JP2019091548A - Power storage device separator and power storage device - Google Patents

Abstract

To provide a power storage device separator that is excellent in the permeability of ions such as lithium ions, and can constitute a power storage device for high output applications such as high performance lithium ion batteries and capacitors, in which short circuit of a positive electrode and a negative electrode due to dendrite and sharp decrease in discharge capacity are unlikely to occur even when used for high power applications.SOLUTION: A power storage battery separator device according to the present invention includes a synthetic resin and a micropore, and has an air permeation resistance of 30 sec/100 mL/16 μm or more and 100 sec/100 mL/16 μm or less, and in small angle X-ray scattering measurement (SAXS), a scattering vector q has a first scattering peak in the stretching direction within a range of 0.0030 nmor more and 0.0080 nmor less.SELECTED DRAWING: None

Description

  The present invention relates to a storage device separator and a storage device.

  Conventionally, storage devices such as lithium ion batteries, capacitors, and capacitors have been used. For example, a lithium ion battery is generally configured by disposing a positive electrode, a negative electrode, and a separator in an electrolytic solution. The positive electrode is formed by applying lithium cobaltate or lithium manganate to the surface of an aluminum foil. The negative electrode is obtained by applying carbon to the surface of a copper foil. And a separator is arrange | positioned so that a positive electrode and a negative electrode may be partitioned, and the short circuit of a positive electrode and a negative electrode is prevented.

  At the time of charging of the lithium ion battery, lithium ions are released from the positive electrode and enter the negative electrode. On the other hand, when the lithium ion battery is discharged, lithium ions are released from the negative electrode and move to the positive electrode. Such charge and discharge are repeated in the lithium ion battery. Therefore, the separator used in the lithium ion battery is required to be able to transmit lithium ions well.

  When charge and discharge of the lithium ion battery are repeated, dendrites (dendrites) of lithium are generated on the end face of the negative electrode. The dendrite breaks through the separator to cause a minute short circuit (dendrite short) between the positive electrode and the negative electrode.

  BACKGROUND ART In recent years, large-sized batteries such as lithium ion batteries for automobiles are increasing in output power, and there is a demand for reduction in resistance when lithium ions pass through a separator. Therefore, the separator is required to have high air permeability. Furthermore, in the case of a large lithium ion battery, it is also important to guarantee long life and long-term safety.

Patent Document 1 is a porous polypropylene film containing a polypropylene resin and a β crystal nucleating agent, and the size in the width direction is 5% and the temperature at which the heat shrinks by 5% is 130 to 200 ° C., and the air resistance is 50 to 500. There is disclosed a porous polypropylene film which has a second rate of 100 ml, a porosity of 35 to 70%, and satisfies the following relational expression.
G + 15 × ε ≦ 1,200

WO 2012/105661

  However, the porous polypropylene film of Patent Document 1 has low air permeability and insufficient lithium ion permeability. Therefore, it is difficult to use such a polypropylene microporous film for a lithium ion battery which requires high output.

  Moreover, when the holes are not uniformly formed in the separator, the lithium ion permeability also becomes nonuniform. Therefore, in the separator, a site having high lithium ion permeability and a site having low lithium ion permeability are generated. Such separators have the problem that dendrites are generated at sites where lithium ion permeability is high and micro shorts are likely to occur, and the long life and long-term safety are not sufficient.

  The present invention is excellent in the permeability of ions such as lithium ions, and can constitute power storage devices such as high performance lithium ion batteries, capacitors, capacitors, etc. Even if used for high power applications, positive and negative electrodes by dendrites The present invention provides a storage device separator that is unlikely to cause a short circuit or a sudden decrease in discharge capacity.

[Separator for electricity storage device]
The electric storage device separator of the present invention is
Containing synthetic resin and micropores, gas permeation resistance is 30sec / 100mL / 16μm or more and 100sec / 100mL / 16μm or less, and in small angle X-ray scattering measurement (SAXS), scattering vector q is 0.0030 nm ^-1 or more , And has a first scattering peak in the stretching direction within the range of 0.0080 nm ^-1 or less.

  The storage device separator contains a synthetic resin. As a synthetic resin, an olefin resin is preferable, an ethylene resin and a propylene resin are preferable, and a propylene resin is more preferable.

  50 mass% or more is preferable, as for content of the olefin resin in a synthetic resin, 70 mass% or more is more preferable, 80 mass% or more is especially preferable, and 100 mass% is the most preferable.

  Examples of the propylene-based resin include homopolypropylene and copolymers of propylene and other olefins. When the separator for a storage battery device is manufactured by the stretching method, homopolypropylene is preferable. The propylene resins may be used alone or in combination of two or more. The copolymer of propylene and other olefin may be either a block copolymer or a random copolymer. 50 mass% or more is preferable, and, as for content of the propylene component in propylene-type resin, 80 mass% or more is more preferable.

  In addition, as an olefin copolymerized with propylene, for example, ethylene, 1-butene, 1-pentene, 4-methyl-1-pentene, 1-hexene, 1-octene, 1-nonene, 1-decene and the like α -An olefin etc. is mentioned, Ethylene is preferable.

  Examples of the ethylene-based resin include ultra low density polyethylene, low density polyethylene, linear low density polyethylene, medium density polyethylene, high density polyethylene, ultra high density polyethylene, and an ethylene-propylene copolymer. Moreover, as long as the ethylene-based resin microporous film contains an ethylene-based resin, it may contain another olefin-based resin. The content of the ethylene component in the ethylene-based resin is preferably more than 50% by mass, more preferably 80% by mass or more.

  Although the weight average molecular weight of an olefin resin is not specifically limited, 30,000-500,000 are preferable and 50,000-480,000 are more preferable. The weight average molecular weight of the propylene-based resin is not particularly limited, but is preferably 250,000 to 500,000, and more preferably 280,000 to 480,000. The weight average molecular weight of the ethylene-based resin is not particularly limited, but is preferably 30,000 to 250,000, and more preferably 50,000 to 200,000. According to the olefin resin having a weight average molecular weight within the above range, it is possible to provide a storage battery device separator excellent in air permeability.

  The molecular weight distribution (weight-average molecular weight Mw / number-average molecular weight Mn) of the olefin resin is not particularly limited, but 5 to 30 is preferable, and 7.5 to 25 is more preferable. The molecular weight distribution of the propylene-based resin is not particularly limited, but is preferably 7.5 to 12 and more preferably 8 to 11. Although the molecular weight distribution of ethylene resin is not specifically limited, 5.0-30 are preferable and 8.0-25 are more preferable. According to the olefin resin having a molecular weight distribution within the above range, a storage battery device separator excellent in air permeability can be provided.

  Here, the weight average molecular weight and the number average molecular weight of the olefin resin are values in terms of polystyrene measured by GPC (gel permeation chromatography) method. Specifically, 6 to 7 mg of an olefin resin is collected, and the collected olefin resin is supplied to a test tube, and o-b containing 0.05% by mass of BHT (dibutylhydroxytoluene) in the test tube. A diluted solution is prepared by adding a DCB (ortho-dichlorobenzene) solution and diluting so that the olefin resin concentration becomes 1 mg / mL.

  The diluent is shaken at a rotational speed of 25 rpm for 1 hour at 145 ° C. using a dissolution filtration apparatus to dissolve the olefin resin in the o-DCB solution to obtain a measurement sample. The weight average molecular weight and the number average molecular weight of the olefin resin can be measured by the GPC method using this measurement sample.

The weight average molecular weight and the number average molecular weight of the olefin resin can be measured, for example, with the following measuring device and measuring conditions.
Measuring device made by TOSOH, trade name "HLC-8121GPC / HT"
Measurement conditions Column: TSK gel GMH HR-H (20) HT x 3
TSKguard column-HHR (30) HT x 1
Mobile phase: o-DCB 1.0 mL / min
Sample concentration: 1 mg / mL
Detector: Bryce-type refractometer
Standard substance: Polystyrene (TOSOH molecular weight: 500 to 8420000)
Elution conditions: 145 ° C
SEC temperature: 145 ° C

  Although melting | fusing point of an olefin resin is not specifically limited, 130-170 degreeC is preferable and 133-165 degreeC is more preferable. The melting point of the propylene-based resin is not particularly limited, but is preferably 160 to 170 ° C., and more preferably 160 to 165 ° C. The melting point of the ethylene-based resin is not particularly limited, but is preferably 130 to 140 ° C., and more preferably 133 to 139 ° C. According to the olefin resin having a melting point in the above-mentioned range, it is possible to provide a storage battery device separator excellent in air permeability.

  In the present invention, the melting point of the olefin resin can be measured according to the following procedure using a differential scanning calorimeter (for example, Seiko Instruments Inc. device name “DSC220C” or the like). First, 10 mg of an olefin resin is heated from 25 ° C. to 250 ° C. at a heating rate of 10 ° C./min and held at 250 ° C. for 3 minutes. Next, the olefin resin is cooled from 250 ° C. to 25 ° C. at a temperature decrease rate of 10 ° C./min and held at 25 ° C. for 3 minutes. Subsequently, the olefin resin is reheated from 25 ° C. to 250 ° C. at a heating rate of 10 ° C./min, and the temperature at the top of the endothermic peak in this reheating step is taken as the melting point of the olefin resin.

  The storage device separator includes minute holes. The micropores preferably penetrate in the thickness direction of the film, which can impart excellent air permeability to the electric storage device separator. Such a storage device separator can transmit ions such as lithium ions in the thickness direction. Note that the thickness direction of the storage device separator means a direction orthogonal to the main surface of the storage device separator. The main surface of the storage device separator is the surface with the largest area among the surfaces of the storage device separator.

  In the electric storage device separator, preferably, the micropores are formed by stretching. In the cross section along the thickness direction of the storage device separator, the average pore diameter of the micropores is preferably 20 to 100 nm, more preferably 20 to 70 nm, and particularly preferably 30 to 50 nm.

  The average pore diameter of the micropores refers to the value measured in the following manner. First, the storage device separator is cut along its thickness direction and extension direction (along a plane orthogonal to the main surface of the storage device separator and along the extension direction), and a scanning electron microscope (SEM) is obtained. Take an enlarged photograph of the cut surface at a magnification of 10,000 times using. The vertical direction of the enlarged photograph is adjusted to be the thickness direction, and the central portion in the thickness direction is taken as an imaging location. The entire range of the obtained magnified image is defined as the measurement zone.

  The SEM photograph of the cut surface of the storage device separator is taken in the following manner. First, after reinforcing the electric storage device separator so as to be easily cut with a copper tape or the like, a cross section polisher (for example, a cross section polisher commercially available from Nippon Denshi under the trade name "IB-19500 CP") is used. Disconnect. Next, after depositing a metal film (for example, a metal film such as gold, platinum, osmium, carbon, etc.) on the cut surface in order to prevent disturbance of the image due to charge-up, SEM (for example, trade name “S The cut surface is photographed under the condition of an acceleration voltage of 1.0 kV using a SEM (commercially available under "-4800 S"). Although it becomes possible to take a clear magnified photograph by measuring in the above manner, it is not limited to the method described above as long as a clear magnified photograph can be obtained.

  Next, an ellipse that encloses the micropores appearing in the magnified photograph and in which the major axis and the minor axis are both shortest is drawn for each micropore. The arithmetic mean value of the major axis length and the minor axis length of this ellipse is taken as the pore diameter of the micropores. The arithmetic mean value of the pore sizes of the micropores in the measurement section is taken as the average pore size of the micropores. In addition, only the micropore part which has all contained in the measurement division is made into a measuring object.

  40-70% is preferable, 50-67% of the porosity of the separator for electrical storage devices is more preferable, and its 53-60% is especially more preferable. The storage device separator having a porosity in the above range is excellent in air permeability.

The porosity of the storage battery device separator can be measured in the following manner. First, a separator for a storage device is cut to obtain a flat square (area of 100 cm ² ) of 10 cm long × 10 cm wide. Next, the weight W (g) and thickness T (cm) of the test piece are measured, and the apparent density ρ (g / cm ³ ) is calculated by the following. In addition, thickness of a test piece measures thickness of a test piece 15 places using a dial gauge (for example, signal ABS dejimatic indicator made by Mitutoyo Co., Ltd.), and makes it the arithmetic mean value. Then, using this apparent density ((g / cm ³ ) and the density _{0 0} (g / cm ³ ) of the synthetic resin itself that constitutes the storage device separator, the porosity of the storage device separator based on the following (%) Can be calculated.
Apparent density ((g / cm ³ ) = W / (100 × T)
Porosity [%] = 100 × [(ρ ₀ −ρ) / ρ ₀ ]

  The thickness of the electric storage device separator is preferably 6 μm or more and 25 μm or less, more preferably 9 μm or more and 20 μm or less, and particularly preferably 12 μm or more and 18 μm or less. When the thickness of the storage device separator is 6 μm or more, a short circuit between the positive and negative electrodes can be prevented even when foreign matter is mixed. When the thickness of the storage device separator is 25 μm or less, when used as a storage device separator, the total number of stacked storage device separators can be increased, and the battery capacity per unit volume can be increased.

  In the present invention, the thickness of the storage device separator can be measured according to the following procedure. That is, measurement is made at 10 arbitrary locations of the storage device separator using a dial gauge, and the arithmetic mean value thereof is taken as the thickness of the storage device separator.

  The air permeation resistance of the separator for a storage battery is 30 sec / 100 mL / 16 μm or more and 100 sec / 100 mL / 16 μm or less, preferably 30 sec / 100 mL / 16 μm or more and 80 sec / 100 mL / 16 μm or less, and 30 sec / 100 mL / 16 μm or more and 60 sec / 100 mL / 16 μm or less is more preferable. The storage battery separator having an air permeation resistance within the above range is excellent in ion permeability.

  The air resistance of the storage battery separator is a value measured in the following manner. Measure the air permeability at any 10 locations of the storage device separator according to JIS P8117 in an atmosphere with a temperature of 23 ° C and a relative humidity of 65%, and divide the arithmetic mean by the thickness of the storage device separator. And a value normalized to a thickness of 16 μm is taken as air resistance (sec / 100 mL / 16 μm).

The inventors intensively studied the relationship between the first scattering peak in the stretching direction and the scattering vector q, which were measured in small-angle X-ray scattering measurement (SAXS). In the graph in which the horizontal axis is the scattering vector q (nm ^-1 ) and the vertical axis is the scattering intensity (au), the scattering vector q is 0.0030 nm ^-1 or more and 0.0080 nm ^-1 or less. When the scattering intensity has the first scattering peak within the range of the above, it has been found that the storage device separator has the following advantages. That is, the micropores of the storage device separator are formed to extend linearly in the thickness direction of the storage device separator while suppressing meandering and bending as much as possible. It has been found that excellent air permeability can be imparted.

In the small-angle X-ray scattering measurement (SAXS), the first scattering peak in the stretching direction is present in the range where the scattering vector q is 0.0030 nm ⁻¹ or more and 0.0080 nm ¹ or less. In the small angle X-ray scattering measurement (SAXS), the first scattering peak in the stretching direction is preferably present at a scattering vector q of 0.0040 nm ⁻¹ or more and 0.0080 nm ¹ or less. In the small angle X-ray scattering measurement (SAXS), it is more preferable that the first scattering peak in the stretching direction is present at a scattering vector q of 0.0050 nm ⁻¹ or more and 0.0080 nm ¹ or less. In the small angle X-ray scattering measurement (SAXS), it is particularly preferable that the first scattering peak in the stretching direction is present at a scattering vector q of 0.0060 nm ⁻¹ or more and 0.0080 nm ⁻¹ or less. When the first scattering peak q is present at 0.0030 nm ⁻¹ or more, the permeability of ions such as lithium ions of the storage device separator is improved. When the first scattering peak q is present at 0.0080 nm ^-1 or less, the micropores of the storage device separator are uniformly formed, and the generation of dendrite can be substantially suppressed.

  Small-angle X-ray scattering measurement (SAXS) measures scattered X-rays appearing in a low-angle region of 2θ <10 ° among X-rays scattered by irradiating X-rays to a separator for a storage device. It is a measurement method to measure the regular structure at the level of several nanometers. The scattering vector q is represented by 4π sin θ / λ. Here, λ is the wavelength of X-rays incident on the storage device separator. 2θ is the scattering angle.

  In the storage battery separator, in the lamellar structure in which the noncrystalline portion and the crystalline portion are formed to overlap with each other, the noncrystalline portion is stretched to form a micropore. That is, in the storage device separator, the layered crystal parts are arranged in parallel to each other with a predetermined distance, and a part of the non-crystal part existing between the crystal parts is stretched to open the opening Are continuously formed in the thickness direction of the storage device separator to form micro pores.

  In the present invention, small-angle X-ray scattering measurement (SAXS) finds the phenomenon that a scattering peak occurs when an ordered structure is present, and when the distance between adjacent crystal parts becomes large, θ becomes large. In the phenomenon of becoming

That is, in the range in which the scattering vector q is 0.0030 nm ^-1 or more and 0.0080 nm ^-1 or less, when the first scattering peak in the stretching direction (the arrangement direction of the layered crystal portion) is present, the crystal portion is Have found that they are parallel to one another with a reasonable spacing. Then, it has been found that the micropores are formed while being substantially suppressed from being meandered and bent in the thickness direction of the storage device separator, between the crystal portions arranged in parallel.

  Therefore, in the storage device separator, micropores of appropriate size in the thickness direction are formed while the meandering and bending are substantially suppressed in the thickness direction of the storage device separator, and the storage device separator is It is excellent in permeability such as ions.

  Then, in the storage device separator, the micropores can be formed substantially uniformly between the layered crystal parts, so that the lithium ion permeability can be made uniform, and the generation of dendrite can be substantially suppressed. It is possible to improve the long life and long-term safety of the storage device using the storage device separator.

  In addition, layered crystal parts are regularly arranged in parallel, and between the layered crystal parts, the micropores are formed in a nearly linear state while being substantially suppressed from meandering and bending in the thickness direction of the storage device separator. It is done. Therefore, sufficient thickness can be given to a layered crystal part, fully forming a minute pore part, and the separator for storage devices has the outstanding mechanical strength.

  Furthermore, it is preferable that the storage device separator is uniaxially stretched. When the storage device separator is uniaxially stretched, stretching stress applied at the time of uniaxial stretching slightly remains as a residual stress in the storage device separator. Therefore, when the inside of the storage device becomes abnormally high temperature, the storage device separator is slightly deformed to such an extent that the positive electrode and the negative electrode are not short-circuited due to the residual stress, and the minute pores extend in the thickness direction The ion permeability is lowered by positively bending the As a result, the abnormal reaction in the storage device can be suppressed, the abnormal high temperature in the storage device can be alleviated, and the safety can be improved.

  In the present invention, small angle X-ray scattering measurement (SAXS) is performed as follows. Small angle X-ray scattering measurement (SAXS) is measured using an X-ray diffractometer according to the following procedure. First, eight flat square test pieces each having a side of 30 mm are cut out from the storage device separator. In addition, it adjusts so that one side of any one of a test piece corresponds with the extending | stretching direction. The obtained eight test pieces are stacked in the thickness direction to prepare a test body. The test body was attached to a measuring jig, and X-rays were made incident on the test body. The irradiation direction of the X-rays is adjusted to be orthogonal to the surface direction of the test piece constituting the test body. As the X-ray diffraction apparatus, for example, an apparatus commercially available from Rigaku Corporation under the trade name “X-ray diffraction apparatus SmartLab” can be used.

  As a light source, a CuKα ray (wavelength: 0.154 nm) is used at an output of 45 kV and 200 mA, and a high resolution PB-Ge (220) × 2 arrangement is used. The measurement is performed in steps of 0.0006 ° in a scan range of 0 to 0.5 °, and the scan rate is 0.02 ° / min.

  When the stretching direction is y-axis, and the direction orthogonal to the stretching direction is x-axis, the scattering vector q in the stretching direction is the horizontal axis, and the scatter intensity is plotted on the vertical axis. The scattering peak appearing on the side is taken as the first scattering peak in the stretching direction.

  As described above, the storage battery separator has excellent air permeability and can substantially suppress the formation of dendrite. Therefore, the storage device separator is a storage device requiring high output (lithium ion battery, nickel hydrogen battery, nickel cadmium battery, nickel zinc battery, silver zinc battery, capacitor (electric double layer capacitor, lithium ion capacitor), capacitor Etc.] can be suitably used.

[Method of Manufacturing Separator for Storage Device]
The manufacturing method of the separator for electrical storage devices is demonstrated.
The separator for the storage device is
An extrusion step of supplying a synthetic resin to an extruder, melt-kneading, and extruding from a T-die attached to the tip of the extruder to obtain a synthetic resin film;
A curing step of curing the synthetic resin film obtained in the extrusion step for at least 1 minute so that the surface temperature becomes (melting point of synthetic resin-30 ° C) to (melting point of synthetic resin-1 ° C);
Uniaxially stretching the synthetic resin film after the curing step at a strain rate of 10 to 250% / min and a stretch ratio of 1.5 to 2.8 times;
And an annealing step of annealing the synthetic resin film after the stretching step. Hereinafter, the method of manufacturing the storage device separator will be described in order.

(Extrusion process)
First, the synthetic resin is supplied to an extruder, melt-kneaded, and extruded from a T-die attached to the tip of the extruder to carry out an extrusion step for obtaining a synthetic resin film.

  The temperature of the synthetic resin when melt-kneading the synthetic resin with an extruder is preferably (melting point of synthetic resin + 20 ° C) to (melting point of synthetic resin + 100 ° C), and (melting point of synthetic resin + 25 ° C) to (synthetic resin Melting point + 80 ° C) is more preferable. When the temperature of the synthetic resin is in the above range, the orientation of the synthetic resin is improved, and lamellas of the synthetic resin can be highly formed.

  The draw ratio at the time of extruding a synthetic resin into a film from an extruder is preferably 50 to 300, more preferably 55 to 280, particularly preferably 65 to 250, and most preferably 68 to 250. When the draw ratio is 50 or more, the synthetic resin can be sufficiently molecularly oriented to sufficiently form lamella of the synthetic resin. The film formation stability of a synthetic resin film can be improved as a draw ratio is 300 or less, and the thickness accuracy and width accuracy of a synthetic resin film can be improved.

  The draw ratio is a value obtained by dividing the lip clearance of the T-die by the thickness of the synthetic resin film extruded from the T-die. To measure the lip clearance of the T-die, measure the lip clearance of the T-die at 10 points or more using a clearance gauge (for example, JIS clearance gauge manufactured by Nagai Gauge Mfg. Co., Ltd.) according to JIS B 7524 It can be done by finding the value. Also, the thickness of the synthetic resin film extruded from the T-die is measured at 10 or more points of the thickness of the synthetic resin film extruded from the T-die using a dial gauge (for example, Signal ABS Digimatic Indicator manufactured by Mitutoyo Co., Ltd.) , Can be performed by determining the arithmetic mean value.

  10-300 m / min is preferable, as for the film-forming speed | rate of a synthetic resin film, 15-250 m / min is more preferable, and 15-30 m / min is especially preferable. When the film forming speed of the synthetic resin film is 10 m / min or more, the synthetic resin can be sufficiently molecularly oriented, and the lamella of the synthetic resin can be sufficiently generated. Moreover, film forming stability of a synthetic resin film can be improved as the film forming speed of a synthetic resin film is 300 m / min or less, and thickness accuracy and width accuracy of a synthetic resin film can be improved.

  It is preferable to cool the synthetic resin film extruded from T-die until the surface temperature becomes (melting point of synthetic resin−100 ° C.) or less. This can promote the crystallization of the synthetic resin to form lamellae. By extruding the melt-kneaded synthetic resin, the synthetic resin molecules constituting the synthetic resin film are oriented in advance, and then the synthetic resin film is cooled to allow lamellae in the portions where the synthetic resin is oriented. It can promote generation.

  The surface temperature of the cooled synthetic resin film is preferably 100 ° C. or less lower than the melting point of the synthetic resin, more preferably 140 ° C. to 110 ° C. lower than the melting point of the synthetic resin, and 135 to 120 ° C. Temperatures as low as ° C are particularly preferred. When the surface temperature of the cooled synthetic resin film is equal to or lower than the temperature 100 ° C. lower than the melting point of the synthetic resin, lamellas of the synthetic resin constituting the synthetic resin film can be sufficiently generated.

(Care process)
Next, the synthetic resin film obtained by the above-mentioned extrusion process is cured. The curing step of the synthetic resin film is performed to grow lamellas formed in the synthetic resin film in the extrusion step. By this, it is possible to form a laminated lamella structure in which crystallized portions (lamellae) and non-crystal portions are alternately arranged in the extrusion direction of the synthetic resin film, and in the stretching step of the synthetic resin film described later It is possible to generate a crack between lamellas, not inside, and form a minute through hole (minute hole) starting from this crack.

  The curing temperature of the synthetic resin film is preferably (melting point of synthetic resin-30 ° C) to (melting point of synthetic resin-1 ° C), and (melting point of synthetic resin-25 ° C) to (melting point of synthetic resin-5 ° C) More preferable. When the curing temperature of the synthetic resin film is (the melting point of the synthetic resin −30 ° C.) or more, the molecules of the synthetic resin can be sufficiently oriented to grow the lamella sufficiently. In addition, when the curing temperature of the synthetic resin film is (the melting point of the synthetic resin-1 ° C or less), the molecules of the synthetic resin can be sufficiently oriented to allow the lamellar to grow sufficiently. The curing temperature of the synthetic resin film refers to the surface temperature of the synthetic resin film.

  The curing time of the synthetic resin film is preferably 1 minute or more, more preferably 3 minutes or more, particularly preferably 5 minutes or more, and most preferably 10 minutes or more. By curing the synthetic resin film for 1 minute or more, the lamella of the synthetic resin film can be sufficiently and uniformly grown. If the curing time is too long, the synthetic resin film may be thermally deteriorated. Therefore, 30 minutes or less are preferable and 20 minutes or less of a curing time are more preferable.

(Stretching process)
Next, a stretching step of uniaxially stretching the synthetic resin film after the curing step is performed. In the stretching step, the synthetic resin film is preferably uniaxially stretched only in the extrusion direction.

  The method for stretching the synthetic resin film in the stretching step is not particularly limited as long as the synthetic resin film can be uniaxially stretched, for example, a method of uniaxially stretching the synthetic resin film at a predetermined temperature using a uniaxial stretching device, etc. It can be mentioned. The stretching of the synthetic resin film is preferably sequential stretching performed by dividing into plural times. By sequentially stretching, the air resistance can be improved while suppressing the porosity of the obtained separator for a storage battery low.

The strain rate at the time of stretching of the synthetic resin film is preferably 10 to 250% / min, more preferably 30 to 245% / min, and particularly preferably 35 to 240% / min. By adjusting the strain rate at the time of stretching of the synthetic resin film within the above range, cracks do not occur irregularly between lamellas, but are arranged at predetermined intervals in the stretching direction of the synthetic resin film, and the synthetic resin film Cracks occur regularly between lamellas which are on an imaginary straight line extending in the thickness direction of the. Therefore, in the electric storage device separator, the supporting portion (layered crystal portion) extending substantially in the thickness direction is formed, and the micropores are formed in a linear shape continuous in the thickness direction as much as possible. The strain rate at the time of extending | stretching of a synthetic resin film means the value calculated based on the following formula. In addition, deformation strain ε [% / min] per unit time is calculated based on the draw ratio λ [%], the line conveyance speed V [m / min], and the drawing section path length F [m]. The line conveyance speed V refers to the conveyance speed of the synthetic resin film at the entrance of the drawing section. The stretching section path length F refers to the transport distance from the entrance to the exit of the stretching section.
Strain rate ε = λ × V / F

  In the stretching step, the surface temperature of the synthetic resin film is preferably (melting point of synthetic resin-100 ° C) to (melting point of synthetic resin-5 ° C), and (melting point of synthetic resin-30 ° C) to (melting point of synthetic resin- 10 ° C.) is more preferred. When the surface temperature is in the above range, cracks can be generated smoothly in the non-crystalline portion between the lamellas to generate micropores without breaking the synthetic resin film.

  In the stretching step, the stretch ratio of the synthetic resin film is preferably 1.5 to 3.0 times, more preferably 2.0 to 2.9 times, and particularly preferably 2.3 to 2.8 times. A minute pore can be uniformly formed in a synthetic resin film as the above-mentioned draw ratio is in the above-mentioned range.

  In addition, the draw ratio of a synthetic resin film means the value which remove | divided the length of the synthetic resin film after extending | stretching by the length of the synthetic resin film before extending | stretching.

(Annealing process)
Next, an annealing process is performed to anneal the synthetic resin film after the stretching process. The annealing step is performed to reduce the residual strain produced in the synthetic resin film by the stretching applied in the stretching step described above, and to suppress the occurrence of thermal contraction due to heating in the obtained separator for a storage battery.

  The surface temperature of the synthetic resin film in the annealing step is preferably (melting point of synthetic resin-40 ° C) to (melting point of synthetic resin-5 ° C). If the surface temperature is (the melting point of the synthetic resin-40 ° C) or more, the synthetic resin film leaves a residual stress which shrinks so as not to cause a short circuit between the positive and negative electrodes at an abnormally high temperature. It is possible to shrink and bend the micropores, to suppress the permeability of ions and the like, and to effectively suppress the abnormal high temperature. In addition, when the surface temperature is equal to or lower than (melting point of synthetic resin-5 ° C), clogging of the micropores formed in the stretching step can be prevented.

  The shrinkage rate of the synthetic resin film in the annealing step is preferably 30% or less. If the shrinkage ratio is 30% or less, the synthetic resin film leaves a residual stress that shrinks so as not to cause a short circuit between positive and negative electrodes at an abnormally high temperature, and shrinks slightly at an abnormally high temperature to It can be bent to suppress the permeability of ions etc. to effectively suppress abnormal high temperature, or the shape of the micropores can be maintained.

  The shrinkage rate of the synthetic resin film means the value obtained by dividing the shrinkage length of the synthetic resin film in the stretching direction during the annealing process by the length of the synthetic resin film in the stretching direction after the stretching process and multiplying by 100. Say.

  The separator for a storage battery device of the present invention is excellent in permeability to ions such as lithium ions, and can constitute a storage battery device such as a high performance lithium ion battery, a capacitor, a capacitor, etc. A short circuit between the positive electrode and the negative electrode due to dendrite and a rapid decrease in discharge capacity are unlikely to occur.

  Examples of the present invention will be described below, but the present invention is not limited by these examples.

[Examples 1 to 4, Comparative Examples 1 and 2]
(Extrusion process)
Homopolypropylene having a weight average molecular weight Mw, a number average molecular weight Mn, a molecular weight distribution (Mw / Mn) and a melting point shown in Table 1 is supplied to an extruder and melt-kneaded at a resin temperature shown in Table 1 The film was extruded from a T-die attached to the tip of the. Thereafter, the film was cooled to a surface temperature of 30 ° C. to obtain an elongated homopolypropylene film having a thickness of 18 μm and a width of 200 mm. The film forming speed, the extrusion amount and the draw ratio were as shown in Table 1.

(Care process)
Next, the homopolypropylene film was cured for the time shown in Table 1 (curing time) such that the surface temperature was the curing temperature shown in Table 1.

(Stretching process)
Next, the cured homopolypropylene film was uniaxially stretched only in the extrusion direction at the draw ratio shown in Table 1 at the strain rate shown in Table 1 so that the surface temperature became the temperature shown in Table 1. It uniaxially stretched using.

(Annealing process)
After that, the homopolypropylene film is supplied to a hot air furnace, and the homopolypropylene film is allowed to run for 1 minute so that the surface temperature becomes the temperature shown in Table 1 and without applying tension to the homopolypropylene film. Then, the homopolypropylene film was annealed to obtain a long storage device separator. The thickness of the storage device separator was 16 μm. The shrinkage rate of the homopolypropylene film in the annealing step was a value shown in Table 1.

[Evaluation]
The air resistance, the porosity, and the thickness of the obtained electric storage device separator were measured in the above manner, and the results are shown in Table 1.

  Small-angle X-ray scattering measurement (SAXS) was performed on the obtained separator for a storage device, and the value of the scattering vector q giving the first scattering peak is shown in Table 1.

  The direct current resistance, the dielectric breakdown voltage and the dendrite resistance of the obtained separator for a storage battery device were measured in the following manner, and the results are shown in Table 1.

(DC resistance)
The positive electrode and the negative electrode were produced in the following manner, and a small battery was produced. The direct current resistance of the obtained small battery was measured.
<Method of producing positive electrode>
Li ₂ CO ₃ and a coprecipitated hydroxide represented by Ni _0.5 Co _0.2 Mn _0.3 (OH) ₂ in an Ishikawa formula mortar such that the molar ratio of Li to the entire transition metal is 1.08: 1 after mixing Te, by grinding after heat treatment for 20 hours at 950 ° C. in air atmosphere, as a cathode active material, the average secondary particle diameter of _{Li 1.04 Ni 0.5 Co 0.2 Mn 0.3} O 2 of about 12μm Obtained.

The positive electrode active material obtained as described above, acetylene black (HS-100 manufactured by Denki Kagaku Kogyo Co., Ltd.) as a conductive support agent, polyvinylidene fluoride (trade name "# 7208" manufactured by Kureha Co., Ltd.) as a binder Were mixed in the ratio of 91: 4.5: 4.5 (mass%), and this mixture was added to and mixed with N-methyl-2-pyrrolidone to prepare a slurry-like solution. The slurry-like solution was applied to an aluminum foil (manufactured by Tokai Toyo Aluminum Sales Co., Ltd., thickness: 20 μm) by a doctor blade method and dried. The application amount of the slurry-like solution was 1.6 g / cm ³ . The aluminum foil was pressed and cut to prepare a positive electrode.

<Method of manufacturing negative electrode>
Lithium titanate (trade name “XA-105” manufactured by Ishihara Sangyo Co., Ltd., median diameter: 6.7 μm), acetylene black (trade name “HS-100” manufactured by Denki Kagaku Kogyo Co., Ltd.) as a conductive aid, and binder It mixed with the polyvinylidene fluoride (Kureha Co., Ltd. make, # 7208) by the ratio of 90: 2: 8 (mass%). This mixture was mixed with N-methyl-2-pyrrolidone to prepare a slurry solution. The slurry-like solution was applied to an aluminum foil (manufactured by Tokai Toyo Aluminum Sales Co., Ltd., thickness: 20 μm) by a doctor blade method and dried. The application amount of the slurry-like solution was 2.0 g / cm ³ . The aluminum foil was pressed and cut to prepare a negative electrode.

<Measurement of DC resistance>
The positive electrode was punched into a circular shape having a diameter of 14 mm, and the negative electrode was punched into a circular shape having a diameter of 15 mm. The small battery was configured by impregnating the storage battery separator with the electrolytic solution in a state in which the storage battery separator was interposed between the positive electrode and the negative electrode.

As an electrolytic solution, an electrolytic solution in which lithium hexafluorophosphate (LiPF ₆ ) was dissolved to 1 M in a mixed solvent of ethylene carbonate (EC) and diethyl carbonate (DEC) in a volume ratio of 3: 7 was used. .

The small battery was charged at a current density of 0.20 mA / cm ² to a preset upper limit voltage. The discharge was performed at a current density of 0.20 mA / cm ² up to a preset lower limit voltage. The upper limit voltage was 2.7 V and the lower limit voltage was 2.0 V. The discharge capacity obtained in the first cycle was taken as the initial capacity of the battery. Thereafter, measurement was charged up to 30% of the initial volume, 60 mA (I ₁₎ for 10 seconds discharged voltage when (E _1), 144mA voltage when discharged for 10 seconds at (I ₂₎ (E _2), respectively did.

The direct current resistance (Rx) at 30 ° C. was calculated by the following equation using the above measured values.
Rx = | (E ₁ −E ₂ ) / discharge current (I ₁ −I ₂ ) |

(Breakdown voltage)
The dielectric breakdown voltage in the separator for a power storage device was measured according to the following procedure using a dielectric breakdown tester (trade name "HAT-300-100 RHO" manufactured by Yamazaki Sangyo Co., Ltd.). Specifically, first, a flat square test piece with a side of 100 mm was cut out from the storage device separator. The test pieces were subjected to a discharge treatment. An upper electrode (made of SUS) was brought into contact with a mark having a diameter of about 25 mm formed at the center of the upper surface of the test piece, and a lower electrode (made of SUS) was brought into contact with the lower surface of the test piece to measure the breakdown voltage. As the measurement conditions, the atmosphere medium was air, the test temperature was 25 ° C., the relative humidity was 50%, and the temperature rising rate was 100 V / sec. Three test pieces were prepared, and the arithmetic mean value of the dielectric breakdown voltage of each test piece was made into the dielectric breakdown voltage of the separator for electrical storage devices.

(Dendrite resistance)
After producing the positive electrode and the negative electrode under the following conditions, a small battery was produced. Dendrite resistance of the obtained small battery was evaluated.
<Method of producing positive electrode>
Coprecipitated hydroxides represented by Li ₂ CO ₃ and Ni _0.33 Co _0.33 Mn _0.33 (OH) ₂ in an Ishikawa type mortar such that the molar ratio of Li to the entire transition metal is 1.08: 1 After heat treatment and heat treatment at 950 ° C. for 20 hours in an air atmosphere, the mixture was pulverized to obtain Li _1.04 Ni _0.33 Co _0.33 Mn _0.33 O ₂ having an average secondary particle diameter of about 12 μm.

The positive electrode active material obtained as described above, acetylene black (trade name "HS-100" manufactured by Denki Kagaku Kogyo Co., Ltd.) as a conductive support agent, polyvinylidene fluoride (trade name "# 7208" manufactured by Kureha) as a binder And 92: 4: 4 (mass%) to make a mixture. The mixture was poured into N-methyl-2-pyrrolidone and mixed to prepare a slurry-like solution. The slurry-like solution was applied to an aluminum foil (manufactured by Tokai Toyo Aluminum Sales Co., Ltd., thickness 15 μm) by a doctor blade method and dried. The application amount of the slurry-like solution was 2.9 g / cm ³ . The aluminum foil was pressed to produce a positive electrode.

<Method of manufacturing negative electrode>
Natural graphite (average particle diameter 10 μm) as a negative electrode active material, acetylene black (HS-100 manufactured by Denki Kagaku Kogyo Co., Ltd.) as a conductive aid, polyvinylidene fluoride (Kureha Co., Ltd. trade name "# 7208" as a binder ) Was mixed at a ratio of 95.7: 0.5: 3.8 (% by mass) to prepare a mixture. The mixture was added to and mixed with N-methyl-2-pyrrolidone to prepare a slurry solution. The slurry-like solution was applied to rolled copper foil (manufactured by Japan Foil Co., Ltd., thickness 10 μm) by a doctor blade method and dried. The application amount of the slurry-like solution was 1.5 g / cm ³ . The rolled copper foil was pressed to produce a negative electrode.

<Dendrite resistance measurement>
The positive electrode was punched into a circle with a diameter of 14 mm and the negative electrode with a diameter of 15 mm to prepare an electrode. The small battery was configured by arranging a storage device separator between the positive electrode and the negative electrode, and adding an electrolytic solution to the storage device separator. As the electrolyte, a volume ratio of ethylene carbonate (EC) and diethyl carbonate (DEC) 3: 7 in a mixed solvent, the electrolytic solution obtained by dissolving lithium hexafluorophosphate (LiPF ₆₎ so as to 1M used. The small battery was charged at a current density of 0.2 mA / cm ² to a preset upper limit voltage of 4.6 V. The small battery described above was placed in a 60 ° C. air-blowing oven and voltage changes were observed for 6 months. After 6 months, it was confirmed whether or not a short circuit occurred between the positive electrode and the negative electrode in the small battery.

The presence or absence of a short circuit between the positive electrode and the negative electrode was confirmed for three small batteries as described above, and evaluation was made based on the number of batteries in which the short circuit occurred.
A: It was 0.
B: It was one.
C: Two or three.

  The separator for a storage battery device of the present invention is excellent in permeability to ions such as lithium ion, sodium ion, calcium ion, and magnesium ion, and can substantially suppress the formation of dendrite. Therefore, the storage device separator is suitably used as a storage device separator.

Claims (5)

Containing synthetic resin and micropores, gas permeation resistance is 30sec / 100mL / 16μm or more and 100sec / 100mL / 16μm or less, and in small angle X-ray scattering measurement (SAXS), scattering vector q is 0.0030 nm ^-1 or more A separator for a storage battery having a first scattering peak in the stretching direction within a range of 0.0080 nm ^-1 or less.   The separator for a storage battery device according to claim 1, wherein the synthetic resin contains an olefin resin.   The separator for a storage battery device according to claim 2, wherein the olefin resin has a weight average molecular weight of 30,000 or more and 500,000 or less and a melting point of 130 ° C or more and 170 ° C or less.   The separator for a storage battery device according to any one of claims 1 to 3, which is uniaxially stretched.   A storage device comprising the storage device separator according to any one of claims 1 to 4.