- C08L23/04—Homopolymers or copolymers of ethene
- C08L23/06—Polyethene
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L23/00—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers
- C08L23/02—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers not modified by chemical after-treatment
- C08L23/10—Homopolymers or copolymers of propene
- C08L23/12—Polypropene
Abstract
Provided is a microporous polyolefin membrane which is excellent in terms of appearance and high-temperature shape retentivity and which can pass a safety evaluation test with high certainty. The microporous polyolefin membrane contains 5-20% by weight polypropylene having a weight-average molecular weight of 1,500,000-3,000,000, 5-20% by weight polyethylene having a weight-average molecular weight of 1,500,000-2,500,000, and 60-90% polyethylene having a weight-average molecular weight of 200,000-500,000 and has a single-layer structure.
Description
Technical field
The present invention relates to a kind of excellent polyolefin micro porous polyolefin membrane of the shape retention under outward appearance, high temperature.
Background technology
Micro- as the polyolefin containing polyethylene (hereinafter also referred to as " PE ") and polypropylene (hereinafter also referred to as " PP ")
Perforated membrane is it is known that have the polyolefin micro porous polyolefin membrane of various compositions.
In patent documentation 1, disclose one kind containing weight average molecular weight (hereinafter also referred to as " Mw ") 100,000～4,000,000
The polyolefin micro porous polyolefin membrane of PP and PE.In this micro-porous film, width when 135～145 DEG C is (hereinafter also referred to as " TD side
To ") maximum contraction on melting rate be less than or equal to 40%, micro-porous film has the closing (shutdown) less than or equal to 135 DEG C
Temperature (hereinafter also referred to as " SD temperature ") and fusing (meltdown) temperature more than or equal to 150 DEG C are (hereinafter also referred to as " MD temperature
Degree ").
In patent documentation 2, disclose a kind of polyolefin micro porous polyolefin membrane of PP and PE containing Mw30 ten thousand～1,500,000.Should
Micro-porous film has 130～140 DEG C of SD temperature and 160～200 DEG C of MD temperature.
In patent documentation 3, disclose a kind of polyolefin micro porous polyolefin membrane containing PP and PE, overall the gluing of polyolefin is divided equally
Son amount (hereinafter also referred to as " Mv ") is 100,000～1,200,000.
In patent documentation 4, disclose a kind of polyolefin micro porous polyolefin membrane of PP and PE being more than or equal to 300,000 containing Mv.Should
Micro-porous film has 130～140 DEG C of SD temperature and the MD temperature more than or equal to 160 DEG C.
In patent documentation 5, disclose a kind of polyolefin micro porous polyolefin membrane of PP and PE being more than or equal to 500,000 containing Mw.Should
Micro-porous film has 120～140 DEG C of SD temperature and the MD temperature more than or equal to 165 DEG C.
And, the propulsion with energy capacity, current battery car battery needs barrier film thinner and guarantees
The safeties such as thermostability.Tightened up condition is required in the safety evaluatios of battery such as HotBox test.[prior art literature]
Patent documentation 1：International Publication WO2007/060990.
Patent documentation 2：Japanese Patent Laid 2010-540744 publication.
Patent documentation 3：Japanese Patent Laid-Open 2013-256606 publication.
Patent documentation 4：Japanese Patent Laid-Open 2008-266457 publication.
Patent documentation 5：Japanese Patent Laid-Open 2004-196870 publication.
Content of the invention
[inventing problem to be solved]
Although the polyolefin micro porous polyolefin membrane disclosed in patent documentation 1～5 is in achieving as used in battery etc.
The optimization of barrier film, but the shape having thrown a flood of light on the deciding factor for guaranteeing safety may not necessarily be said.
Therefore, problem to be solved by this invention is to provide a kind of polyolefin micro porous polyolefin membrane, the shape under its outward appearance, high temperature
Shape retentivity and the excellent in uniformity of micro-porous film physical property, and can be tested by safety evaluatio with high reliability.
[technological means of solve problem]
In order to solve the above problems, the polyolefin micro porous polyolefin membrane of the present invention is characterised by, with 5%～20% weight ratio
The polypropylene containing weight average molecular weight 150～3,000,000 for the example, with 5%～20% part by weight contain weight average molecular weight 150～
2500000 polyethylene, is contained the polyethylene of weight average molecular weight 20～500,000, has single layer structure with 60%～90% ratio.
Polyacrylic weight average molecular weight is preferably greater than and is equal to 2,000,000, is further preferably greater than equal to 2,500,000.Additionally, it is polyacrylic
Part by weight is preferably 6～15% or 7.5～10%.And, the weight of the polyolefin entirety being formed by polyethylene, polypropylene etc.
Ratio is preferably 20～25%.It should be noted that weight average molecular weight for example can pass through Japanese Patent Laid-Open 2013-32545
Assay method number described in publication is obtaining.
The polyolefin micro porous polyolefin membrane of the present invention has the composition of PP and PE as described above, particularly with the weight of regulation
Ratio contains the PE of the super high molecular weight of weight average molecular weight 150～2,500,000, although being thus the monofilm with single layer structure,
Shape retention in high-temperature area is excellent.By using above-mentioned specific like that resin formula, it is possible to increase in micro-porous film
Polyacrylic dispersibility.As a result, the fusing-off temperature of micro-porous film and appearance uniform and good can be made.Using so
The excellent in safety of battery produced of polyolefin micro porous polyolefin membrane.Herein, so-called " single layer structure " refers to：In micro-porous film
On film thickness direction and be not configured with forming, using raw material or physical property layer different from each other structure, in other words, refer in film
Composition on thick direction, using raw material or the consistent structure of physical property.Therefore, in single layer structure, a certain in micro-porous film
Optional position and with respect to this optional position on film thickness direction detached position, composition, consistent with each other using raw material, physical property.
Temperature in the polyolefin micro porous polyolefin membrane of the present invention, in the state of the contraction inhibiting length direction, to 150 DEG C
Under the conditions of degree, in 15 minutes, the amount of contraction of produced width is measured and the thermal contraction of obtained width
Rate is preferably 35%～50%, more preferably 35%～40%.So, the percent thermal shrinkage in TD direction is set as prescribed limit
Interior numerical value, thus, as the barrier film of battery, even if the shape that (hereinafter also referred to as " MD direction ") is rolled alongst
Under state, also can show good battery behavior.
In the state of the contraction inhibiting length direction, even if polyolefin micro porous polyolefin membrane is preferably in 150 DEG C of temperature strip
Under part, heating also will not occur film to break and keep film shape for 30 minutes.Additionally, under 105 DEG C of temperature conditionss in 8 hours institute
The amount of contraction of the width producing is measured and obtained percent thermal shrinkage is preferably 0～5%.
And, polyolefin micro porous polyolefin membrane preferably has a choke degree of 80～200sec/100cc, more preferably 100～
150sec/100cc.Preferably there is the puncture strength of 150～400g, more preferably 250～400g.In order to improve battery
Performance, micro-porous film has the heat shrinkability characteristic improving, i.e. more preferable dimensional stability under high temperature, and thermostability, choke
Degree and the balancing good of puncture strength.
In the polyolefin micro porous polyolefin membrane of the present invention, there are 133 DEG C～138 DEG C of closing temperature and 160 DEG C～170 DEG C
Fusing-off temperature, the difference of described closing temperature and described fusing-off temperature is preferably greater than and is equal to 26.5 DEG C.It should be noted that SD
Temperature and MD temperature can be formed by feed change and raw material mixing condition being adjusted.By by micro- for polyolefin porous
The SD temperature of film and MD temperature are set as the numerical value in such scope, can manufacture the battery that ensure that safety.Additionally,
The deviation (R value) of fusing-off temperature is preferably less than and is equal to 10 DEG C, is further preferably less than equal to 5 DEG C.
When manufacturing the polyolefin micro porous polyolefin membrane of the present invention, for example can be using following method.Specifically, first, will
The raw material being formed by polyolefin composition carry out melting mixing in double screw extruder with solvent with molding such as liquid paraffin and
Form polyolefin solution, the polyolefin solution being formed is extruded from the T-shaped mould head of double screw extruder, is carried out using chill roll
Cooled down while extraction, to be obtained gluey sheet material.Then, by biaxial orientation stretching machine on MD direction and TD direction to this
Gluey sheet material is simultaneously bi-directionally stretched, and this gluey sheet material having carried out thermal finalization process with this state be impregnated in dichloromethane
In the rinse bath of bath, remove liquid paraffin.It is then possible to adopt following methods：Obtaining to by removing liquid paraffin
After sheet material is dried, is redrawn in TD direction by width stretching-machine and relaxed, made the stretching times in TD direction
After rate (TD is dried stretching ratio) is adjusted to such as 1.1～1.6, preferably 1.1～1.5, thermal finalization process is carried out with this state, cold
But to room temperature.Dried micro-porous film can also be in the MD direction with such as 1.0～1.6, preferably 1.1～1.5 stretching times
Rate (MD is dried stretching ratio) is stretched.In the case of being somebody's turn to do, TD is dried stretching ratio and is preferably greater than equal to the dry stretching of MD again
Rate, sequentially or simultaneously can be stretched on MD direction and TD direction.To dried micro-porous film MD direction with
And in the case of being stretched successively on TD direction, stretched in TD direction after preferably being stretched in the MD direction.
Additionally, the polyolefin micro porous polyolefin membrane of the present invention preferably obtains as follows：Will be containing molding solvent, to be less than
Part by weight equal to 30% contains gluey sheet material obtained from polyolefinic polyolefin solution extrusion molding and is stretched, and then
It is dried after removing described molding solvent and obtain.Polyolefinic content (part by weight) in polyolefin solution enters one
Step is preferably less than and is equal to 25%.
[The effect of invention]
A kind of polyolefin micro porous polyolefin membrane according to the present invention, using the teaching of the invention it is possible to provide polyolefin micro porous polyolefin membrane, under its outward appearance, high temperature
Shape retention is excellent, can be tested by safety evaluatio with high reliability.
Brief description
Fig. 1 is the schematic diagram of the manufacturing process of the polyolefin micro porous polyolefin membrane representing one embodiment of the present invention.
Specific embodiment
Hereinafter, referring to the drawings, by embodiment, the preferable embodiment of the present invention is illustrated.
Embodiment
Embodiment 1
[manufacture method of micro-porous film]
Fig. 1 is the schematic diagram of the manufacturing process of polyolefin micro porous polyolefin membrane 1 representing embodiment 1.To by weight average molecular weight (Mw) 2.6
×106Acrylic resin 5 mass parts, Mw2.0 × 106Ultra-high molecular weight polyethylene 15 mass parts, Mw2.8 × 105Highly dense
Polyolefin composition 100 mass parts that degree polyethylene 80 mass parts are formed, are dry mixed four [methylene -3- (3,5- di-t-butyl -4-
Hydroxy phenyl)-propionic ester] methane 0.2 mass parts as antioxidant, obtain raw material 2.This raw material 2 is put into twin-screw extrusion
Machine 11, and then side feeder supply liquid paraffin (50cst during at 40 DEG C) from double screw extruder 11, in twin-screw extrusion
To being mixed with polyolefin composition 25 mass parts in machine, the raw material 2 of liquid paraffin 75 mass parts carries out dissolving mixing, prepares polyene
Hydrocarbon solution.This dissolving compounding conditions is as follows.That is, carry out under the conditions of following melting mixing：Temperature is 210 DEG C, vistanex
The ratio Q/Ns with respect to screw speed Ns (rpm) for input amount Q (kg/h) of solution is 0.2kg/h/rpm, and Ns is 420rpm.From double
The T-shaped mould head of screw extruder 11 extrudes this polyolefin solution, is extracted using the chill roll 12 that temperature adjustment is 40 DEG C
Cooled down simultaneously, formed gluey sheet material.When 120 DEG C, by biaxial orientation stretching machine 13 on MD direction and TD direction by institute
The gluey sheet material obtaining simultaneously bi-directionally is stretched to 5 times, is fixed on biaxial orientation stretching machine 13 with this state, and at a temperature of 120 DEG C
Carry out thermal finalization process, so that there is no change in size on MD direction and TD direction both direction.
Then, the gluey sheet material after stretching be impregnated in the rinse bath 14 of bath of dichloromethane, thus remove (cleaning) liquid
Body paraffin, is dried to the micro-porous film being obtained using drying machine 15.When 128 DEG C, by width stretching-machine 23
TD direction redraws the micro-porous film being obtained to 1.41 times, then, TD direction makes its pine with relaxation rate 15%
Relax and after the stretching ratio in TD direction is set to 1.2, is fixed on width stretching-machine 23, and carries out thermal finalization when 130 DEG C
Process, so that there is no change in size on MD direction and TD direction both direction.Then, micro-porous film is cooled to room temperature,
Batched using takers-in 22, manufactured the polyolefin micro porous polyolefin membrane 1 of 12 μm of thickness.
(1) polyolefinic viscosity-average molecular weight Mv
Based on ASTM-D4020, obtain the limiting viscosity [η] (dl/g) when 135 DEG C for the naphthalane solvent.
With regard to polyethylene, calculated according to following formula.
[η]=6.77 × 10- 4×Mv0.67
With regard to polypropylene, Mv is calculated according to following formula.
[η]=1.10 × 10- 4×Mv0.80
[thickness (average film thickness)]
From the square of the optional position cut-out length direction 5cm of micro-porous film, width 5cm, make test film.Using connecing
Touch thickness gauge measures at any the 5 of this test film, and its measurement result is averaged, thus as the thickness of this test film.
For same micro-porous film, prepare 10 pieces of test films and be measured.Will be micro- many as this for the meansigma methodss of all 10 pieces of test films
The thickness of pore membrane.Thickness measuring instrument uses Mitsutoyo LIGHTOMATIC VL-50A.
[choke degree (average)]
Using Asahi Seiko Kabushiki Kaisha's numeric type Wang Yan formula air permeability testing machine EGO1, by the micro-porous film corrugationless of the present invention
Ground is fixed on determination part, is measured according to JIS P-8117 (2009).Sample is made 5cm square, measuring point is sample
At the 1 of central part, using measured value as this sample choke degree [second].10 test films coming from optional position collection are implemented
Same mensure, takes the choke degree (sec/100ml) as this micro-porous film for the meansigma methodss of 10 measured values.
[puncture strength of polyolefin micro porous polyolefin membrane]
Puncture strength is defined as：Using having spherical top end surface (radius of curvature R：The pin of diameter 1mm 0.5mm) is with 2mm/
The peak load that when speed of second punctures to the micro-porous film with T1 thickness, (power " gf " with gram unit) is measured.
[percent thermal shrinkage (%) of length direction/width when 105 DEG C]
By the square of micro-porous film cut-out length direction 9cm, width 9cm, make test film.On each side of test film
The position at midpoint adds labelling.It is pointed to the distance between the midpoint on opposed facing side and be measured (L0).In 105 DEG C of heat
After 8 hours heat treatments being carried out to this test film in wind circulation baking oven, it is taken out in room temperature, stands 30 minutes.Same with before heat treatment
Sample ground, is measured (L1) to the distance between the midpoint on opposed facing each side, now, percent thermal shrinkage calculates according to following formula
(unit：%).
Percent thermal shrinkage (%)=100 × (L0-L1)/L0
For same micro-porous film, make five pieces of different test films, same mensure is implemented to each test film.By five times
The meansigma methodss of measurement result are as 105 DEG C of percent thermal shrinkages.
[closing temperature (TSD) and fusing-off temperature (TMD)]
For closing temperature：While being heated to micro-porous film with 5 DEG C/min of programming rate, saturating by Wang Yan formula
Manner instrument (Asahi Seiko Kabushiki Kaisha's system, EGO-1T) measure choke degree, obtain choke degree reach as detectable limit 1 ×
105sec/100cm3When temperature, as closing temperature.
After reaching above-mentioned closing temperature, proceed to heat with 5 DEG C/min of programming rate further, obtain choke degree
Reach 1 × 10 again5sec/100cm3When temperature, as fusing-off temperature.
It should be noted that TSDAnd TMDMeansigma methodss using sample number N (=10).Additionally, TMDDeviation (R value) set
For TMDMaximum-minima (DEG C).
[150 DEG C of rupture of membranes tests]
With the size of MD direction 50mm × TD direction 50mm to the micro- porous of polyolefin being obtained by the manufacture method of the present embodiment
Film 1 is sampled, and with adhesive tape, the MD direction of sample is fixed on ground paper, places and be more than or equal to 30 minutes in 150 DEG C of baking oven.
By occur within 10 minutes rupture of membranes be set to unqualified (×), by occur more than 10 minutes and within 30 minutes rupture of membranes be set to close
, will there is not being set to well (zero) of rupture of membranes more than 30 minutes in lattice (△).
[mensure of 150 DEG C × 15min percent thermal shrinkage (MD fixes in direction)]
With the size of MD direction 50mm × TD direction 50mm to the micro- porous of polyolefin being obtained by the manufacture method of the present embodiment
Film 1 is sampled, and with adhesive tape, the MD direction of sample is fixed on ground paper, places 15 minutes in 150 DEG C of baking oven.According to TD side
To obtain shrinkage factor to the change of length.
[evaluation of outward appearance]
Sample size width 95mm × length will be cut out by the polyolefin micro porous polyolefin membrane 1 that the manufacture method of the present embodiment obtains
95mm, in the magnifier with illumination (using equipment：ILLUMINATING LUPE, PEAK company system) upper corrugationless ground expansion, profit
Use viewed in transmitted light micro-porous film.Count the transparent speckle that major diameter is more than or equal to 0.3cm, within speckle number is 5
It is evaluated as ◎ (excellent), zero (good) will be evaluated as more than 5 and within 10, △ will be evaluated as more than 10 and within 30
(qualified), will be evaluated as × (unqualified) more than 30.The quantity of the speckle for evaluating adopts putting down of sample number N (=6)
Average.
[to the application of battery separator]
The polyolefin micro porous polyolefin membrane of the present invention is preferred for lithium rechargeable battery, lighium polymer secondary battery, the secondary electricity of ni-mh
The barrier film of the secondary cells such as pond, NI-G secondary cell, Ni-MH secondary battery, silver-colored zinc secondary cell, but particularly preferred for lithium
Ion secondary battery barrier film.Hereinafter, lithium rechargeable battery is illustrated, but the application of the present invention is not limited to
Lithium rechargeable battery.
Lithium rechargeable battery has positive pole and negative pole across barrier film lamination, and barrier film contains electrolyte (electrolyte).Electrode
Structure is not particularly limited, and can be known structure.For example, can be using the electricity of discoid positive pole and the opposed arranging of negative pole
The electrode structure (lamination-type) of pole structure (coin shape), flat positive pole and negative pole alternative stacked, the positive pole of banding and
Electrode structure (convoluted) of the overlapping winding of negative pole etc..
Positive pole generally has collector and is formed at its surface and the layer containing positive active material, wherein this positive-active
Material can occlusion release lithium ion.As positive active material, the compound of transition metal oxide, lithium and transition metal can be enumerated
Inorganic compound such as oxide (lithium composite xoide) and transient metal sulfide etc., as transition metal, can enumerate V,
Mn, Fe, Co, Ni etc..As the preferred example of lithium composite xoide, can enumerate with lithium nickelate, cobalt acid lithium, LiMn2O4, α-
NaFeO2Type structure is stratiform lithium composite xoide of parent etc..Negative pole has collector and is formed at its surface and contains negative pole
The layer of active substance.As negative electrode active material, the carbonaceous such as graphite, native graphite, Delanium, coke class, white carbon black can be enumerated
Material.
Electrolyte can be by obtain lithium salts dissolving in organic solvent.As lithium salts, LiClO can be enumerated4、LiPF6、
LiAsF6、LiSbF6、LiBF4、LiCF3SO3、LiN(CF3SO2)2、LiC(CF3SO2)3、Li2B10Cl10、LiN(C2F5SO2)2、
LiPF4(CF3)2、LiPF3(C2F5)3, lower aliphatic carboxylic acid's lithium salts and LiAlCl4Deng.They can be used alone, and also can make
Used for mixture of more than two kinds.As organic solvent, ethylene carbonate, Allyl carbonate, methyl ethyl carbonate can be enumerated
The high boiling points such as ester, gamma-butyrolacton and the organic solvent of high-k, oxolane, 2- methyltetrahydrofuran, dimethoxy
The low boilings such as ethane, dioxolanes, dimethyl carbonate, diethyl carbonate and low viscous organic solvent.They can be used alone,
Also can be used as mixture of more than two kinds.Because the organic solvent viscosity of high-k is high, low viscous organic molten
Agent dielectric constant is low, therefore preferably uses both mixture.
During assembled battery, electrolysis immersion is made to contain to barrier film.So, it is possible barrier film (multilayer microporous membrane) imparting ion is oozed
Permeability.To carry out leaching by impregnated in multilayer microporous membrane at normal temperatures containing process in electrolyte.In assembling cylinder battery
In the case of, the barrier film that for example by positive plate, formed by multilayer microporous membrane and negative plate according to this sequentially carry out lamination,
Winding, and insert battery can, leaching contains electrolyte, then, doubles as the battery possessing the positive terminal of relief valve via pad riveting
Lid.
[HotBox test]
Make square battery according to below step, implement the safety testing of battery.Using lithium cobalt composite oxide LiCoO2
As positive active material, graphite is used as negative electrode active material, using the 1mol/L of the mixed solvent being prepared in EC/DMC
LiPF6As electrolyte, by positive pole, after the barrier film negative pole that formed by micro-porous film and micro-porous film lamination, make volume
Around electrode body, insert battery can, leaching contains electrolyte, sealed.
With the current value of 1C by after constant-current charging of battery assembled as described above to voltage 4.2V, the constant voltage carrying out 4.2V is filled
Electricity, is then discharged with the electric current of 1C, until the final voltage of 3.0V.Then, with the current value constant-current charge of 1C to 4.2V
Afterwards, carry out the constant-voltage charge of 4.2V.
Then, battery is put into baking oven, with 5 DEG C/min after room temperature starts to warm up, place 30 minutes when 150 DEG C.?
After reaching 150 DEG C, by smolder within 10 minutes or on fire be set to unqualified (×), rise within exceeding 10 minutes and 30 minutes
Fire be set to qualified (△), be set to good (zero) by fire more than 30 minutes and within 1 hour, will exceed 1 hour not on fire
Be set to excellent (◎).
Show resin composition, the knot of manufacturing condition, micro-porous film physical property and cell evaluation of embodiment 1 in Table 1
Really.
[table 1]
[table 2]
[embodiment 2]
Except using by Mw2.6 × 106Acrylic resin 7.5 mass parts, Mw2.0 × 106Ultra-high molecular weight polyethylene 15
Mass parts, Mw2.8 × 105High density polyethylene (HDPE) 77.5 mass parts formed polyolefin composition as polyolefin composition with
Outward, make polyolefin micro porous polyolefin membrane similarly to Example 1, implement various tests.
[embodiment 3]
Except using by Mw2.6 × 106Acrylic resin 10 mass parts, Mw2.0 × 106Ultra-high molecular weight polyethylene 15 matter
Amount part, Mw2.8 × 105High density polyethylene (HDPE) 75 mass parts formed polyolefin composition as polyolefin composition beyond,
Make polyolefin micro porous polyolefin membrane similarly to Example 1, implement various tests.
[embodiment 4]
Except using by Mw2.6 × 106Acrylic resin 15 mass parts, Mw2.0 × 106Ultra-high molecular weight polyethylene 15 matter
Amount part, Mw2.8 × 105High density polyethylene (HDPE) 70 mass parts formed polyolefin composition as polyolefin composition beyond,
Make polyolefin micro porous polyolefin membrane similarly to Example 1, implement various tests.
[embodiment 5]
Except using by Mw2.6 × 106Acrylic resin 20 mass parts, Mw2.0 × 106Ultra-high molecular weight polyethylene 15 matter
Amount part, Mw2.8 × 105High density polyethylene (HDPE) 65 mass parts formed polyolefin composition as polyolefin composition beyond,
Make polyolefin micro porous polyolefin membrane similarly to Example 1, implement various tests.
[embodiment 6]
Except using by Mw2.6 × 106Acrylic resin 7.5 mass parts, Mw2.0 × 106Ultra-high molecular weight polyethylene 20
Mass parts, Mw2.8 × 105High density polyethylene (HDPE) 72.5 mass parts formed polyolefin composition as polyolefin composition with
Outward, make polyolefin micro porous polyolefin membrane similarly to Example 1, implement various tests.
[embodiment 7]
Except using by Mw2.6 × 106Acrylic resin 10 mass parts, Mw2.0 × 106Ultra-high molecular weight polyethylene 20 matter
Amount part, Mw2.8 × 105High density polyethylene (HDPE) 70 mass parts formed polyolefin composition as polyolefin composition beyond,
Make polyolefin micro porous polyolefin membrane similarly to Example 1, implement various tests.
[embodiment 8]
In addition to Ns is set to 310rpm, makes the polyolefin micro porous polyolefin membrane that thickness is 9 μm similarly to Example 2, implement
Various tests.
[embodiment 9]
In addition to Q/Ns is set to 0.25, makes the polyolefin micro porous polyolefin membrane that thickness is 16 μm similarly to Example 2, implement
Various tests.
[embodiment 10]
Except using Mw1.5 × 106Acrylic resin 10 mass parts substituting Mw2.6 × 106Acrylic resin 10 mass
Beyond part, make polyolefin micro porous polyolefin membrane similarly to Example 3, implement various tests.
[embodiment 11]
Except using Mw2.0 × 106Acrylic resin 10 mass parts substituting Mw2.6 × 106Acrylic resin 10 mass
Beyond part, make polyolefin micro porous polyolefin membrane similarly to Example 3, implement various tests.
[embodiment 12]
In addition to the concentration of polyolefin solution is set to 30 weight %, make polyolefin micro porous polyolefin membrane similarly to Example 2,
Implement various tests.
[embodiment 13]
In addition to Ns is set to 310rpm, makes the polyolefin micro porous polyolefin membrane that thickness is 3 μm similarly to Example 3, implement
Various tests.
[embodiment 14]
In addition to Ns is set to 310rpm, makes the polyolefin micro porous polyolefin membrane that thickness is 5 μm similarly to Example 3, implement
Various tests.
[embodiment 15]
In addition to Ns is set to 310rpm, makes the polyolefin micro porous polyolefin membrane that thickness is 7 μm similarly to Example 3, implement
Various tests.
[embodiment 16]
Using by Mw2.0 × 106Ultra-high molecular weight polyethylene 18 mass parts, Mw2.8 × 105High density polyethylene (HDPE) 72 mass
The polyolefin composition that part is formed is as polyolefin composition.Q is set to 48kg/h, Ns is set to 320rpm.Except being set to draw
Stretch 110 DEG C of temperature, redraw multiplying power 1.6, beyond final stretching ratio 1.45, making thickness similarly to Example 3 is 3 μm
Polyolefin micro porous polyolefin membrane, implements various tests.
[embodiment 17]
In addition to stretching ratio (MD × TD) is set to 7 × 7, make the polyolefin that thickness is 3 μm similarly to Example 16 micro-
Perforated membrane, implements various tests.
[embodiment 18]
Except being obtained by drying when 95 DEG C using the difference of roller with roller mode by length direction stretching-machine 20
Micro-porous film redraw in the MD direction to 1.2 times, then, by width stretching-machine 23 carry out TD direction redraw with
Outward, make the polyolefin micro porous polyolefin membrane that thickness is 12 μm similarly to Example 4, implement various tests.
[embodiment 19]
Except being obtained by drying when 95 DEG C using the difference of roller with roller mode by length direction stretching-machine 20
Micro-porous film redraw to 1.5 times in addition in the MD direction, making thickness similarly to Example 18 is 12 μm of polyolefin
Micro-porous film, implements various tests.
[comparative example 1]
Except using by Mw2.0 × 106Ultra-high molecular weight polyethylene 15 mass parts, Mw2.8 × 105High density polyethylene (HDPE) 85
Beyond the polyolefin composition that mass parts are formed is as polyolefin composition, make the micro- porous of polyolefin similarly to Example 1
Film, implements various tests.Show that resin composition, manufacturing condition, micro-porous film physical property and the battery of comparative example are commented in table 2
The result of valency.
[comparative example 2]
Except using by Mw2.6 × 106Acrylic resin 7.5 mass parts, Mw2.0 × 106Ultra-high molecular weight polyethylene 30
Mass parts, Mw2.8 × 105High density polyethylene (HDPE) 62.5 mass parts formed polyolefin composition as polyolefin composition with
Outward, make polyolefin micro porous polyolefin membrane similarly to Example 1, implement various tests.
[comparative example 3]
Except using by Mw2.6 × 106Acrylic resin 25 mass parts, Mw2.0 × 106Ultra-high molecular weight polyethylene 15 matter
Amount part, Mw2.8 × 105High density polyethylene (HDPE) 60 mass parts formed polyolefin composition as polyolefin composition beyond,
Make polyolefin micro porous polyolefin membrane similarly to Example 1, implement various tests.
[comparative example 4]
Except using Mw6.8 × 105Acrylic resin 7.5 mass parts substituting Mw2.6 × 106Acrylic resin 7.5 matter
Beyond amount part, make polyolefin micro porous polyolefin membrane similarly to Example 2, implement various tests.
[comparative example 5]
Except using Mw7.5 × 105Acrylic resin 7.5 mass parts substituting Mw2.6 × 106Acrylic resin 7.5 matter
Beyond amount part, make polyolefin micro porous polyolefin membrane similarly to Example 2, implement various tests.
[comparative example 6] (is equivalent to the comparative example 1-12 of Japanese Patent No. 4789274)
Prepare polyethylene 46 mass parts of homopolymer, polyethylene 47 matter of the homopolymer of Mv70 ten thousand of viscosity-average molecular weight (Mv) 200,000
Amount part, polypropylene 7 mass parts of the homopolymer of Mv40 ten thousand, liquid paraffin 65 mass parts as plasticizer, as antioxidant
Tetramethylolmethane-four-[3- (3,5- di-tert-butyl-hydroxy phenyl) propionic ester] 1 mass parts, using Henschel mixer pair
They carry out premixing.In order to melting mixing is carried out to the mixture being obtained, to the charging aperture of twin shaft screw extruder in the same direction
Supplied.Additionally, liquid paraffin is carried out side-fed to the machine barrel of twin shaft screw-type extruder in the same direction, so that liquid paraffin
50 mass parts are accounted in the total mixture that amount kneads being melted and extrudes.Melting mixing condition is set to：200 DEG C of design temperature, spiral shell
Bar rotating speed 200rpm, output 15kg/h.
Then, using the chill roll of temperature adjustment to 25 DEG C, the molded body extruded is extracted, while with 10
DEG C/sec speed it is carried out with Slow cooling, form the gluey sheet material of 1050 microns of thickness.Using tentering stretching-machine, at 118 DEG C
When so that 7 times on MD direction, on TD direction, 6.4 times of stretching ratio is simultaneously bi-directionally stretched to gluey sheet material.By obtained
Stretched film is fixed on frame plate (size：20cm × 20cm, aluminum), impregnated in the dichloromethane rinse bath that temperature adjustment is 25 DEG C
In, shaken 3 minutes with 100rpm, be carried out simultaneously.After at room temperature the film being obtained being dried, it is fixed on tentering
Machine, carries out thermal finalization process.With design temperature 123 when 1.5 times of maximum tension multiplying power, 1.3 times of final stretching ratio, maximum tension
DEG C, the heat set conditions of final 128 DEG C of temperature when stretching to make polyolefin micro porous polyolefin membrane, implement various tests.
[comparative example 7]
Except using by Mw2.0 × 106Ultra-high molecular weight polyethylene 15 mass parts, Mw2.8 × 105High density polyethylene (HDPE) 85
Beyond the polyolefin composition that mass parts are formed is as polyolefin composition, make the micro- porous of polyolefin similarly to Example 19
Film, implements various tests.
The resin composition of embodiment 2～19 and comparative example 1～8, manufacturing condition, micro-porous film is shown in table 1,2
Physical property and the result of cell evaluation.
[industrial utilizability]
The polyolefin micro porous polyolefin membrane of the present invention can be secondary as lithium rechargeable battery, lighium polymer secondary battery, ni-mh
The secondary cell of battery, NI-G secondary cell, Ni-MH secondary battery, silver-colored zinc secondary cell etc. with barrier film utilized.
In figure：
1 polyolefin micro porous polyolefin membrane
2 raw materials
11 double screw extruders
12nd, 22 roller
13rd, 23 stretching-machine
14 rinse baths
15 drying machines
Claims (4)
1. a kind of polyolefin micro porous polyolefin membrane it is characterised in that
Contain the polypropylene of weight average molecular weight 150～3,000,000 with 5%～20% part by weight, with 5%～20% weight ratio
The polyethylene containing weight average molecular weight 150～2,500,000 for the example, contains weight average molecular weight 20～500,000 with 60%～90% ratio
Polyethylene, has single layer structure.
2. polyolefin micro porous polyolefin membrane according to claim 1 is it is characterised in that contraction on inhibiting length direction
Under state, under 150 DEG C of temperature conditionss in 15 minutes the amount of contraction of produced width be measured and obtained
Width percent thermal shrinkage be 35%～50%.
3. polyolefin micro porous polyolefin membrane according to claim 1 and 2 is it is characterised in that described polyolefin micro porous polyolefin membrane has
The fusing-off temperature of 133 DEG C～138 DEG C of closing temperature and 160 DEG C～170 DEG C, described closing temperature and described fusing-off temperature it
Difference is more than or equal to 26.5 DEG C.
4. polyolefin micro porous polyolefin membrane according to any one of claim 1 to 3 is it is characterised in that the deviation of fusing-off temperature
It is less than or equal to 10 DEG C.
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| JP2014-093765 | 2014-04-30 | ||
| JP2014093765 | 2014-04-30 | ||
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| JP2014-205634 | 2014-10-06 | ||
| PCT/JP2015/062416 WO2015166878A1 (en) | 2014-04-30 | 2015-04-23 | Microporous polyolefin membrane |
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| JP (1) | JP6627753B2 (en) |
| KR (1) | KR102294981B1 (en) |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN114269817A (en) * | 2019-08-22 | 2022-04-01 | 东丽株式会社 | Polyolefin microporous membrane, laminate, and battery |
| WO2024011978A1 (en) * | 2022-07-11 | 2024-01-18 | 宁德时代新能源科技股份有限公司 | Polyolefin-based film and preparation method therefor, separator, secondary battery, and electric device |
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| KR20220051166A (en) * | 2019-08-22 | 2022-04-26 | 도레이 카부시키가이샤 | Polyolefin microporous membranes, laminates, and batteries |
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| CN102215944A (en) * | 2008-11-17 | 2011-10-12 | 东丽东燃机能膜合同会社 | Microporous membranes and methods for producing and using such membranes |
| CN102414015A (en) * | 2009-04-23 | 2012-04-11 | 东丽东燃机能膜合同会社 | Thermoplastic film, methods for making such film, and use of such film as battery separator film |
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| JP4121846B2 (en) | 2002-12-16 | 2008-07-23 | 東燃化学株式会社 | Polyolefin microporous membrane and production method and use thereof |
| RU2430772C2 (en) | 2005-11-24 | 2011-10-10 | Торей Тонен Спешиалти Сепарейтор Годо Кайса | Microporous polyolefin membrane, method of its production, storage battery separator and storage battery |
| US7700182B2 (en) * | 2006-05-15 | 2010-04-20 | Tonen Chemical Corporation | Microporous polyolefin membrane, its production method, and battery separator |
| JP5235324B2 (en) | 2007-04-20 | 2013-07-10 | 旭化成イーマテリアルズ株式会社 | Polyolefin microporous membrane |
| WO2009044227A1 (en) | 2007-10-05 | 2009-04-09 | Tonen Chemical Corporation | Microporous polymer membrane |
| WO2009064296A1 (en) * | 2007-11-14 | 2009-05-22 | Tonen Chemical Corporation | Multi-layer, microporous membrane, battery separator formed by such a membrane and battery comprising such a separator |
| CN102802771B (en) * | 2009-06-19 | 2015-02-04 | 东丽电池隔膜株式会社 | Microporous membranes, methods for making these membranes, and the use of these membranes as battery separator films |
| KR101800685B1 (en) * | 2009-06-19 | 2017-11-23 | 도레이 카부시키가이샤 | Microporous membranes, methods for making such membranes, and the use of such membranes as battery separator film |
| CN103328552B (en) * | 2011-01-25 | 2014-12-10 | 东丽电池隔膜株式会社 | Microporous membrane, method for producing same, and battery separator using same |
| JP5909411B2 (en) | 2012-06-13 | 2016-04-26 | 旭化成イーマテリアルズ株式会社 | Polyolefin microporous membrane and method for producing the same |
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| CN102215944A (en) * | 2008-11-17 | 2011-10-12 | 东丽东燃机能膜合同会社 | Microporous membranes and methods for producing and using such membranes |
| CN102414015A (en) * | 2009-04-23 | 2012-04-11 | 东丽东燃机能膜合同会社 | Thermoplastic film, methods for making such film, and use of such film as battery separator film |
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| CN114269817A (en) * | 2019-08-22 | 2022-04-01 | 东丽株式会社 | Polyolefin microporous membrane, laminate, and battery |
| WO2024011978A1 (en) * | 2022-07-11 | 2024-01-18 | 宁德时代新能源科技股份有限公司 | Polyolefin-based film and preparation method therefor, separator, secondary battery, and electric device |
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| JP6627753B2 (en) | 2020-01-08 |
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| CN106459467B (en) | 2019-06-07 |
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| JPWO2015166878A1 (en) | 2017-04-20 |
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