JP2012102198A - Polyolefin microporous film, and electricity storage device - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a polyolefin microporous film capable of achieving an electricity storage device capable of satisfying both of safety (evaluated by nail-piercing test) and a high output character (evaluated by high rate character).SOLUTION: This polyolefin microporous film includes an effective diffusion coefficient in the thickness direction D(Z)as shown by formula (1) of ≥2.8×10, and a Bruggeman index shown as α in formula (2) of 1.50≤α<2.60 and a piercing strength of ≥2.4 N/20 μm and ≤20.0 N/20 μm: the formula (1) represents D(Z)=D(Z)×ε, and the formula (2) represents ε=D(Z)/D, wherein D(Z) is the diffusion coefficient in thickness direction of the polyolefin microporous film, measured by a magnetic field gradient NMR method, Dis the diffusion coefficient of electrolyte liquid used in the measurement of the magnetic field gradient NMR method, and ε is the porosity of the polyolefin microporous film.

Description

  The present invention relates to a polyolefin microporous membrane and an electricity storage device including the same.

In recent years, power storage devices such as lithium ion secondary batteries and electric double layer capacitors (including those called lithium ion capacitors and non-aqueous lithium power storage elements) have been actively developed. In a power storage device, a microporous membrane (separator) is usually provided between the positive and negative electrodes. Such a separator has a function of preventing contact between positive and negative electrodes and transmitting ions.
Here, the separator is required to have a certain physical strength or more from the viewpoint of ensuring good safety of the electricity storage device. That is, pressure from the electrodes may be applied to the separator as the electricity storage device is charged / discharged, and the electrodes may break through the separator and cause a short circuit between the electrodes.

  Under such circumstances, for example, Patent Document 1 proposes a microporous film using ultrahigh molecular weight polyethylene. Patent Documents 2 and 3 propose microporous membranes made of a mixture of high density polyethylene and high molecular weight polypropylene.

Japanese Patent No. 2794179 JP 2002-105235 A

On the other hand, the separator may be required to achieve the high output characteristics of the electricity storage device. For example, in a lithium ion secondary battery for in-vehicle use, a polyolefin microporous film having a relatively large film thickness (a film thickness exceeding 20 μm) is used from the viewpoint of ensuring high safety. However, the microporous membranes described in Patent Documents 1 to 3 still have room for improvement from the viewpoint of achieving high output characteristics.
An object of the present invention is to provide a polyolefin microporous membrane capable of realizing an electricity storage device capable of achieving both safety (evaluated by a nail penetration test) and high output characteristics (evaluated by high rate characteristics).

D (Z) is the diffusion coefficient in the thickness direction of the polyolefin microporous film measured by the magnetic field gradient NMR method, D _{0 is} the diffusion coefficient of the electrolyte used in the measurement of the magnetic field gradient NMR method, and the porosity of the polyolefin microporous film Where ε is an effective diffusion coefficient D (Z) _{eff in} the thickness direction, is represented by the following equation (1), and the numerical value represented by α in the following equation (2) is called the Burgman index.
D (Z) _eff = D (Z) × ε ·· (1)
ε ^α = D (Z) _eff / D ₀ (2)
The inventors of the present invention provide a polyolefin microporous membrane in which the effective diffusion coefficient in the thickness direction of the polyolefin microporous membrane measured by the magnetic field gradient NMR method, the Burgman index, and the piercing strength are adjusted to a specific range. The present inventors have found that this can be solved and have completed the present invention.

That is, the present invention is as follows.
[1]
D (Z) is the diffusion coefficient in the thickness direction of the polyolefin microporous film measured by the magnetic field gradient NMR method, D _{0 is} the diffusion coefficient of the electrolyte used in the measurement of the magnetic field gradient NMR method, and the porosity of the polyolefin microporous film Is an effective diffusion coefficient D (Z) _{eff in} the thickness direction represented by the following equation (1) is 2.8 × 10 ⁻¹¹ or more, and is represented by α in the following equation (2). A polyolefin microporous membrane having a Burgmann index of 1.50 ≦ α <2.60 and a puncture strength of 2.4 N / 20 μm or more and 20.0 N / 20 μm or less.
D (Z) _eff = D (Z) × ε ·· (1)
ε ^α = D (Z) / D ₀ (2)
[2]
The polyolefin microporous membrane according to [1], wherein the polyolefin resin forming the polyolefin microporous membrane contains high-density polyethylene.
[3]
An electricity storage device comprising the polyolefin microporous membrane according to [1] or [2] as a separator.

  According to the present invention, a polyolefin microporous membrane capable of realizing an electricity storage device that can achieve both safety (evaluated by a nail penetration test) and high output characteristics (evaluated by high rate characteristics) can be obtained.

  Hereinafter, a mode for carrying out the present invention (hereinafter abbreviated as “the present embodiment”) will be described in detail. In addition, this invention is not limited to the following embodiment, It can implement by changing variously within the range of the summary.

The polyolefin microporous membrane of the present embodiment has a diffusion coefficient D (Z) in the thickness direction of the polyolefin microporous membrane measured by the magnetic field gradient NMR method, and the diffusion coefficient of the electrolyte used for the measurement of the magnetic field gradient NMR method. Is D ₀ , and the porosity of the polyolefin microporous film is ε, the effective diffusion coefficient D (Z) _{eff in} the thickness direction represented by the following formula (1) is 2.80 × 10 ⁻¹¹ or more, In the formula (2), the Burgman index indicated by α is adjusted to 1.50 ≦ α <2.60.
D (Z) _eff = D (Z) × ε ·· (1)
ε ^α = D (Z) _eff / D ₀ (2)

In this embodiment, D (Z) is the diffusion coefficient in the film thickness direction of the polyolefin microporous film measured by the magnetic field gradient NMR method, and D ₀ is the electrolyte solution used for the measurement measured by the magnetic field gradient NMR method. Indicates the diffusion coefficient. The inventors measured D (Z) as the diffusion coefficient in the thickness direction of the polyolefin microporous membrane measured by the magnetic field gradient NMR method, D _{0 as} the diffusion coefficient of the electrolyte used for the measurement, and the polyolefin microporous used in the measurement. When the porosity of the film is ε, the effective thickness direction diffusion coefficient D (Z) _{eff represented} by the following equation (1) and the Burgman index numerical range represented by α in the following equation (2) are: It has been discovered that a microporous membrane having a specific range and a puncture strength defined in a specific range can influence the high rate characteristics of the electricity storage device when the microporous membrane is used as a separator.
D (Z) _eff = D (Z) × ε ·· (1)
ε ^α = D (Z) _eff / D ₀ (2)
By controlling the numerical values of the diffusion coefficient D (Z) _eff and the Burgman index α in the thickness direction within a specific range, an electricity storage device having excellent high rate characteristics can be obtained. The reason for this is not clear, but it is estimated that defining the flow path that is the path of ions by the Z-direction parameters of the microporous membrane correlates with the smoothness of lithium ion entry and exit and affects the high-rate characteristics. Is done.

The numerical range of the effective diffusion coefficient D (Z) _eff in the effective thickness direction of the polyolefin microporous membrane of the present embodiment is 2.80 × 10 ⁻¹¹ or more, preferably 3.00 × 10 ⁻¹¹ or more, more preferably Is 3.50 × 10 ⁻¹¹ or more, particularly preferably 4.00 × 10 ⁻¹¹ or more. When D (Z) _eff is less than 2.80 × 10 ⁻¹¹ , there is a tendency that sufficient permeability cannot be secured.

The numerical range of the Burgmann index α of the polyolefin microporous membrane of the present embodiment is 1.50 ≦ α <2.60, preferably 1.85 or more, more preferably 1.90 or more, and still more preferably 2.00. The upper limit is preferably less than 2.60, more preferably less than 2.55, and still more preferably less than 2.50.
Here, if it exceeds 2.60, there is a tendency that sufficient permeability cannot be secured when a battery is produced.

  Examples of means for adjusting the value of the Burgman index α to the above specific range include a method of adjusting the concentration of the polymer constituting the microporous membrane, a method of adjusting the stretching conditions and the heat fixing / thermal relaxation conditions, and the like. . More specifically, in order to reduce the value of the Burgman index α, the polymer concentration is decreased, the stretching ratio during the stretching process is decreased, and the temperature during the heat fixing / thermal relaxation process is kept low. Furthermore, the draw ratio is reduced, and the draw ratio in the extrusion direction (hereinafter referred to as “MD direction”) and the width direction (hereinafter referred to as “TD direction”) is used as the total draw ratio. Adjusting so that is isotropic. On the other hand, in order to increase the value of the Burgman index α, the stretching ratio during the stretching process is increased, the stretching is performed at a high temperature during the heat setting / thermal relaxation process, and the stretching ratio is increased. For example, the total draw ratio may be adjusted so that one of the draw ratios in the MD direction and the TD direction is larger than the other. The magnetic field gradient NMR method and the porosity measurement can be performed according to the methods described in the examples described later.

  The polyolefin microporous film of the present embodiment is formed from a polyolefin resin composition containing a polyolefin resin. Examples of the polyolefin resin used in the present embodiment include polymers obtained by polymerizing monomers such as ethylene, propylene, 1-butene, 4-methyl-1-pentene, 1-hexene, and 1-octene ( Homopolymers, copolymers, multistage polymers, etc.). These polymers can be used alone or in combination of two or more.

  Examples of the polyolefin resin include low density polyethylene, linear low density polyethylene, medium density polyethylene, high density polyethylene, ultrahigh molecular weight polyethylene, isotactic polypropylene, atactic polypropylene, polybutene, and ethylene propylene rubber. May be.

Here, from the viewpoint of reducing the melting point of the polyolefin microporous membrane or improving the puncture strength, the polyolefin resin preferably contains high-density polyethylene.
The proportion of the high density polyethylene in the polyolefin resin is preferably 10% by mass or more, more preferably 30% by mass or more, still more preferably 50% by mass or more, and may be 100% by mass.

  The viscosity average molecular weight (Mv) of the whole polyolefin resin is preferably 100,000 or more and 1.2 million or less. More preferably, it is 300,000 or more and 800,000 or less. When the Mv is 100,000 or more, the film-breaking resistance at the time of melting tends to be easily developed, and when it is 1.2 million or less, the extrusion process tends to be easy, and the shrinkage force at the time of melting is alleviated. It tends to be faster and heat resistance is improved.

  If necessary, the polyolefin resin composition may include an antioxidant such as phenol, phosphorus, or sulfur; a metal soap such as calcium stearate or zinc stearate; an ultraviolet absorber, a light stabilizer, an antistatic agent, Various additives such as an antifogging agent and a coloring pigment can be mixed and used.

The polyolefin resin composition may include inorganic particles as necessary.
Examples of such inorganic particles include oxide ceramics such as alumina, silica (silicon oxide), titania, zirconia, magnesia, ceria, yttria, and zinc oxide, and nitrides such as silicon nitride, titanium nitride, and boron nitride. Ceramics, silicon carbide, calcium carbonate, aluminum sulfate, aluminum hydroxide, potassium titanate, talc, kaolin clay, kaolinite, halloysite, pyrophyllite, montmorillonite, sericite, mica, amicite, bentonite, asbestos, zeolite, Examples thereof include ceramics such as calcium silicate, magnesium silicate, diatomaceous earth, and silica sand, and glass fiber. These can be used alone or in combination of two or more. Among these, from the viewpoint of electrochemical stability, silica, alumina, and titanium are more preferable, and silica is particularly preferable.

As a manufacturing method of the polyolefin microporous film of this Embodiment, the manufacturing method containing each process of following (1)-(5) can be used, for example.
(1) a kneading step of kneading a polyolefin resin, a plasticizer, and if necessary, inorganic particles to form a kneaded product,
(2) After the kneading step, the kneaded product is extruded, formed into a sheet (regardless of being a single layer or a laminate), and cooled and solidified.
(3) After the sheet forming step, if necessary, a plasticizer and inorganic particles are extracted, and further, a stretching step in which the sheet is stretched in a uniaxial or more direction,
(4) After the step, if necessary, a plasticizer and inorganic particles are extracted, and a stretching step for further stretching the sheet in a direction of one axis or more,
(5) A post-processing step in which a plasticizer or an inorganic agent is extracted as necessary after the stretching step and further heat-treated.
Hereinafter, each step will be described.

Step (1) is a kneading step in which a polyolefin resin, a plasticizer, and inorganic particles as necessary are kneaded to form a kneaded product.
The plasticizer used in the step (1) is preferably a non-volatile solvent capable of forming a uniform solution at a temperature equal to or higher than the melting point of the polyolefin resin when mixed with the polyolefin resin. Moreover, it is preferable that it is a liquid at normal temperature.
Examples of the plasticizer include hydrocarbons such as liquid paraffin and paraffin wax; esters such as diethylhexyl phthalate and dibutyl phthalate; higher alcohols such as oleyl alcohol and stearyl alcohol; and the like.
In particular, when polyethylene is included as the polyolefin resin, the use of liquid paraffin as the plasticizer suppresses interfacial peeling between the polyolefin resin and the plasticizer, and from the viewpoint of carrying out uniform stretching or achieving high piercing strength preferable. In addition, it is preferable to use diethylhexyl phthalate from the viewpoint of increasing the load when melt-extruding the kneaded product and improving the dispersibility of the inorganic particles (realizing a high-quality film).

  The proportion of the plasticizer in the kneaded product is preferably 30% by mass or more, more preferably 40% by mass or more, and the upper limit is preferably 80% by mass or less, preferably 70% by mass or less. is there. Setting the ratio to 80% by mass or less is preferable from the viewpoint of maintaining high melt tension during melt molding and ensuring moldability. On the other hand, it is preferable that the ratio is 30% by mass or more from the viewpoint of securing moldability and efficiently stretching the lamellar crystals in the crystalline region of the polyolefin. Here, the fact that the lamellar crystal is efficiently stretched means that the polyolefin chain is efficiently stretched without causing the polyolefin chain to be broken, and the formation of a uniform and fine pore structure, the strength of the polyolefin microporous membrane, and It can contribute to improvement of crystallinity.

Examples of the method for kneading the polyolefin resin, the plasticizer, and, if necessary, the inorganic particles include the following methods (a) and (b).
(A) A method in which a polyolefin resin and inorganic particles are put into a resin kneading apparatus such as an extruder or a kneader, and a plasticizer is further introduced and kneaded while the resin is heated and melt-kneaded.
(B) A step of pre-kneading a polyolefin resin, inorganic particles and a plasticizer in advance at a predetermined ratio using a Henschel mixer or the like, and then introducing the kneaded product into an extruder and introducing a plasticizer while heating and melting. Kneading method.

Step (2) is a sheet forming step in which the kneaded product is extruded after the kneading step, formed into a sheet (whether it is a single layer or a laminated layer), and cooled and solidified.
The step (2) is, for example, a step of extruding the kneaded material into a sheet shape via a T-die or the like and bringing it into contact with a heat conductor to cool and solidify. As the heat conductor, metal, water, air, plasticizer itself, or the like can be used. Moreover, it is preferable to cool and solidify by sandwiching between rolls from the viewpoint of increasing the film strength of the sheet-like molded body and improving the surface smoothness of the sheet-like molded body.

Step (3) is a stretching step in which a plasticizer and inorganic particles are extracted as necessary after the sheet forming step, and the sheet is further stretched in a uniaxial direction or more.
Examples of the stretching method in the step (3) include methods such as simultaneous biaxial stretching, sequential biaxial stretching, multistage stretching, and multiple stretching. Among these, it is preferable to employ the simultaneous biaxial stretching method from the viewpoint of increasing the puncture strength of the polyolefin microporous membrane and making the film thickness uniform.
The total surface magnification is preferably 8 times or more, more preferably 15 times or more, and even more preferably 30 times or more, from the viewpoint of film thickness uniformity, tensile elongation, and porosity balance. When the total surface magnification is 30 times or more, a high strength and low elongation product is easily obtained. Here, the total surface magnification means a value obtained by multiplying the MD-direction stretching magnification by the TD-direction stretching magnification.

  The stretching temperature in the step (3) is preferably a melting point temperature of −50 ° C. or higher, more preferably a melting point temperature of −30 ° C. or higher, more preferably a melting point temperature of −20 ° C. or higher, with the melting point temperature of the polyolefin resin as a reference temperature. The upper limit is preferably a melting point temperature of −2 ° C. or lower, more preferably a melting point temperature of −3 ° C. or lower. Setting the stretching temperature to -50 ° C. or higher allows the interface between the polyolefin resin and the inorganic particles or the interface between the polyolefin resin and the plasticizer to adhere well, in a local and micro region of the polyolefin microporous membrane. It is preferable from the viewpoint of improving compression resistance. For example, when high density polyethylene is used as the polyolefin resin, the stretching temperature is preferably 115 ° C. or higher and 132 ° C. or lower. When a plurality of polyolefins are mixed and used, the melting point of the polyolefin having the larger heat of fusion can be used as a reference.

  Step (4) is a stretching step in which after the step, a plasticizer and inorganic particles are extracted as necessary, and the sheet is further stretched in a uniaxial direction or more.

In the steps (3) and (4), the plasticizer and the inorganic particles can be extracted by a method of immersing or showering in an extraction solvent. The extraction solvent is preferably a poor solvent for polyolefin, a good solvent for plasticizers and inorganic particles, and a boiling point lower than the melting point of polyolefin. Examples of such extraction solvents include hydrocarbons such as n-hexane and cyclohexane, halogenated hydrocarbons such as methylene chloride, 1,1,1-trichloroethane, and fluorocarbons, alcohols such as ethanol and isopropanol, and acetone. And ketones such as 2-butanone and alkaline water. An extraction solvent can be used individually or in mixture of 2 or more types.
When inorganic particles are used, the whole amount or a part thereof may be extracted in any of the entire steps, or may be left in the product. Moreover, there is no restriction | limiting in particular about the order of extraction, a method, and the frequency | count. The extraction of the inorganic particles may not be performed as necessary.

Step (5) is a post-processing step in which a plasticizer and an inorganic agent are extracted as necessary after the stretching step and further subjected to heat treatment.
The step (5) is preferably a step of performing heat fixation and / or heat relaxation.
Examples of the heat treatment method include a heat setting method in which stretching and relaxation operations are performed at a predetermined temperature using a tenter or a roll stretching machine. The relaxation operation is a reduction operation performed at a certain relaxation rate on the MD and / or TD of the film. The relaxation rate is a value obtained by dividing the MD dimension of the film after the relaxation operation by the MD dimension of the film before the operation, or a value obtained by dividing the TD dimension after the relaxation operation by the TD dimension of the film before the operation, or MD, TD When both are relaxed, it is a value obtained by multiplying the MD relaxation rate and the TD relaxation rate. The predetermined temperature is preferably 100 ° C. or more from the viewpoint of thermal shrinkage, and is preferably less than 135 ° C. from the viewpoint of porosity and permeability. The predetermined relaxation rate is preferably 0.9 or less, and more preferably 0.8 or less, from the viewpoint of the heat shrinkage rate. Moreover, it is preferable that it is 0.6 or more from a viewpoint of wrinkle generation | occurrence | production prevention, a porosity, and permeability | transmittance. The relaxation operation may be performed in both the MD and TD directions. However, even with the relaxation operation of only one of the MD and TD, it is possible to reduce the thermal contraction rate not only in the operation direction but also in the operation and the vertical direction.

  In addition to the steps (1) to (5), as a method for producing the microporous membrane, a step of superimposing a plurality of single layer bodies can be employed as a step for obtaining a laminate. In addition, a surface treatment process such as electron beam irradiation, plasma irradiation, surfactant coating, chemical modification, etc. may be employed.

The puncture strength of the polyolefin microporous membrane of the present embodiment is preferably 2.4 N / 20 μm or more, more preferably 3.0 N / 20 μm or more, and further preferably 3.5 N / 20 μm or more. It is preferably 20.0 N / 20 μm or less, more preferably 10.0 N / 20 μm or less, still more preferably 8.0 N / 20 μm or less, and particularly preferably 7.5 N / 20 μm or less. Setting the puncture strength to 2.4 N / 20 μm or more is preferable from the viewpoint of suppressing membrane breakage due to the dropped active material or the like during battery winding. Moreover, it is preferable also from a viewpoint which can reduce the risk of a short circuit by the expansion and contraction of the electrode accompanying charging / discharging. On the other hand, 20.0 N / 20 μm or less is preferable from the viewpoint of reducing width shrinkage due to orientation relaxation during heating.
The puncture strength can be adjusted by a method of adjusting the molecular weight of the polyolefin resin, the ratio of the polyolefin resin, the stretching temperature and the stretching ratio in the step (3), and the like.
Here, the puncture strength was determined by fixing the microporous membrane with a sample holder having a diameter of 11.3 mm using a handy compression tester KES-G5 (trademark) manufactured by Kato Tech, and then fixing the microporous membrane. The value of the maximum piercing load (N) measured by performing a piercing test in a 23 ± 2 ° C. atmosphere at a radius of curvature of the needle tip of 0.5 mm and a piercing speed of 2 mm / sec at the center of the membrane.

The porosity of the polyolefin microporous membrane of the present embodiment is preferably 30% or more, more preferably 35% or more, and further preferably 40% or more from the viewpoint of following the rapid movement of lithium ions at the high rate. . Further, from the viewpoint of film strength and self-discharge, it is preferably 90% or less, more preferably 80% or less.
The porosity is adjusted by a method for adjusting the stretching temperature and the stretching ratio in the step (3) and / or a method for adjusting the temperature and the magnification in the heat fixing and thermal relaxation step (5). Is possible.

The heat shrinkage rate in the width direction at 140 ° C. of the polyolefin microporous membrane of the present embodiment is preferably 33% or less, more preferably 20% or less. By setting the heat shrinkage rate in the width direction at 140 ° C. to 33% or less, when there is a heating process during the production of the electricity storage device, the risk of shrinkage and contact between the electrodes may be reduced. Also, small shrinkage is preferable from the viewpoint of ensuring long-term reliability.
In addition, the said heat shrinkage rate can be adjusted by the method of adjusting the temperature of the heat fixation and heat relaxation process of said (5), and a magnification.
Here, the thermal shrinkage rate was measured after a polyolefin microporous membrane was cut into 100 mm squares so that each side was parallel to MD and TD, and left in an oven adjusted to a temperature of 140 ° C. for 1 hour. The value of heat shrinkage rate.

  The film thickness of the polyolefin microporous membrane of the present embodiment is preferably 2 μm or more, more preferably 5 μm or more, and the upper limit is preferably 100 μm or less, more preferably 60 μm or less, and even more preferably 50 μm or less. Setting the film thickness to 2 μm or more is preferable from the viewpoint of improving the mechanical strength. On the other hand, it is preferable to set the film thickness to 100 μm or less because the occupied volume of the separator is reduced, which tends to be advantageous in terms of increasing the capacity of the battery.

The air permeability of the polyolefin microporous membrane of the present embodiment is preferably 10 seconds / 100 cc or more, more preferably 50 seconds / 100 cc or more, and the upper limit is preferably 1000 seconds / 100 cc or less, preferably 500 seconds. / 100 cc or less, more preferably 300 seconds / 100 cc or less. The air permeability is preferably 10 seconds / 100 cc or more from the viewpoint of suppressing self-discharge of the electricity storage device. On the other hand, setting it to 1000 seconds / 100 cc or less is preferable from the viewpoint of obtaining good charge / discharge characteristics.
The air permeability can be adjusted by a method of adjusting the temperature and magnification of the heat fixing and heat relaxation steps of (5).

The polyolefin microporous membrane of the present embodiment is particularly useful as a separator for an electricity storage device using a non-aqueous electrolyte. The electricity storage device of the present embodiment uses the above-described polyolefin microporous film as a separator, and includes a positive electrode, a negative electrode, and an electrolytic solution.
The electricity storage device, for example, prepares the polyolefin microporous membrane as a vertically long separator having a width of 10 to 500 mm (preferably 80 to 500 mm) and a length of 200 to 4000 m (preferably 1000 to 4000 m). The positive electrode-separator-negative electrode-separator or negative electrode-separator-positive electrode-separator are stacked in this order, wound into a circular or flat spiral shape to obtain a wound body, and the wound body is stored in a battery can. It can manufacture by inject | pouring electrolyte solution.
The electricity storage device is manufactured through a process of laminating a flat plate in the order of positive electrode-separator-negative electrode-separator or negative electrode-separator-positive electrode-separator, laminating with a bag-like film, and injecting an electrolyte solution. You can also.

  The power storage device of this embodiment is particularly useful as an electric vehicle or a hybrid vehicle because it has high output and excellent long-term reliability.

  In addition, about the measuring method of the various parameters mentioned above, unless there is particular notice, it measures according to the measuring method in the Example mentioned later.

  Next, the present embodiment will be described more specifically with reference to examples and comparative examples. However, the present embodiment is not limited to the following examples unless it exceeds the gist. In addition, the physical property in an Example was measured with the following method.

(1) Viscosity average molecular weight (Mv)
Based on ASTM-D4020, the intrinsic viscosity [η] at 135 ° C. in a decalin solvent was determined.
Mv of polyethylene was calculated by the following formula.
[Η] = 6.77 × 10 −4 Mv ^0.67
Mv of polypropylene was calculated by the following formula.
[Η] = 1.10 × 10 −4 Mv ^0.80

(2) Film thickness It measured at room temperature 23 degreeC using the micro thickness measuring device (type KBM by Toyo Seiki).

(3) Porosity A 10 cm × 10 cm square sample was cut from the microporous membrane, and its volume (cm ³ ) and mass (g) were determined. For the polypropylene microporous membrane, the membrane density was 0.91 (g / cm ³ ) Using the following formula.
Porosity = (1−mass / volume / 0.91) × 100
For the polyethylene microporous membrane, the membrane density was calculated as 0.95 (g / cm ³ ) using the following formula.
Porosity = (1−mass / volume / 0.95) × 100

(4) Air permeability It measured using the Gurley type air permeability meter (made by Toyo Seiki) based on JIS P-8117.

(5) Puncture strength Using a handy compression tester KES-G5 (trademark) manufactured by Kato Tech, a microporous membrane was fixed with a sample holder having a diameter of 11.3 mm at the opening, and then the fixed microporous membrane The central portion was determined as the value of the maximum piercing load measured by performing a piercing test in a 23 ± 2 ° C. atmosphere at a needle radius of curvature of 0.5 mm and a piercing speed of 2 mm / sec.

(6) 3C rate (high rate characteristics,%)
a. Production of Positive Electrode 92.2% by mass of lithium cobalt composite oxide LiCoO ₂ as a positive electrode active material, 2.3% by mass of flake graphite and acetylene black as conductive materials, and polyvinylidene fluoride (PVDF) 3.2 as a binder, respectively. A slurry was prepared by dispersing mass% in N-methylpyrrolidone (NMP). This slurry was applied to an aluminum foil serving as a positive electrode current collector with a die coater, dried, and compression molded with a roll press to produce a positive electrode.
b. Preparation of Negative Electrode 96.9% by mass of artificial graphite as a negative electrode active material, 1.4% by mass of ammonium salt of carboxymethyl cellulose and 1.7% by mass of styrene-butadiene copolymer latex as a binder were dispersed in purified water to prepare a slurry. did. The slurry was applied to a copper foil serving as a negative electrode current collector with a die coater, dried, and compression molded with a roll press to produce a negative electrode.
c. Preparation of Nonaqueous Electrolytic Solution Prepared by dissolving LiPF ₆ as a solute in a mixed solvent of ethylene carbonate: ethyl methyl carbonate = 1: 2 (volume ratio) to a concentration of 1.0 mol / liter.
d. Battery assembly The separator was cut into a circle of 18 mmφ, the positive electrode and the negative electrode were cut into a circle of 16 mmφ, and the positive electrode, the separator, and the negative electrode were stacked in this order so that the active material surfaces of the positive electrode and the negative electrode faced, The container and the lid were insulated, and the container was in contact with the negative electrode copper foil and the lid was in contact with the positive electrode aluminum foil. The above-mentioned non-aqueous electrolyte was poured into this container and sealed. After standing at room temperature for 1 day, the battery voltage was charged to 4.2V at a current value of 3mA (0.5C) in a 25 ° C atmosphere, and the current value was reduced from 3mA so as to maintain 4.2V after reaching the battery voltage. By the method of starting, the first charge after making a battery for a total of 6 hours was performed. Subsequently, the battery was discharged to a battery voltage of 3.0 V at a current value of 3 mA (0.5 C).
e. 1C capacity measurement (mAh)
Charging to a battery voltage of 3.6V at a current value of 1.1A (1.0C) in an atmosphere of 25 ° C., and further reducing the current value from 1.1A so as to maintain 3.6V. The battery was charged for 3 hours. Next, the battery was discharged to a battery voltage of 2.0 V at a current value of 1.1 A (1.0 C) to obtain a 1 C discharge capacity.
f. High-rate characteristics In a 25 ° C atmosphere, the battery voltage is charged to 3.6 V at a current value of 1.1 A (1.0 C), and the current value starts to be reduced from 1.1 A so that 3.6 V is maintained. The battery was charged for a total of 3 hours. Next, the battery was discharged to a battery voltage of 2.0 V at a current value of 3.3 A (3.0 C) to obtain a 3 C discharge capacity.
The ratio of the 3C discharge capacity to the 1C discharge capacity was defined as the 3C capacity retention rate (%) and used as an indicator of the high rate characteristics.

(7) Nail penetration test The electrode plate laminated body was produced by stacking the negative electrode, the polyolefin microporous film, the positive electrode, and the polyolefin microporous film in this order and winding in a spiral shape. The electrode plate laminate is housed in a stainless steel container having an outer diameter of 18 mm and a height of 65 mm, and an aluminum tab derived from the positive electrode current collector is used as a container lid terminal portion, and a nickel tab derived from the negative electrode current collector Was welded to the container wall. Thereafter, vacuum drying was performed, and the battery was assembled by injecting and sealing the non-aqueous electrolyte into the container in an argon box.
The assembled battery is charged at a constant current of 1 / 3C to a voltage of 4.2V, then charged at a constant voltage of 4.2V for 5 hours, and then discharged at a current of 1 / 3C to a final voltage of 3.0V. went. Next, after constant current charging to a voltage of 4.2 V with a current value of 1 C, 4.2 V constant voltage charging was performed for 2 hours, and then discharging was performed to a final voltage of 3.0 V with a current of 1 C. Finally, after constant voltage charging of 4.2 V with a current value of 1 C, constant voltage charging of 4.2 V was performed for 2 hours. In this way, a pretreated battery was obtained.
Further, with respect to the battery after the pretreatment, in a room temperature of 23 ± 2 ° C., an iron nail having a diameter of 2.7 mm is placed outside the case and 3 mm from the end of the laminated body at a speed of 5 mm / second. Punctured to a depth of 2 mm. The temperature reached after 30 seconds was measured with a thermocouple attached to the side of the battery away from the nail penetration position. When the temperature at this time was 50 ° C. or less, ◎, when it exceeded 50 ° C. and below 60 ° C., and when it exceeded 60 ° C. were used as indexes for nail penetration test evaluation.

(8) Effective diffusion coefficient D (Z) _{eff in} the thickness direction, diffusion coefficient D ₀
A circular sample having a diameter narrowed by 0.1 to 0.3 mm from the inner diameter of the NMR measurement sample tube is prepared. When the obtained circular sample was laminated to a thickness of 4 to 5 cm and set in a sample tube for NMR measurement, lithium salt LiN (SO ₂ CF ₃ ) ₂ (LiTFSI) was added to ethylene carbonate inside the laminated sample. The diffusion coefficient D (Z) of lithium ions at 30 ° C. is determined by a magnetic field gradient NMR measurement method in a state in which an electrolytic solution dissolved in a mixed solvent in which the ratio of ethylmethyl carbonate to 1: 1 is infiltrated and held. It was. In the magnetic field gradient NMR measurement method, the observed peak height is E, the peak height when no magnetic field gradient pulse is applied is E ₀ , the nuclear magnetic rotation ratio is γ (T ⁻¹ · s ⁻¹ ), and the magnetic field gradient intensity is When g (T · m ⁻¹ ), magnetic field gradient pulse application time is δ (s), diffusion waiting time is Δ (s), and self-diffusion coefficient is D (m ² · s ⁻¹ ), the following equation holds. .
Ln (E / E ₀ ) = D (Z) × γ ² × g ² × δ ² × (Δ−δ / 3)
From the above equation, D (Z) can be obtained by observing the change of the NMR peak by changing g, δ, and Δ. Actually, using the bpp-led-DOSY method as the NMR sequence, Δ and δ are fixed, g is changed from 0 to 10 or more in the range of Ln (E / E ₀ ) ≦ −3, and Ln ( D was obtained from the slope of a straight line plotted with E / E ₀ ) as the Y axis and γ ² × g ² × δ ² × (Δ−δ / 3) as the X axis. The set values of Δ and δ are arbitrary, but the following conditions must be satisfied when the longitudinal relaxation time of the measurement target is T1 (s) and the lateral relaxation time is T2 (s).
10ms <Δ <T1
0.2 ms <δ <T2
In practice, the magnetic field gradient NMR measurement was carried out with Δ = 50 ms and δ with an arbitrary value in the range of 0.4 ms ≦ δ ≦ 3.2 ms. When the self-diffusion is hindered due to the influence of the structure of the porous film, the above plot becomes a downwardly convex curve. In this case, the curve is in the range of Ln (E / E ₀ ) from 0 to −2. A straight line approximation was performed, and D (Z) was obtained from this slope.
The effective diffusion coefficient D (Z) _eff is obtained by multiplying the obtained D (Z) by the porosity (ε) of the microporous film used for the measurement, as shown in the following equation.
D (Z) _eff = D (Z) × ε
The diffusion coefficient D ₀ can be obtained by performing the above operation in the absence of a microporous film.

[Example 1]
47.5% by mass of homopolymer polyethylene with an Mv of 700,000, 47.5% by mass of homopolymer polyethylene with an Mv of 300,000, 5% by mass of polypropylene with an Mv of 400,000 (PP blend amount 5% by mass) Was dry blended using a tumbler blender to obtain a polymer mixture. The obtained polymer mixture was substituted with nitrogen, and then supplied to the twin-screw extruder by a feeder under a nitrogen atmosphere. Further, liquid paraffin (kinematic viscosity at 37.78 ° C .: 7.59 × 10 ⁻⁵ m ² / s) was injected into the extruder cylinder by a plunger pump.
Feeder so that the liquid paraffin content ratio in the total mixture to be melt-kneaded and extruded is 66% by mass (that is, the polymer concentration (sometimes abbreviated as “PC”) is 34% by mass). And the pump was adjusted.
Subsequently, the melt-kneaded material was extruded and cast on a cooling roll controlled at a surface temperature of 25 ° C. through a T-die, thereby obtaining a gel sheet having a thickness of 1370 μm.
Next, it led to the simultaneous biaxial tenter stretching machine, and biaxial stretching was performed. The set stretching conditions were an MD magnification of 7.0 times, a TD magnification of 6.4 times, and a preset temperature of 125 ° C.
Next, the solution was introduced into a methyl ethyl ketone tank and sufficiently immersed in methyl ethyl ketone to extract and remove liquid paraffin, and then the methyl ethyl ketone was removed by drying.
Next, it was led to a TD tenter and heat fixed. The heat setting temperature was 126 ° C., HS (heat setting) was performed at a draw ratio of 1.40 times, and the subsequent TD relaxation rate was set to 0.8 to obtain a microporous film. Table 1 shows the physical properties and evaluation results of the obtained microporous membrane.

[Example 2]
47.5% by mass of homopolymer polyethylene with an Mv of 700,000, 47.5% by mass of homopolymer polyethylene with an Mv of 300,000, 5% by mass of polypropylene with an Mv of 400,000 (PP blend amount 5% by mass) Was dry blended using a tumbler blender to obtain a polymer mixture. The obtained polymer mixture was substituted with nitrogen, and then supplied to the twin-screw extruder by a feeder under a nitrogen atmosphere. Further, liquid paraffin (kinematic viscosity at 37.78 ° C .: 7.59 × 10 ⁻⁵ m ² / s) was injected into the extruder cylinder by a plunger pump.
Feeder so that the liquid paraffin content ratio in the total mixture to be melt-kneaded and extruded is 65% by mass (that is, the polymer concentration (sometimes abbreviated as “PC”) is 35% by mass). And the pump was adjusted.
Next, it led to the simultaneous biaxial tenter stretching machine, and biaxial stretching was performed. The set stretching conditions were an MD magnification of 7.0 times, a TD magnification of 6.4 times, and a preset temperature of 120 ° C.
Next, the sample was introduced into a methylene chloride bath and sufficiently immersed in methylene chloride to extract and remove the liquid paraffin, and then the methylene chloride was removed by drying to obtain a microporous membrane. Table 1 shows the physical properties and evaluation results of the obtained microporous membrane.

[Example 3]
A microporous membrane was obtained by the same method as in Example 2 except that the gel sheet thickness was 2150 μm, the biaxial stretching temperature was 122 ° C., and the extraction solvent was methyl ethyl ketone. Table 1 shows the physical properties and evaluation results of the obtained microporous membrane.

[Example 4]
A microporous membrane was obtained by the same method as in Example 2 except that the gel sheet thickness was 1900 μm, the biaxial stretching temperature was 125 ° C., and the extraction solvent was methylene chloride. Table 1 shows the physical properties and evaluation results of the obtained microporous membrane.

[Example 5]
30.0 mass% of homopolymer polyethylene having a viscosity average molecular weight (Mv) of 700,000, 70.0 mass% of homopolymer polyethylene having an Mv of 300,000, a gel sheet thickness of 1700 μm, and a biaxial stretching temperature of 120 ° C. Except for this, a microporous membrane was obtained in the same manner as in Example 2. Table 1 shows the physical properties and evaluation results of the obtained microporous membrane.

[Example 6]
Example 1 except that the gel sheet thickness was 1900 μm, PC was 35 mass%, biaxial stretching temperature was 123 ° C., extraction solvent was methylene chloride, HS temperature was 127 ° C., and HS magnification was 1.63 times. A microporous membrane was obtained by this method. Table 1 shows the physical properties and evaluation results of the obtained microporous membrane.

[Example 7]
Except that the gel sheet thickness was 1840 μm, the PC was 31% by mass, the biaxial stretching temperature was 127.5 ° C., the extraction solvent was methylene chloride, the HS temperature was 128.5 ° C., and the HS magnification was 1.6 times. A microporous membrane was obtained in the same manner as in Example 1. Table 1 shows the physical properties and evaluation results of the obtained microporous membrane.

[Comparative Example 1]
Example 1 except that the gel sheet thickness was 2000 μm, the PC was 35% by mass, the biaxial stretching temperature was 124 ° C., the extraction solvent was methylene chloride, the HS temperature was 127 ° C., and the HS magnification was 1.7 times. A microporous membrane was obtained by this method. Table 1 shows the physical properties and evaluation results of the obtained microporous membrane.

[Comparative Example 2]
The polypropylene resin was extruded at 220 ° C. with a 2.5 inch extruder and the molten polymer was cooled by blown air. Next, the extruded thin film was annealed at 127 ° C. for 2 minutes, then cold-stretched to 20% at room temperature, then uniaxially stretched to 300%, and then heat-treated at 130 ° C. for 2 minutes. Table 1 shows the physical properties and evaluation results of the obtained separator.

[Comparative Example 3]
The polypropylene resin was extruded at 220 ° C. with a 2.5 inch extruder and the molten polymer was cooled by blown air. Next, the extruded thin film was annealed at 125 ° C. for 2 minutes, then cold-stretched to 20% at room temperature, then uniaxially stretched to 150%, and then heat-treated at 130 ° C. for 2 minutes. Table 1 shows the physical properties and evaluation results of the obtained separator.

[Comparative Example 4]
Example 1 except that the gel sheet thickness was 1950 μm, the PC was 37% by mass, the biaxial stretching temperature was 122 ° C., the extraction solvent was methylene chloride, the HS temperature was 124 ° C., and the HS magnification was 2.0 times. A microporous membrane was obtained by this method. Table 1 shows the physical properties and evaluation results of the obtained microporous membrane.

As apparent from the results in Table 1, the effective diffusion coefficient D (Z) _eff and the value of Brookman index α and the piercing strength of Examples 1 to 7 in the thickness direction were adjusted to a specific range. All batteries using a polyolefin microporous membrane as a separator exhibited good nail penetration test evaluation and excellent high rate characteristics.

  The polyolefin microporous membrane of the present invention has industrial applicability particularly as a separator for an electricity storage device having a high output density.

Claims (3)

D (Z) is the diffusion coefficient in the thickness direction of the polyolefin microporous film measured by the magnetic field gradient NMR method, D _{0 is} the diffusion coefficient of the electrolyte used in the measurement of the magnetic field gradient NMR method, and the porosity of the polyolefin microporous film Is an effective diffusion coefficient D (Z) _{eff in} the thickness direction represented by the following equation (1) is 2.8 × 10 ⁻¹¹ or more, and is represented by α in the following equation (2). A polyolefin microporous membrane having a Burgmann index of 1.50 ≦ α <2.60 and a puncture strength of 2.4 N / 20 μm or more and 20.0 N / 20 μm or less.
D (Z) _eff = D (Z) × ε ·· (1)
ε ^α = D (Z) / D ₀ (2)     The polyolefin microporous membrane according to claim 1, wherein the polyolefin resin forming the polyolefin microporous membrane contains high-density polyethylene.   An electrical storage device comprising the polyolefin microporous membrane according to claim 1 or 2 as a separator.