JP5771045B2 - Propylene resin microporous film and method for producing the same, lithium ion battery separator and lithium ion battery - Google Patents

Description

  The present invention relates to a propylene-based resin microporous film used for a separator of a lithium ion battery and a method for producing the same. Furthermore, this invention relates to the separator for lithium ion batteries which consists of a propylene-type resin microporous film, and a lithium ion battery which uses this.

  Conventionally, lithium ion batteries have been used as batteries for portable electronic devices. This lithium ion battery has a positive electrode formed by applying lithium cobalt oxide or lithium manganate on the surface of an aluminum foil, a negative electrode formed by applying carbon on the surface of a copper foil, and a short circuit between the positive electrode and the negative electrode. The separator which partitions a positive electrode and a negative electrode is arrange | positioned in electrolyte solution.

  Lithium ion batteries are charged and discharged by discharging lithium ions from the positive electrode and entering the negative electrode during charging, and discharging lithium ions from the negative electrode and moving to the positive electrode during discharging. Therefore, the separator used for the lithium ion battery needs to be able to transmit lithium ions.

  Recently, when charging and discharging of a lithium ion battery is repeated, a lithium dendrite (dendritic crystal) is generated on the end face of the negative electrode. This dendrite breaks through the separator and causes a minute internal short circuit (dendritic short) between the positive electrode and the negative electrode. There is a problem that the battery capacity is remarkably deteriorated.

  As a separator used in a lithium ion battery, Patent Document 1 discloses that a composition composed of polypropylene and a polymer having a higher melt crystallization temperature than polypropylene and a β crystal nucleating agent is melt-extruded, and then at a temperature of 90 ° C to 120 ° C. A method for producing a polypropylene microporous film is disclosed, which is formed and held in a sheet shape and then stretched at least uniaxially so that the area magnification is 2.25 to 48 times.

  However, the polypropylene microporous film obtained by the above production method has insufficient lithium ion permeability and cannot sufficiently prevent a short circuit between the positive electrode and the negative electrode due to dendrites. Furthermore, the polypropylene microporous film obtained by the above production method has a low mechanical strength and cannot sufficiently prevent damage when an external force such as impact force is applied.

JP-A 63-199742

  The present invention is excellent in lithium ion permeability, can constitute a high-performance lithium ion battery, has high mechanical strength, and is not easily damaged by external force such as dendrite or impact force. Provided are a propylene-based resin microporous film capable of preventing a short circuit between the anode and the negative electrode and a method for producing the same.

  The propylene-based resin microporous film of the present invention is a propylene-based resin microporous film in which micropores are formed by biaxially stretching a propylene-based resin film, and the propylene-based resin has a molecular weight of 50,000. The following component amounts are 25 to 60% by weight and the molecular weight is 700,000 or more, the component amount is 19 to 30% by weight, the weight average molecular weight is 350,000 to 500,000 and the angular frequency obtained from melt viscoelasticity measurement When ω is 1 rad / s, the relaxation time τ is 0.6 to 0.8 s, the air permeability of the propylene resin microporous film is 40 to 400 s / 100 mL, and the porosity is 40 to 70%. The maximum major axis of the open end of the micropore is 500 nm or less.

  The propylene resin used for the propylene resin microporous film is not particularly limited, and examples thereof include a propylene homopolymer, a copolymer of propylene and another olefin, and the like, and a propylene homopolymer (homopolypropylene). Is preferred. Propylene-type resin may be used independently, or 2 or more types may be used together. The copolymer of propylene and another olefin may be a block copolymer or a random copolymer.

  Examples of the olefin copolymerized with propylene include α such as ethylene, 1-butene, 1-pentene, 4-methyl-1-pentene, 1-hexene, 1-octene, 1-nonene and 1-decene. -Olefin and the like.

  When the weight average molecular weight of the propylene resin is small, it is difficult to improve the air permeability of the propylene resin microporous film. When the weight average molecular weight is large, the film formation becomes unstable, and the thickness accuracy of the propylene resin microporous film decreases. Therefore, it is limited to 350,000 to 500,000, preferably 370,000 to 480,000.

  If the content of the component having a molecular weight of 50,000 or less in the propylene-based resin is small, the air permeability of the propylene-based resin microporous film is difficult to improve, and if it is large, the tensile yield strength of the propylene-based resin microporous film is low. Therefore, it is limited to 25 to 60% by weight, and preferably 30 to 58% by weight.

  If the content of the component having a molecular weight of 700,000 or more in the propylene resin is small, the maximum major axis of the opening end of the propylene resin microporous film becomes too large, and if it is large, the air permeability of the propylene resin microporous film is improved. Therefore, it is limited to 19 to 30% by weight, and preferably 20 to 29% by weight.

  The weight average molecular weight of propylene resin, the content of components having a molecular weight of 50,000 or less and the content of components having a molecular weight of 700,000 or more are, for example, a mixture of a resin having a low weight average molecular weight and a resin having a high weight average molecular weight. And it can control by adjusting the mixing ratio of both.

  Here, the weight average molecular weight of the propylene-based resin is a polystyrene-converted value measured by a GPC (gel permeation chromatography) method. Specifically, 6-7 mg of propylene-based resin was sampled, and the collected propylene-based resin was supplied to a test tube, and then 0.05 wt% BHT (dibutylhydroxytoluene) o-DCB (ortho) was added to the test tube. Dichlorobenzene) solution is added to dilute the propylene resin concentration to 1 mg / mL to prepare a diluted solution.

  The dilution liquid is shaken for 1 hour at a rotation speed of 25 rpm at 145 ° C. using a dissolution filter, and the propylene resin is dissolved in the BHT o-DCB solution to obtain a measurement sample. Using this measurement sample, the weight average molecular weight of the propylene-based resin can be measured by the GPC method.

  The amount of the component having a molecular weight of 50,000 or less in the propylene resin is calculated by integrating the content ratio every elution time of 500 ms using the GPC method in the same manner as described above, and the component having a molecular weight of 50,000 or less in terms of polystyrene. Sum the weight. Based on this total amount, the content (% by weight) of a component having a molecular weight of 50,000 or less in the propylene-based resin is calculated.

  The amount of the component having a molecular weight of 700,000 or more in the propylene resin can be measured in the same manner as in the case of measuring the amount of a component having a molecular weight of 50,000 or less.

  The weight average molecular weight, the component weight having a molecular weight of 50,000 or less, and the component weight having a molecular weight of 700,000 or more in the propylene resin can be measured, for example, with the following measuring apparatus and measurement conditions.

Product name “HLC-8121GPC / HT” manufactured by TOSHO
Measurement conditions Column: TSKgelGMHHR-H (20) HT x 3
TSK guard column-HHR (30) HT x 1
Mobile phase: o-DCB 1.0 mL / min
Sample concentration: 1 mg / mL
Detector: Bryce refractometer
Standard material: polystyrene (Molecular weight: 500-8420000, manufactured by TOSHO)
Elution conditions: 145 ° C
SEC temperature: 145 ° C

  In the propylene-based resin, when the angular frequency ω obtained from the melt viscoelasticity measurement is 1 rad / s, the relaxation time τ is short, the lamella may be insufficiently formed. Since the film becomes unstable and the thickness accuracy of the propylene-based resin microporous film may be lowered, the thickness is limited to 0.6 to 0.8 s, and preferably 0.61 to 0.78 s.

  In the propylene-based resin, the relaxation time τ when the angular frequency ω obtained from melt viscoelasticity measurement is 1 rad / sec is greatly affected by the balance between the amount of high molecular weight components and the amount of low molecular weight components in the propylene resin. It can be controlled by adjusting the molecular weight and molecular weight distribution of the resin. Specifically, the relaxation time τ when the angular frequency ω obtained from the melt viscoelasticity measurement is 1 rad / sec can be adjusted by mixing two or more propylene resins having different weight average molecular weights.

Here, in the propylene-based resin, the relaxation time τ when the angular frequency ω obtained from melt viscoelasticity measurement is 1 rad / s is measured as follows. First, the storage elastic modulus G ′ and the loss elastic modulus G ″ of the propylene-based resin when the angular frequency ω is 1 rad / s are measured at 175 ° C. using a viscoelasticity measuring device. The time τ can be calculated.
Relaxation time τ (s) = G ′ / ω · G ″

Note that the storage elastic modulus G ′ and loss elastic modulus G ″ of the propylene-based resin when the angular frequency ω is 1 rad / s can be measured, for example, with the following measuring apparatus and measurement conditions.
Measuring device: Rotational rheometer, manufactured by Rheometrics, trade name “RMS-800”
Measurement conditions: Temperature 175 ° C
Cone plate φ25mm

  Propylene having a relaxation time τ with a weight average molecular weight, a content of a component having a molecular weight of 50,000 or less, a content of a component having a molecular weight of 700,000 or more, and an angular frequency ω obtained from melt viscoelasticity measurement of 1 rad / s As the resin, for example, it is commercially available from Prime Polymer under the trade name “Prime Polypro”.

  When the melt tension of the propylene-based resin is small, the orientation of the propylene-based resin is reduced when the propylene-based resin film is formed, and when the melt tension is large, the stability when the propylene-based resin film is formed is decreased. 1-32g is preferable and 1.3-3.0g is more preferable.

  Since the melt tension of the propylene-based resin is greatly influenced by the intermolecular interaction (molecular chain entanglement) of the polymer chain, it can be controlled by adjusting the molecular weight of the propylene-based resin or the amount of ethylene component.

  For example, by increasing the amount of the high molecular weight component in the propylene resin, the intermolecular interaction becomes stronger and the melt tension of the propylene resin can be increased, while by increasing the amount of the low molecular weight component in the propylene resin. The intermolecular interaction becomes weak, and the melt tension of the propylene-based resin can be reduced. Specifically, the melt tension of the propylene resin can be adjusted by mixing two or more propylene resins having different weight average molecular weights, and can be designed by appropriately selecting from general-purpose resins. .

  In addition, the melt tension of a propylene-type resin says the value measured based on JISK7199. Specifically, a sample can be prepared according to JIS K7199, and the melt tension of this sample can be measured according to JIS K7199, for example, with the following measuring apparatus and measurement conditions. it can.

Measuring device Capillograph (1B) manufactured by Toyo Seiki Co., Ltd. Measurement conditions with a melt tension tester Temperature conditions 230 ° C, using a heat retaining chamber Extrusion speed 10 mm / min Capillary φ8 mm, L2.095 mm
Take-off speed 3.141m / min

  When the air permeability of the propylene-based resin microporous film is small, the film strength of the propylene-based resin microporous film is reduced. When the air permeability is large, the lithium ion permeability of the propylene-based resin microporous film is decreased. Since the battery performance of the lithium ion battery using a resin microporous film may deteriorate, it is limited to 40 to 400 s / 100 mL, and preferably 50 to 320 s / 100 mL.

  The air permeability of the propylene-based resin microporous film refers to a value measured at 23 ° C. and a relative humidity of 65% in accordance with JIS P8117.

When the value obtained by dividing the tensile yield strength (MPa) in the width direction at 23 ° C. in the propylene-based resin microporous film by the apparent density (g / cm ³ ) of the propylene-based resin microporous film is small, the propylene-based resin micropore The mechanical strength in the extrusion direction of the film is lowered, and when used as a separator of a lithium ion battery, there is a possibility of causing damage and causing a short circuit of the electrode. Therefore, 40 (MPa / (g / cm ³ )) or more is preferable. 45 (MPa / (g / cm ³ )) or more is more preferable.

  In addition, the tensile yield strength of the width direction in 23 degreeC in a propylene-type resin microporous film can be measured in the following way. A strip-shaped test piece having a size of 10 mm in the extrusion direction and 100 mm in the direction orthogonal to the extrusion direction (width direction) is cut out from the propylene-based resin microporous film.

  Next, both ends in the length direction of the above test piece are held by a tensile test apparatus so that the distance between chucks is 50 mm, and then at 23 ° C. according to JIS K 7127 at a tensile speed of 300 mm / min. The tensile strength can be measured, and the tensile yield strength of the propylene-based resin microporous film can be calculated based on the SS curve.

The apparent density of the propylene-based resin microporous film is measured as follows. First, a flat rectangular test piece having a size of 50 cm in the extrusion direction and 14 cm in the direction orthogonal to the extrusion direction (width direction) is cut out from the propylene-based resin microporous film. Measure the thickness at any 15 points on the test piece, and set the arithmetic average value of the thicknesses at the 15 points as the thickness t (cm) of the test piece. Next, the weight W (g) of the test piece is measured, and the apparent density ρ is calculated based on the following formula.
Apparent density ρ (g / cm ³ ) = W / (50 × 14 × t)

  If the porosity of the propylene-based resin microporous film is small, the lithium ion permeability decreases, and the battery performance of the lithium-ion battery using the propylene-based resin microporous film decreases. If the porosity is large, a dendrite short occurs. Since fear becomes high, it is limited to 40 to 70%, and 50 to 65% is preferable.

The porosity of the propylene-based resin microporous film is measured as follows. First, the apparent density ρ (g / cm ³ ) of the propylene-based resin microporous film is measured as described above. And the porosity P of a propylene-type resin microporous film is computable based on a following formula using this apparent density (rho).
Porosity P (%) = 100 × (1−ρ / 0.9)

  If the maximum long diameter of the opening end of the microporous portion in the propylene-based resin microporous film is large, there is a high possibility that a dendrite short will occur, so it is limited to 500 nm or less, and preferably 450 nm or less.

  In addition, the maximum long diameter of the opening end of the micropore part in a propylene-type resin microporous film is measured as follows. First, the surface of the propylene-based resin microporous film is coated with carbon. Next, 10 arbitrary positions on the surface of the propylene-based resin microporous film are photographed at a magnification of 10,000 using a scanning electron microscope. The photographing range is a plane rectangular range of 9.3 μm long × 12.5 μm wide on the surface of the propylene-based resin microporous film.

  The major axis of the opening end of each micropore appearing in the photograph obtained is measured, and the largest major axis is taken as the maximum major axis of the opening end of the micropore. The major axis of the open end of the microhole is defined as the diameter of a perfect circle having the smallest diameter that can surround the open end of the microhole.

  Next, the manufacturing method of a propylene-type resin microporous film is demonstrated. First, a propylene-based resin is supplied to an extruder and melt-kneaded, and then a propylene-based resin film is extruded from a T die attached to the tip of the extruder.

  When the temperature of the propylene resin when melt-kneading the propylene resin with an extruder is low, the thickness of the resulting propylene resin microporous film becomes uneven or the surface smoothness of the propylene resin microporous film decreases. On the other hand, if it is high, the orientation of the propylene resin may be lowered and the propylene resin may not sufficiently form a lamellar structure. Therefore, the temperature of the propylene resin is 20 ° C. or higher than the melting point of the propylene resin. The temperature is limited to 50 ° C. or higher than the melting point, preferably 25 ° C. higher than the melting point of the propylene-based resin, and 40 ° C. higher than the melting point of the propylene-based resin.

  If the draw ratio when extruding a propylene resin into a film from an extruder is small, the tension applied to the propylene resin is reduced, resulting in insufficient molecular orientation of the propylene resin, and the propylene resin has a lamellar structure. If it is large, the molecular orientation of the propylene-based resin is high, but the film-forming stability of the propylene-based resin film decreases, and the thickness accuracy and width accuracy of the resulting propylene-based resin film Is preferably 50 to 300, more preferably 70 to 250. The draw ratio means a value obtained by dividing the clearance of the lip of the T die by the thickness of the propylene-based resin film extruded from the T die.

  If the film formation speed of the propylene resin film is small, the tension applied to the propylene resin is lowered, the molecular orientation of the propylene resin is insufficient, and the propylene resin may not form a sufficient lamellar structure. If it is large, the molecular orientation of the propylene-based resin is high, but the film-forming stability of the propylene-based resin film is lowered, and the thickness accuracy and width accuracy of the resulting propylene-based resin film are lowered. / Min is preferable, and 15 to 250 m / min is more preferable.

  If the birefringence of the extruded propylene-based resin film is small, air permeability may be difficult to improve, so 0.017 or more is preferable.

  In addition, the birefringence of a propylene-type resin film is measured as follows. That is, first, the thickness D of the propylene-based resin film is measured using a micro gauge.

  Next, paraffin wax is entirely applied to the front and back surfaces of the propylene-based resin film to remove the influence of the light transmission amount due to the irregular reflection of light. Two glass plates having a thickness of 1 mm are stacked in the thickness direction, and the propylene-based resin film is placed on the glass plate.

Thereafter, the light transmittance T (%) of the propylene-based resin film was measured using a birefringence measuring apparatus under conditions of an analyzer of 135 ° and a polarizer of 45 °, and the wavelength λ was 550 nm based on the following formula. And the birefringence index Δn is calculated based on the phase difference Re.
Phase difference Re = 550 × arcsin (T ^1/2 ) / π
Birefringence Δn = Re / D

  Next, the obtained propylene-based resin film is cured. This propylene-based resin curing step is performed to promote lamella crystallization of the propylene-based resin film. Accordingly, in the first stretching step of the propylene-based resin film described later, cracks are generated not between the lamellas but between the lamellas, and minute through holes (micropore portions) can be formed starting from the cracks. .

  When the curing temperature of the propylene-based resin film is low, crystallization of the lamella of the propylene-based resin film is not promoted, and in the first stretching process of the propylene-based resin film, minute through-holes are not formed between the lamellae and are high. And the orientation of the propylene-based resin molecules of the propylene-based resin film may be relaxed and the lamellar structure may be destroyed. Therefore, the temperature is 60 ° C. lower than the melting point of the propylene-based resin and higher than the melting point of the propylene-based resin. The temperature is limited to not more than 10 ° C., preferably not less than 50 ° C. lower than the melting point of the propylene resin and not more than 15 ° C. lower than the melting point of the propylene resin.

  If the curing time of the propylene-based resin film is short, crystallization of the lamella of the propylene-based resin film is not promoted, and in the first stretching process of the propylene-based resin film, it is difficult to form minute through holes between the lamellae. It is preferable to secure a sufficient time.

  Next, the propylene-based resin film is stretched in the extrusion direction (first stretching process). The propylene-based resin film is stretched in the extrusion direction by a cold stretching process and a first following the cold stretching process. It consists of a hot stretching process. In the cold stretching step, the propylene-based resin film is uniaxially stretched in the extrusion direction.

  At the time of cold stretching of the propylene-based resin film, the lamella is hardly melted, and by separating the lamellae by stretching, a fine crack is efficiently generated independently in the amorphous part between the lamellae. A large number of micropores are reliably formed starting from this crack.

  If the surface temperature at the time of cold stretching of the propylene-based resin film is low, the propylene-based resin film may be broken at the time of stretching, and if it is high, cracks are less likely to occur in the amorphous part between the lamellae. It is limited to 20 to 40 ° C, and preferably 0 to 30 ° C.

  When the draw ratio of cold stretching of the propylene-based resin film is small, it becomes difficult to form micropores uniformly in the amorphous portion between the lamellae, and when large, the first hot-stretching of the propylene-based resin film described later is Since the draw ratio in is lowered and the air permeability of the propylene-based resin microporous film may be lowered, it is limited to 1.1 to 1.6 times, and preferably 1.2 to 1.5 times.

  In addition, in this invention, the draw ratio of a propylene-type resin film means the value which remove | divided the length of the propylene-type resin film after extending | stretching by the length of the propylene-type resin film before extending | stretching.

  If the stretching speed at the time of cold stretching of the propylene-based resin film is small, it becomes difficult to form micropores uniformly in the amorphous part between the lamellas, so it is 20% / min or more, and if it is too large, the propylene-based resin film Since there exists a possibility that a resin film may fracture | rupture, 20-3000% / min is preferable.

  In addition, in this invention, the extending | stretching speed of a propylene-type resin film means the deformation ratio of the dimension in the extending | stretching direction of the propylene-type resin film per unit time.

  The stretching method in the extrusion direction of the propylene-based resin film in the cold stretching step is not particularly limited as long as the propylene-based resin film can be uniaxially stretched only in the extrusion direction. For example, the propylene-based resin film is uniaxially stretched. Examples thereof include a method of uniaxially stretching at a predetermined temperature using a stretching apparatus.

  Further, the propylene-based resin film after cold stretching is subjected to stretching treatment in the extrusion direction at a surface temperature higher than the surface temperature at the time of cold stretching (first hot stretching step). In this way, a number of micropores formed by cold stretching are obtained by subjecting the propylene-based resin film to a stretching process in the same direction as during cold stretching at a surface temperature higher than the surface temperature during cold stretching. Can grow.

  When the surface temperature during the first hot stretching of the propylene-based resin film is low, the micropores formed during the cold stretching are difficult to grow, and the air permeability of the propylene-based resin microporous film may not be improved. If it is high, the micropores formed at the time of cold drawing are blocked, and the air permeability of the propylene-based resin microporous film may be lowered. Therefore, the temperature is 60 ° C. lower than the melting point of the propylene-based resin and It is limited to a temperature that is 10 ° C. lower than the melting point of the propylene-based resin, preferably a temperature that is 50 ° C. lower than the melting point of the propylene-based resin and 20 ° C. lower than the melting point of the propylene-based resin.

  If the draw ratio during the first hot stretching of the propylene-based resin film is small, the micropores formed during the cold stretching are difficult to grow, and the air permeability of the propylene-based resin microporous film may decrease, If it is large, the micropores formed at the time of cold drawing are blocked, and instead the air permeability of the propylene-based resin microporous film may be lowered, so it is limited to 1.6 to 3 times, 1.8 -2.5 times are preferable.

  If the stretching speed during the first hot stretching of the propylene-based resin film is large, the micropores formed during the cold stretching are difficult to grow, and the air permeability of the propylene-based resin film may decrease. 500% / min or less is preferable, and 400% / min or less is more preferable.

  The method for stretching the propylene-based resin film in the first hot stretching step is not particularly limited as long as the propylene-based resin film can be uniaxially stretched only in the extrusion direction. For example, the propylene-based resin film is uniaxially stretched. A method of uniaxial stretching at a predetermined temperature using

  Next, the propylene-based resin film that has been subjected to the first hot stretching is subjected to an annealing treatment (first annealing step). In this first annealing step, residual strain generated in the propylene-based resin film due to stretching applied in the above-described stretching process in the extrusion direction is alleviated, and heat shrinkage due to heating occurs in the resulting propylene-based resin microporous film. It is done to suppress

  If the surface temperature of the propylene-based resin film in the first annealing step is low, the strain remaining in the propylene-based resin film is insufficiently relaxed, and the dimensional stability during heating of the resulting propylene-based resin microporous film is insufficient. If it is high, there is a possibility that the micropores formed in the first stretching step may be clogged. Therefore, the temperature is higher than the surface temperature of the propylene-based resin film during the first hot stretching and propylene. The temperature is limited to 10 ° C. or lower than the melting point of the resin.

  If the shrinkage ratio of the propylene-based resin film in the first annealing step is large, sagging may occur in the propylene-based resin film, and uniform annealing may not be possible, or the shape of the micropores may not be retained. % Or less is preferable. The shrinkage rate of the propylene-based resin film is the length of the propylene-based resin film in the stretching direction after the first hot stretching step, which is the contraction length of the propylene-based resin film in the stretching direction during the first annealing step. The value obtained by dividing by 100 and dividing.

  Following the first annealing step, the propylene-based resin film is stretched in the width direction (direction perpendicular to the extrusion direction) (second stretching step). It consists of a stretch process.

  As will be described later, the propylene-based resin film formed in the first stretching step (cold stretching step and first hot stretching step) by stretching the propylene-based resin film in the width direction under a predetermined condition. An excellent mechanical strength can be imparted to the propylene-based resin microporous film while maintaining the excellent air permeability of the propylene-based resin microporous film by maintaining the open state of the pores.

  When the surface temperature during the second hot stretching of the propylene-based resin film is low, the micropores are difficult to grow uniformly in the width direction, and the strength of the propylene-based resin microporous film may be reduced. Since the formed micropores are blocked, and the air permeability of the propylene-based resin microporous film may be lowered, the propylene at the temperature of 60 ° C. lower than the melting point of the propylene-based resin and at the time of the first annealing step The surface temperature of the propylene resin film is preferably not higher than the surface temperature of the propylene resin film, not lower than the temperature lower by 50 ° C. than the melting point of the propylene resin and not higher than the surface temperature of the propylene resin film in the first annealing step.

  If the draw ratio during the second hot drawing of the propylene-based resin film is small, the mechanical strength of the propylene-based resin microporous film may be insufficient. Since the pores are blocked and the air permeability of the propylene-based resin microporous film may be lowered, it is limited to 1.05 to 3 times, preferably 1.1 to 2.5 times.

  If the stretching speed during the second hot stretching of the propylene-based resin film is large, the micropores are difficult to grow in the width direction, and therefore, it is preferably 500% / min or less, and more preferably 400% / min or less.

  The stretching method of the propylene-based resin film in the second hot stretching step is not particularly limited as long as the propylene-based resin film can be stretched only in the width direction. For example, a uniaxial stretching device is used for the propylene-based resin film. And a method of stretching at a predetermined temperature.

  Next, the propylene-based resin film that has been subjected to the second hot stretching is subjected to an annealing treatment (second annealing step). In the second annealing step, the residual strain generated in the propylene-based resin film due to the stretching applied in the above-described stretching step in the width direction is alleviated, and heat shrinkage due to heating occurs in the resulting propylene-based resin microporous film. It is done to suppress

  If the surface temperature of the propylene-based resin film in the second annealing step is low, the strain remaining in the propylene-based resin film is insufficiently relaxed, and the dimensional stability during heating of the resulting propylene-based resin microporous film is insufficient. If it is high, the micropores formed in the stretching process may be clogged. Therefore, the surface temperature of the propylene-based resin film during the second hot stretching is higher than the propylene-based resin. The temperature is limited to 10 ° C. or lower than the melting point.

  If the shrinkage ratio of the propylene-based resin film in the second annealing step is large, sagging may occur in the propylene-based resin film, and uniform annealing may not be possible, or the shape of the micropores may not be retained. % Or less is preferable. The shrinkage ratio of the propylene-based resin film refers to the shrinkage length of the propylene-based resin film in the stretching direction in the second hot stretching step during the second annealing step, and the second heat after the second hot stretching step. A value obtained by dividing by the length of the propylene-based resin film in the stretching direction in the intermediate stretching step and multiplying by 100.

  The propylene-based resin microporous film thus obtained has a large number of micropores formed through the film front and back surfaces and has excellent air permeability. Therefore, when a propylene-based resin microporous film is used as a separator for a lithium ion battery, lithium ions can pass through the propylene-based resin microporous film smoothly and uniformly, so that the obtained lithium ion battery is an excellent battery. Demonstrate performance.

  Propylene-based resin microporous film has many micropores formed independently, so it maintains the above-mentioned excellent air permeability, facilitates smooth and uniform permeation of lithium ions, and produces dendrite. In addition, it has excellent mechanical strength by being biaxially stretched in the extrusion direction and the width direction. Accordingly, it is possible to reliably prevent dendrite shorts and prevent problems such as battery capacity deterioration, and even when an impact force is applied to the lithium ion battery, a propylene-based resin microporous film Can maintain the battery performance of the lithium-ion battery without failing to maintain the state in which the positive electrode and the negative electrode are partitioned through the propylene-based resin microporous film in spite of external force. it can.

  As described above, the propylene-based resin microporous film according to the present invention has excellent mechanical strength even though it has excellent air permeability due to the formation of a large number of microporous portions. . Therefore, according to such a propylene-based resin microporous film, it is possible to provide a lithium ion battery that can achieve high output and can maintain high output even when repeated charge and discharge at high speed. Can do.

  Since the propylene-based resin microporous film of the present invention has the above-described configuration, it has excellent air permeability, and when used in a lithium ion battery, the passage of lithium ions is smooth and uniform. The lithium ion battery has excellent battery performance, can substantially prevent the occurrence of dendrites, and the propylene-based resin microporous film also has excellent mechanical strength. Therefore, even when an external force such as an impact force is applied to the lithium ion battery, it is not easily damaged, and the positive electrode and the negative electrode can be reliably partitioned. In particular, according to the propylene-based resin microporous film of the present invention, stable battery performance of a lithium ion battery can be maintained even if charging and discharging at high speed are repeated.

  According to the method for producing a propylene-based resin microporous film of the present invention, the propylene-based resin microporous film as described above can be easily produced.

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

(Examples 1 and 2)
Relaxation time when the molecular weight shown in Table 1 is 50,000 or less, the molecular weight is 700,000 or more, the weight average molecular weight, the melt tension, the melting point, and the angular frequency ω obtained from melt viscoelasticity measurement is 1 rad / s. Homopolypropylene having τ is supplied to an extruder and melt-kneaded at a resin temperature of 200 ° C., extruded from a T-die attached to the tip of the extruder into a film shape, cooled at 30 ° C., and a thickness of 30 μm. A homopolypropylene film having a width of 200 mm was obtained. The extrusion rate was 10 kg / hour, the film forming speed was 22 m / min, and the draw ratio was 83. Further, the birefringence Δn of the obtained homopolypropylene film was as shown in Table 1.

  The obtained homopolypropylene film was supplied into a hot air oven and cured for 24 hours so that the surface temperature became 120 ° C. (curing process).

  Next, the homopolypropylene film was cut into strips of 300 mm in the extrusion direction and 160 mm in the width direction. The homopolypropylene film was stretched 1.2 times at a stretching rate of 50% / min using a uniaxial stretching apparatus (trade name “IMC-18C6” manufactured by Imoto Seisakusho Co., Ltd.) so that the surface temperature was 23 ° C. Cold drawing in the extrusion direction (cold drawing step).

  Subsequently, using a uniaxial stretching device (trade name “IMC-18C6” manufactured by Imoto Seisakusho Co., Ltd.), the homopolypropylene film was doubled at a stretching rate of 42% / min with a surface temperature of 120 ° C. Hot stretching was performed in the extrusion direction (first hot stretching step).

  Thereafter, the homopolypropylene film was allowed to stand for 10 minutes so that its surface temperature was 130 ° C. and no tension was applied to the homopolypropylene film, and the homopolypropylene film was annealed (first annealing). Process). The shrinkage ratio of the homopolypropylene film in the first annealing step was 20%.

  Next, using a uniaxial stretching apparatus (trade name “IMC-18C6” manufactured by Imoto Seisakusho Co., Ltd.), the homopolypropylene film was stretched at a stretching ratio of 1.2% at a stretching rate of 42% / min so that the surface temperature was 120 ° C. The film was hot-drawn twice in the direction orthogonal to the extrusion direction (second hot drawing step).

  Thereafter, the homopolypropylene film is left to stand for 10 minutes so that its surface temperature is 130 ° C. and no tension is applied to the homopolypropylene film, and the homopolypropylene film is annealed to have a thickness of 23 μm. A propylene-based resin microporous film was obtained (second annealing step). The shrinkage ratio of the homopolypropylene film in the second annealing step was 20%.

(Examples 3 and 4)
Relaxation time when the molecular weight shown in Table 1 is 50,000 or less, the molecular weight is 700,000 or more, the weight average molecular weight, the melt tension, the melting point, and the angular frequency ω obtained from melt viscoelasticity measurement is 1 rad / s. Homopolypropylene having τ is supplied to an extruder and melt-kneaded at a resin temperature of 210 ° C., extruded from a T die attached to the tip of the extruder into a film shape, cooled at 30 ° C., and a thickness of 30 μm. A homopolypropylene film having a width of 200 mm was obtained. The extrusion rate was 10 kg / hour, the film forming speed was 22 m / min, and the draw ratio was 83. Further, the birefringence Δn of the obtained homopolypropylene film was as shown in Table 1.

  The obtained homopolypropylene film was supplied into a heated hot air oven and cured for 24 hours so that the surface temperature became 120 ° C. (curing process).

  Next, the homopolypropylene film was cut into strips of 300 mm in the extrusion direction and 160 mm in the width direction. The homopolypropylene film was stretched 1.2 times at a stretching rate of 50% / min using a uniaxial stretching apparatus (trade name “IMC-18C6” manufactured by Imoto Seisakusho Co., Ltd.) so that the surface temperature was 23 ° C. Cold drawing in the extrusion direction (cold drawing step).

  Subsequently, using a uniaxial stretching apparatus (trade name “IMC-18C6” manufactured by Imoto Seisakusho Co., Ltd.), the homopolypropylene film was doubled at a stretching rate of 42% / min so that the surface temperature was 110 ° C. Hot stretching was performed in the extrusion direction (first hot stretching step).

  Thereafter, the homopolypropylene film was allowed to stand for 10 minutes so that its surface temperature was 130 ° C. and no tension was applied to the homopolypropylene film, and the homopolypropylene film was annealed (first annealing). Process). The shrinkage ratio of the homopolypropylene film in the first annealing step was 20%.

  Next, using a uniaxial stretching apparatus (trade name “IMC-18C6” manufactured by Imoto Seisakusho Co., Ltd.), the homopolypropylene film was stretched at a stretching ratio of 1.2% at a stretching rate of 42% / min so that the surface temperature was 110 ° C. The film was hot-drawn twice in the direction orthogonal to the extrusion direction (second hot drawing step).

  Thereafter, the homopolypropylene film is left to stand for 10 minutes so that its surface temperature is 130 ° C. and no tension is applied to the homopolypropylene film, and the homopolypropylene film is annealed to have a thickness of 23 μm. A propylene-based resin microporous film was obtained (second annealing step). The shrinkage ratio of the homopolypropylene film in the second annealing step was 20%.

(Comparative Examples 1-5)
Relaxation time when the molecular weight shown in Table 1 is 50,000 or less, the molecular weight is 700,000 or more, the weight average molecular weight, the melt tension, the melting point, and the angular frequency ω obtained from melt viscoelasticity measurement is 1 rad / s. Homopolypropylene having τ is supplied to an extruder and melt-kneaded at a resin temperature of 200 ° C., extruded from a T-die attached to the tip of the extruder into a film shape, cooled at 30 ° C., and a thickness of 30 μm. A homopolypropylene film having a width of 200 mm was obtained. The extrusion rate was 10 kg / hour, the film forming speed was 22 m / min, and the draw ratio was 83. Further, the birefringence Δn of the obtained homopolypropylene film was as shown in Table 1.

  The obtained homopolypropylene film was supplied into a hot air oven and cured for 24 hours so that the surface temperature became 120 ° C. (curing process).

  Next, the homopolypropylene film was cut into strips of 300 mm in the extrusion direction and 160 mm in the width direction. The homopolypropylene film was stretched 1.2 times at a stretching rate of 50% / min using a uniaxial stretching apparatus (trade name “IMC-18C6” manufactured by Imoto Seisakusho Co., Ltd.) so that the surface temperature was 23 ° C. Cold drawing in the extrusion direction (cold drawing step).

  Subsequently, using a uniaxial stretching device (trade name “IMC-18C6” manufactured by Imoto Seisakusho Co., Ltd.), the homopolypropylene film was doubled at a stretching rate of 42% / min with a surface temperature of 120 ° C. Hot stretching was performed in the extrusion direction (first hot stretching step).

  Thereafter, the homopolypropylene film is allowed to stand for 10 minutes so that its surface temperature is 130 ° C. and no tension is applied to the homopolypropylene film, and the homopolypropylene film is annealed to have a thickness of 25 μm. A propylene-based resin microporous film was obtained (first annealing step). The shrinkage ratio of the homopolypropylene film in the first annealing step was 20%.

  The air permeability, porosity, maximum long diameter of the open end of the microporous part, tensile yield strength in the width direction and apparent density of the obtained propylene-based resin microporous film were measured as described above, and the results are shown in Table 1. Indicated.

  Furthermore, according to the following procedures, lithium ion batteries were prepared using the propylene-based resin microporous films of Examples 1-2 and Comparative Examples 1-4, and the discharge capacity of the lithium ion batteries was measured. The results are shown in Table 1.

(Production of lithium ion battery)
For positive electrode formation by mixing and stirring 92% by weight of LiMn ₂ O ₄ (average particle size: 26 μm) as a positive electrode active material, 4% by weight of carbon black as a conductive additive, and 4% by weight of polyvinylidene fluoride as a binder resin A composition was prepared, and this positive electrode forming composition was applied to one surface of an aluminum foil as a positive electrode current collector using a comma coater and dried to prepare a positive electrode active material layer. Thereafter, a positive electrode current collector having a positive electrode active material layer formed on one surface was punched into a plane rectangle of 30 mm length × 60 mm width to obtain a positive electrode.

  Next, a composition for forming a negative electrode was prepared by mixing and stirring 91% by weight of graphite particles as a negative electrode active material, 5% by weight of carbon black as a conductive additive, and 4% by weight of polyvinylidene fluoride as a binder resin. Prepare an electrolytic copper foil with one surface roughened by an electrolysis method as a negative electrode current collector, apply the composition for forming a negative electrode on the roughened surface of this electrolytic copper foil using a comma coater, and dry it. Thus, a negative electrode active material layer was produced. Thereafter, a negative electrode current collector having a negative electrode active material layer formed on one surface was punched into a plane rectangle of 30 mm length × 60 mm width to obtain a negative electrode.

Next, the positive electrode, the propylene-based resin microporous film, and the negative electrode are stacked so that the positive electrode active material layer and the negative electrode active material layer face each other with the propylene-based resin microporous film interposed therebetween, thereby forming a laminate. After arranging a tab on each electrode, the laminate was dried under reduced pressure at 80 ° C. for 12 hours. After drying the laminated body under reduced pressure, the laminated body was housed in an exterior material, and an electrolyte solution was injected in an argon gas atmosphere, and then the exterior material was sealed under reduced pressure to produce a lithium ion battery. Incidentally, the electrolyte, ethylene carbonate and ethyl methyl carbonate 3: 7 LiPF ₆ solution a mixed solution obtained by mixing at a volume ratio as a solvent (1 mol / L) was used.

(Discharge capacity)
The lithium ion battery is installed in a constant temperature bath at 20 ° C., and the lithium ion battery is charged to a voltage of 4.2 V at a current corresponding to 1 C. After that, the lithium ion battery is charged at a voltage of 2.7 V at a current corresponding to 5 C. Charging / discharging for discharging was defined as one cycle, and charging / discharging was performed 200 cycles under the same conditions. Then, the initial discharge capacity A ₁ (mAh) of the lithium ion battery after charging and discharging for one cycle and the discharge capacity A ₂₀₀ (mAh) of the lithium ion battery after charging and discharging for 200 cycles were measured. The discharge capacity retention ratio ((%) = A ₂₀₀ / A ₁ × 100) relative to the initial discharge capacity A ₁ was calculated.

Claims (4)

  A propylene-based resin microporous film in which micropores are formed by biaxially stretching a propylene-based resin film, wherein the propylene-based resin has a component amount of 25 to 60% by weight with a molecular weight of 50,000 or less. In addition, the amount of the component having a molecular weight of 700,000 or more is 19 to 30% by weight, the weight average molecular weight is 350,000 to 500,000, and the relaxation time τ when the angular frequency ω obtained from melt viscoelasticity measurement is 1 rad / s. 0.6 to 0.8 s, and the air permeability of the propylene resin microporous film is 40 to 400 s / 100 mL, the porosity is 40 to 70%, and the maximum major axis of the open end of the micropore is A propylene-based resin microporous film having a thickness of 500 nm or less.   A separator for a lithium ion battery, comprising the propylene-based resin microporous film according to claim 1.   A lithium ion battery comprising the lithium ion battery separator according to claim 2 incorporated therein.   The amount of components having a molecular weight of 50,000 or less is 25 to 60% by weight, the amount of components having a molecular weight of 700,000 or more is 19 to 30% by weight, the weight average molecular weight is 350,000 to 500,000, and the angular frequency ω obtained from melt viscoelasticity measurement Is supplied at a temperature of 20 ° C. higher than the melting point of the propylene resin, and the melting point of the propylene resin is higher than the melting point of the propylene resin. A step of extruding a propylene-based resin film from a T die attached to the tip of the extruder by melting and kneading at a temperature not higher than 50 ° C. and 60 ° C. above the melting point of the propylene-based resin. A curing step of curing at a temperature higher than a low temperature and 10 ° C lower than the melting point of the propylene-based resin, and a surface temperature of the propylene-based resin film after the curing step is -20 to 4 A cold stretching step of stretching 1.1 to 1.6 times in the extrusion direction at 0 ° C., and a temperature of the surface temperature of the propylene-based resin film after this cold stretching step is 60 ° C. lower than the melting point of the propylene-based resin The first hot stretching step in which the stretching is performed 1.6 to 3 times in the extrusion direction at a temperature lower than the melting point of the propylene-based resin by 10 ° C. or less, and the propylene-based resin film after the first hot stretching step. A first annealing step in which the surface annealing is performed at a temperature not lower than the surface temperature of the propylene-based resin film at the time of the first hot stretching step and not more than 10 ° C. lower than the melting point of the propylene-based resin; Table of the propylene-based resin film after the process has a surface temperature of 60 ° C. lower than the melting point of the propylene-based resin and the first annealing step. A second hot stretching step of stretching 1.05 to 3 times in the width direction at a temperature lower than the temperature, and a surface temperature of the propylene-based resin film after the second hot stretching step when the second hot stretching is performed And a second annealing step of annealing at a temperature not lower than the surface temperature of the propylene-based resin film and not higher than 10 ° C. lower than the melting point of the propylene-based resin, and a method for producing a propylene-based resin microporous film.