JP2019050226A - Separator for nonaqueous electrolyte secondary battery - Google Patents

Abstract

To provide a separator for a nonaqueous electrolyte secondary battery capable of realizing a nonaqueous electrolyte secondary battery having a low rate of battery resistance after aging charge and discharge of the nonaqueous electrolyte secondary battery and after repeating charge and discharge cycle.SOLUTION: The separator for nonaqueous electrolyte secondary battery includes a polyolefin porous film. The magnitude of a slope of a tangent of a region III in an ultrasonic attenuation rate curve of the separator for a nonaqueous electrolyte secondary battery immersed in an electrolytic solution is 3.5 mV/s or more and 14 mV/s or less.SELECTED DRAWING: None

Description

  The present invention relates to a separator for a non-aqueous electrolyte secondary battery.

  Non-aqueous electrolyte secondary batteries such as lithium secondary batteries are currently widely used as batteries for use in devices such as personal computers, mobile phones, and portable information terminals, or on-vehicle batteries.

  As a separator in such a nonaqueous electrolyte secondary battery, for example, a porous film mainly composed of polyolefin as described in Patent Document 1 is known.

  By the way, in Patent Document 2, in order to provide an electrode plate for a non-aqueous electrolyte secondary battery that exhibits excellent high output characteristics during rapid charge and discharge, the electrode plate is immersed in a measurement solvent and immediately after the immersion. The invention that focused on the maximum value of the rate of increase in ultrasonic transmission intensity during the period from the start of measurement until the saturation of ultrasonic transmission intensity when measuring the temporal change in ultrasonic transmission intensity from It is disclosed.

JP 11-130900 A (published May 18, 1999) JP 2007-103040 A (published April 19, 2007)

  However, the conventional non-aqueous electrolyte secondary battery including the separator for a non-aqueous electrolyte secondary battery including Patent Document 1 may have increased battery resistance after charge / discharge, and needs to be improved. was there. Therefore, the problem to be solved by the present invention is to provide a non-aqueous electrolyte secondary battery separator capable of realizing a non-aqueous electrolyte secondary battery with low battery resistance after charge and discharge.

The present invention includes the inventions shown in the following [1] to [4].
[1] A separator for a non-aqueous electrolyte secondary battery including a polyolefin porous film,
The non-aqueous electrolyte solution 2 has a tangential slope of region III in the ultrasonic attenuation rate curve of the separator for a non-aqueous electrolyte secondary battery immersed in the electrolyte solution of 3.5 mV / s to 14 mV / s. Secondary battery separator.
(Here, the region III is an ultrasonic attenuation rate curve showing a time change of the ultrasonic attenuation rate with respect to 2 MHz ultrasonic waves of the separator for a non-aqueous electrolyte secondary battery immersed in the electrolytic solution. The area after the inflection point is shown.)
[2] A laminated separator for a nonaqueous electrolyte secondary battery comprising the separator for a nonaqueous electrolyte secondary battery according to [1] and an insulating porous layer.
[3] A positive electrode, a separator for a nonaqueous electrolyte secondary battery according to [1], or a laminated separator for a nonaqueous electrolyte secondary battery according to [2], and a negative electrode are arranged in this order. A member for a non-aqueous electrolyte secondary battery.
[4] A nonaqueous electrolyte secondary battery comprising the nonaqueous electrolyte secondary battery separator according to [1] or the nonaqueous electrolyte secondary battery laminated separator according to [2].

  In Patent Document 2, in order to provide an electrode plate for a non-aqueous electrolyte secondary battery that exhibits high output characteristics, the temporal change in ultrasonic transmission intensity of the electrode plate for a non-aqueous electrolyte secondary battery is measured. However, the invention described in Patent Document 2 and the present invention are completely different from the problems and objects to be solved.

  The separator for a non-aqueous electrolyte secondary battery according to an embodiment of the present invention has a low battery resistance after charge / discharge of the non-aqueous electrolyte secondary battery incorporating the non-aqueous electrolyte secondary battery separator. There is an effect that the cycle characteristics of the nonaqueous electrolyte secondary battery are improved.

It is a schematic diagram which shows the measuring apparatus and measuring method of the ultrasonic attenuation factor of the separator for nonaqueous electrolyte secondary batteries immersed in the electrolytic solution. It is a figure which shows an example of the ultrasonic attenuation rate curve (t = 0-300 second) of the separator for nonaqueous electrolyte secondary batteries immersed in electrolyte solution. FIG. 5 is an enlarged view showing t = 0 to 5 seconds of the ultrasonic attenuation rate curve shown in FIG. 2.

  An embodiment of the present invention will be described below, but the present invention is not limited to this. The present invention is not limited to each configuration described below, and various modifications are possible within the scope shown in the claims, and various technical means disclosed in different embodiments are appropriately combined. The obtained embodiments are also included in the technical scope of the present invention. Unless otherwise specified in this specification, “A to B” indicating a numerical range means “A or more and B or less”.

[Embodiment 1: Nonaqueous electrolyte secondary battery separator]
A separator for a non-aqueous electrolyte secondary battery according to Embodiment 1 of the present invention is a separator for a non-aqueous electrolyte secondary battery including a polyolefin porous film, and is a non-aqueous electrolyte secondary battery immersed in the electrolyte. The magnitude of the tangential slope of region III in the ultrasonic attenuation rate curve of the secondary battery separator is 3.5 mV / s to 14 mV / s.

  Here, the region III is an ultrasonic attenuation rate curve showing a time change of the ultrasonic attenuation rate with respect to 2 MHz ultrasonic waves of the separator for a non-aqueous electrolyte secondary battery immersed in the electrolytic solution. The area after the inflection point is shown.

  The “ultrasonic attenuation rate” is the ratio of the intensity of the ultrasonic wave that has passed through the separator for a non-aqueous electrolyte secondary battery to the intensity of the ultrasonic wave to be irradiated. The “ultrasonic attenuation rate curve” refers to the ultrasonic attenuation rate when the ultrasonic wave is irradiated to the separator for a non-aqueous electrolyte secondary battery immersed in the non-aqueous electrolyte, and the immersion time t. It is a curve which shows the relationship. An example of the ultrasonic attenuation rate curve is shown in FIGS. FIG. 2 is a diagram showing an example of an ultrasonic attenuation rate curve (t = 0 to 300 seconds) of a separator for a non-aqueous electrolyte secondary battery immersed in an electrolytic solution. FIG. 3 is an enlarged view showing t = 0 to 5 seconds of the ultrasonic attenuation rate curve shown in FIG. For the measurement method of the ultrasonic attenuation rate and the method of creating the ultrasonic attenuation curve, reference is made to the description to be described later and the description in the examples.

  The ultrasonic attenuation rate (vertical axis) in the ultrasonic attenuation curves shown in FIG. 2 and FIG. 3 is expressed by being converted to the voltage (mV) of the DC-DC converter as shown in the examples described later. Here, it is shown that the higher the voltage, the smaller the ultrasonic attenuation rate, that is, the easier the ultrasonic wave is transmitted.

  As shown in FIG. 3, the voltage in the ultrasonic attenuation rate curve increases with the passage of time and starts to decrease immediately after the separator for the non-aqueous electrolyte secondary battery is immersed in the non-aqueous electrolyte. After that, as shown in FIG. 2, the voltage in the ultrasonic attenuation rate curve starts to increase again. In other words, the ultrasonic attenuation rate decreases with the passage of time immediately after the non-aqueous electrolyte secondary battery separator is immersed in the non-aqueous electrolyte, and the first inflection point (first inflection point). ) And then increases again and then decreases again at the second inflection point (second inflection point). That is, it can be said that as time passes, the ultrasonic wave is less likely to be transmitted from the first inflection point, and thereafter, the ultrasonic wave is easily transmitted from the second inflection point. Here, in this specification, “region I” indicates the first inflection point (first inflection point of the ultrasonic attenuation rate curve from the start of the immersion of the non-aqueous electrolyte secondary battery separator in the electrolyte (t = 0). 1), “region II” is a region from the first inflection point to the second inflection point of the ultrasonic attenuation rate curve, and “region III” is This is the area after the second inflection point of the sound wave attenuation rate curve (see FIGS. 2 and 3).

  When the non-aqueous electrolyte secondary battery separator is immersed in the non-aqueous electrolyte, the non-aqueous electrolyte (liquid) penetrates into the voids of the non-aqueous electrolyte secondary battery separator. In region I, a phenomenon occurs in which the non-aqueous electrolyte adheres to the surface of the separator for the non-aqueous electrolyte secondary battery, and in region II, the electrolyte enters the void inside the separator. A phenomenon occurs in which large air gaps (bubbles) are generated by gathering of air present in a plurality of air gaps. In region III, a phenomenon occurs in which large bubbles generated in region II escape from the inside of the separator to the outside.

  Here, it is known that the attenuation rate of ultrasonic waves (sound) varies depending on the propagation medium, and that the attenuation rate of liquid is lower than that of air.

  In the region I where the non-aqueous electrolyte begins to permeate the separator for the non-aqueous electrolyte secondary battery, the ultrasonic attenuation rate is reduced because the air on the separator surface is replaced with the non-aqueous electrolyte that easily transmits ultrasonic waves. As a result, the voltage of the ultrasonic attenuation rate curve increases. In region II, large air bubbles are formed by the air present in the voids inside the non-aqueous electrolyte secondary battery separator moving and gathering due to the pressure of the non-aqueous electrolyte. Since large bubbles (air) are more likely to scatter ultrasonic waves than small bubbles, the ultrasonic attenuation rate increases in region II (that is, the voltage of the ultrasonic attenuation rate curve decreases). On the other hand, in the region III, the large bubbles (air) formed in the region II escape from the inside of the non-aqueous electrolyte secondary battery separator to the outside, so that the ultrasonic attenuation rate becomes low. As a result, the voltage of the ultrasonic attenuation rate curve increases. In addition, since the speed at which air in region III escapes is slower than the speed at which air in region I escapes, the voltage increase rate in region III is smaller than the voltage increase rate in region I.

  From the above, it can be said that the magnitude of the tangential slope of the ultrasonic attenuation rate curve in region III indicates the speed at which large bubbles (air) escape from the voids of the separator for the nonaqueous electrolyte secondary battery in region III. . That is, it is considered that the larger the inclination of the tangent, the thicker the flow path inside the gap, the easier the large air can escape, and the fewer branches that prevent the passage of large bubbles. In addition, it is considered that the smaller the inclination of the tangent, the narrower the flow path inside the gap, the more difficult it is for air to escape, and the more branches that prevent the passage of large bubbles.

  Therefore, when the magnitude of the tangential slope in the region III of the ultrasonic attenuation rate curve is too large, the unevenness of the charge density of lithium ions or the like increases due to factors such as the channel being too thick. It is considered that the battery resistance increases due to local deterioration. In addition, when the magnitude of the inclination is too small, decomposition products such as an electrolyte generated inside the battery adhere to the narrow flow path, and further narrow the flow path and sometimes clog the lithium ion or the like. It is considered that the battery resistance is increased because the movement of charges is inhibited.

  For this reason, the magnitude | size of the inclination of the tangent in the area | region III of an ultrasonic attenuation rate curve is 3.5 mV / s or more, 3.7 mV / s or more is preferable and 4.0 mV / s or more is more preferable. In addition, the magnitude of the tangential slope in the region III of the ultrasonic attenuation rate curve of the separator for a non-aqueous secondary battery according to one embodiment of the present invention is 14 mV / s or less, preferably 13.5 mV / s or less. 14 mV / s or less is more preferable.

  In addition, the battery resistance after the aging charge / discharge mentioned above is a degassing operation usually performed in the manufacturing process of the nonaqueous electrolyte secondary battery, and then charge / discharge is performed at a low rate (for example, , Voltage range at 25 ° C .; 4.1 to 2.7 V, charging current value; CC-CV charging of 0.2 C (end current condition 0.02 C), CC discharging of discharge current value 0.2 C (1 hour rate The battery at the time of discharging when performing aging charge / discharge is repeated under several conditions (for example, 3 cycles) under the condition that the current value for discharging the rated capacity by the discharge capacity in 1 hour is 1 C, and so on) Resistance. Here, CC-CV charging is a charging method in which charging is performed with a set constant current, and after reaching a predetermined voltage, the voltage is maintained while the current is reduced. The CC discharge is a method of discharging to a predetermined voltage with a set constant current, and the same applies to the following.

  The battery resistance after the charge / discharge cycle refers to the charge / discharge cycle after performing aging charge / discharge, and at least the separator for the nonaqueous electrolyte secondary battery, the penetration of the nonaqueous electrolyte into the electrode, and the nonaqueous It is the battery resistance after performing a sufficient number of cycles for the gas generated by the decomposition of the electrolytic solution to reach the surplus portion where the electrode inside the battery does not exist. The number of cycles of the charge / discharge cycle is not particularly limited, but is generally 20 cycles or more.

  Here, the creation of the ultrasonic attenuation rate curve and the determination of the magnitude of the tangent slope in the region III of the ultrasonic attenuation rate curve are performed as follows, for example. The measurement of the ultrasonic attenuation rate can be carried out using a dynamic liquid permeability measuring apparatus (EMC Corporation dynamic liquid permeability measuring apparatus: PDA.C.02 Module Standard). FIG. 1 shows a schematic diagram of a dynamic liquid permeability measuring apparatus.

  First, ethyl carbonate (may be described as “EC”) / ethyl methyl carbonate (may be described as “EMC”) / diethyl carbonate (may be described as “DEC”) = 3/5/2 A non-aqueous electrolyte prepared by mixing (volume ratio) is prepared. Next, the non-aqueous electrolyte is added to the bathtub 1 attached to the dynamic liquid permeability measuring device until the reference line of the bathtub 1 is satisfied.

  Then, using the double-sided tape attached to the dynamic liquid permeability measuring device to the sample holder 2 attached to the dynamic liquid permeability measuring device, the sample affixing position provided in the sample holder 2 is non-aqueous. An electrolyte secondary battery separator 3 is attached to prepare a sample before measurement.

  Subsequently, the pre-measurement sample is attached to the dynamic liquid permeability measurement device, and using the attached software of the dynamic liquid permeability measurement device, the measurement conditions are as follows: Algorithm: General, Measurement frequency: 2 MHz, Measurement diameter: The ultrasonic attenuation rate is measured by setting to 10 mm.

At that time, the measurement is started by pressing the test start button of the dynamic liquid permeability measuring apparatus. The time when the test start button is pressed is t = 0 ms. When the test start button is pushed, the pre-measurement sample equipped with the sample holder 2 by the constant speed motor starts to drop into the bathtub 1 filled with the nonaqueous electrolyte at a constant speed, and the drop time (t = 6 ms) The measurement position of the bathtub 1 is reached. Thereafter, measurement data of the first ultrasonic attenuation rate is measured at time: (t = 7 ms), and thereafter the ultrasonic attenuation rate is measured every measurement interval of 4 ms. Immediately after the start of measurement, the value of the minimum point appearing on the vertical axis of the measurement state monitoring graph on the computer is written, and the value of the minimum point is taken as the intensity of the ultrasonic attenuation rate at t = 7 ms.

  The minimum point is not described in units on the computer, but indicates the voltage value of the DC-DC converter. Therefore, the unit of the ultrasonic attenuation rate measured by the above method is mV.

  By measuring the ultrasonic attenuation rate, the change of the ultrasonic attenuation rate over time is plotted, and an ultrasonic attenuation rate curve as shown in FIG. 2 is created. In the region III of the ultrasonic attenuation rate curve, the time to reach the point (second inflection point) at which the ultrasonic attenuation rate changes from increasing to decreasing is defined as t = Dms, and the ultrasonic attenuation rate at t = Dms. And a tangent line using the least square method, and the time when the correlation coefficient of the least square method is closest to 0.985 is t = Ems, and t = Dms And the magnitude of the slope of the straight line connecting the ultrasonic attenuation rate at t = Ems is calculated and defined as the magnitude c of the tangential slope in the region III of the ultrasonic attenuation rate curve.

  Note that another ultrasonic attenuation rate curve may be created by setting the intensity of the ultrasonic attenuation rate at the initial data measurement time (t = 7 ms) as 100%. Based on the other ultrasonic attenuation rate curve, the tangential slope magnitude c ′ in the region III of the other ultrasonic attenuation rate curve may be calculated by the same method as the above calculation method. In this case, the magnitude c ′ of the tangential slope of the region III of the ultrasonic attenuation rate curve of the separator for a non-aqueous electrolyte secondary battery according to an embodiment of the present invention is 0.02% / s or more (more preferably Is 0.025% / s or more, more preferably 0.03% / s or more), 0.097% / s or less (more preferably 0.090% / s or less, more preferably 0.085% / s or less). ).

  In the above ultrasonic attenuation rate measurement method, a mixed electrolyte of EC / EMC / DEC = 3/5/2 (volume ratio) was used as a nonaqueous electrolyte, but it was used for a nonaqueous electrolyte secondary battery. Other non-aqueous electrolytes that can be used can also be used. The non-aqueous electrolyte that can be used for the non-aqueous electrolyte secondary battery has a viscosity, polarity, and ionic conductivity within a certain range, and as described above, the tangential line in the region III of the ultrasonic attenuation rate curve described above. The magnitude of the inclination depends on factors other than the affinity between the inner wall of the gap inside the separator for a nonaqueous electrolyte secondary battery and the electrolyte, such as the gap structure inside the separator. Therefore, even when the other non-aqueous electrolyte is used, when the non-aqueous electrolyte secondary battery separator to be measured is the same, in the region III of the ultrasonic attenuation rate curve described above, The magnitude of the tangent slope is almost the same.

  The separator for a nonaqueous electrolyte secondary battery according to Embodiment 1 of the present invention includes a polyolefin porous film, and preferably includes a polyolefin porous film. Here, the “polyolefin porous film” is a porous film containing a polyolefin resin as a main component. Further, “based on a polyolefin-based resin” means that the proportion of the polyolefin-based resin in the porous film is 50% by volume or more of the entire material constituting the porous film, preferably 90% by volume or more, More preferably, it means 95% by volume or more.

  The polyolefin porous film can be a base material for a separator for a non-aqueous electrolyte secondary battery according to an embodiment of the present invention or a laminated separator for a non-aqueous electrolyte secondary battery according to an embodiment of the present invention described later. . The polyolefin porous film has a large number of pores connected to the inside thereof, and allows gas or liquid to pass from one surface to the other surface.

It is more preferable that the polyolefin resin contains a high molecular weight component having a weight average molecular weight of 3 × 10 ⁵ to 15 × 10 ⁶ . Particularly, when the polyolefin resin contains a high molecular weight component having a weight average molecular weight of 1,000,000 or more, the strength of the polyolefin porous film and the laminated separator for a nonaqueous electrolyte secondary battery including the polyolefin porous film is high. Since it improves, it is more preferable.

  The polyolefin-based resin that is the main component of the polyolefin porous film is not particularly limited. For example, a thermoplastic resin such as ethylene, propylene, 1-butene, 4-methyl-1-pentene, and 1-hexene can be used. Examples include homopolymers (for example, polyethylene, polypropylene, polybutene) or copolymers (for example, ethylene-propylene copolymer) obtained by (co) polymerizing the monomers. The polyolefin porous film may be a layer containing these polyolefin resins alone or a layer containing two or more of these polyolefin resins. Among these, polyethylene can be more preferable because it can prevent (shut down) an excessive current from flowing at a lower temperature, and high molecular weight polyethylene mainly including ethylene is particularly preferable. In addition, a polyolefin porous film does not prevent containing components other than polyolefin in the range which does not impair the function of the said layer.

Examples of polyethylene include low density polyethylene, high density polyethylene, linear polyethylene (ethylene-α-olefin copolymer), ultrahigh molecular weight polyethylene having a weight average molecular weight of 1,000,000 or more, and of these, the weight average molecular weight is Ultra high molecular weight polyethylene of 1 million or more is more preferable, and it is more preferable that a high molecular weight component having a weight average molecular weight of 5 × 10 ⁵ to 15 × 10 ⁶ is contained.

  Although the film thickness of the said polyolefin porous film is not specifically limited, It is preferable that it is 4-40 micrometers, and it is more preferable that it is 5-20 micrometers.

  If the film thickness of the said porous polyolefin film is 4 micrometers or more, it is preferable from a viewpoint that the internal short circuit of a battery can fully be prevented.

  On the other hand, if the film thickness of the said porous polyolefin film is 40 micrometers or less, it is preferable from a viewpoint that the enlargement of a nonaqueous electrolyte secondary battery can be prevented.

The weight per unit area of the polyolefin porous film is usually preferably 4 to 20 g / m ² so that the weight energy density and volume energy density of the battery can be increased, and preferably 5 to 12 g. / M ² is more preferable.

  The air permeability of the polyolefin porous film is preferably a Gurley value of 30 to 500 sec / 100 mL, more preferably 50 to 300 sec / 100 mL, from the viewpoint of exhibiting sufficient ion permeability.

  The porosity of the polyolefin porous film is 20% by volume to 80% by volume so as to increase the amount of electrolyte retained and to reliably prevent the excessive current from flowing (shut down) at a lower temperature. %, And more preferably 30 to 75% by volume.

  The pore diameter of the pores of the polyolefin porous film is preferably 0.3 μm or less from the viewpoint of sufficient ion permeability and prevention of entering of particles constituting the electrode, and is 0.14 μm or less. More preferably.

The separator for a non-aqueous electrolyte secondary battery according to an embodiment of the present invention may be an insulating porous layer (hereinafter, also simply referred to as “porous layer”), if necessary, in addition to the polyolefin porous film. May be included. Examples of the porous layer include a porous layer constituting a non-aqueous electrolyte laminated separator described later, and examples of other porous layers include known porous layers such as a heat-resistant layer, an adhesive layer, and a protective layer.

[Polyolefin porous film production method]
The method for producing the polyolefin porous film is not particularly limited. For example, a polyolefin resin composition and an additive are kneaded and then extruded to prepare a sheet-like polyolefin resin composition, and the polyolefin resin composition Examples of the method include stretching the product, washing with a suitable solvent, drying and heat setting.

Specifically, the method shown below can be mentioned.
(A) A step of adding a polyolefin-based resin and an additive (i) that is solid at room temperature (approximately 25 ° C.) to a kneader and melt-kneading to obtain a molten mixture;
(B) adding the additive (ii) that is liquid at room temperature to a kneader and kneading the resulting molten mixture to obtain a polyolefin resin composition;
(C) Extruding the obtained polyolefin resin composition from a T-die of an extruder, forming into a sheet shape while cooling, and obtaining a sheet-like polyolefin resin composition;
(D) a step of stretching the obtained sheet-like polyolefin resin composition,
(E) a step of washing the stretched polyolefin resin composition using a washing liquid;
(F) A step of obtaining a polyolefin porous film by drying and heat-setting the washed polyolefin resin composition.

  In the step (A), the amount of the polyolefin resin powder used is preferably 6% by weight to 45% by weight, and 9% by weight to 36% by weight, when the weight of the resulting polyolefin resin composition is 100% by weight. It is more preferable that

  Examples of the additive (i) used in the step (A) include petroleum resins. As the petroleum resin, an aliphatic hydrocarbon resin having a softening point of 90 ° C. to 125 ° C. and an alicyclic saturated hydrocarbon resin having a softening point of 90 ° C. to 125 ° C. are preferable, and an alicyclic group having the above softening point. Saturated hydrocarbon resins are more preferred. The amount of the additive (i) used is preferably 0.5% to 40% by weight, preferably 1% to 30% by weight, when the weight of the resulting polyolefin resin composition is 100% by weight. More preferably.

  Additives (ii) used in step (B) include phthalates such as dioctyl phthalate, unsaturated higher alcohols such as oleyl alcohol, saturated higher alcohols such as stearyl alcohol, and low molecular weights such as paraffin wax. Examples include polyolefin resins and liquid paraffin. Preferably, a plasticizer such as liquid paraffin that functions as a pore forming agent is used.

  The amount of the additive (ii) used is preferably 50% by weight to 90% by weight and preferably 60% by weight to 85% by weight when the weight of the polyolefin resin composition obtained is 100% by weight. More preferred.

  In the step (B), the temperature inside the kneader when the additive (ii) is added to the kneader is preferably 140 ° C. or higher and 200 ° C. or lower, more preferably 160 ° C. or higher and 180 ° C. or lower, Preferably they are 166 degreeC or more and 180 degrees C or less.

If the temperature inside the kneader when adding the additive (ii) is low, the dispersion uniformity becomes coarse, and therefore the flow path inside the gap of the separator tends to be thick. On the other hand, if the temperature inside the kneader when adding the additive (ii) is high, the dispersion uniformity becomes dense, so that the flow path inside the gap of the separator tends to be narrow.

  In the step (C), the T die extrusion temperature when the melt mixture is extruded from the T die is preferably 200 ° C to 220 ° C, more preferably 205 ° C to 215 ° C.

  In the step (D), a commercially available stretching apparatus can be used for stretching the sheet-like polyolefin resin composition. Specifically, a method of stretching by grabbing the edge of the sheet with a chuck, a method of stretching by changing the rotation speed of a roll that conveys the sheet, or a sheet using a pair of rolls may be used. You may use the method of rolling.

  The stretching is preferably performed in both the MD direction and the TD direction. As a method of stretching in both the MD direction and the TD direction, after stretching in the MD direction, the subsequent biaxial stretching in which the stretching is performed in the TD direction, and the simultaneous biaxial stretching in which the stretching in the MD direction and the TD direction are performed simultaneously. Is mentioned.

  In the step (D), the stretching ratio when the sheet-like polyolefin resin composition is stretched to MD is preferably 4.0 to 7.5 times, and preferably 4.0 to 6.5 times. It is more preferable. The draw ratio at the time of drawing to TD is preferably 4.0 to 7.5 times, and more preferably 4.0 to 6.5 times. The temperature of the sheet-like polyolefin resin composition during stretching is preferably 130 ° C. or lower, and more preferably 100 to 130 ° C.

  Further, the ratio of the draw ratio in the MD direction to the TD direction (the value obtained by dividing the draw ratio in the MD direction by the draw ratio in the TD direction, or vice versa) is preferably 0.55 to 1.85, 0.62 to 1.63 is more preferable. It is considered that the larger the ratio of the draw ratio, the higher the anisotropy of the voids, so that the passage of large bubbles tends to become narrower. That is, it is considered that as the ratio of the draw ratio is higher, the magnitude of the tangential slope in the region III of the ultrasonic attenuation rate curve tends to be smaller.

  The cleaning liquid used in the step (E) is not particularly limited as long as it is a solvent that can remove additives such as a pore forming agent, and examples thereof include heptane and dichloromethane.

  The washing solvent is removed by drying from the polyolefin resin composition from which the additive has been removed in the step (F). The drying is preferably heat-treated at a specific temperature simultaneously with the subsequent heat setting operation.

  The temperature of the heat treatment is preferably 80 ° C. or higher and 140 ° C. or lower, and more preferably 100 ° C. or higher and 135 ° C. or lower. The time for the heat treatment is preferably 0.5 to 30 minutes, more preferably 1 to 15 minutes.

  By performing the heat treatment in the above temperature range and time, the number of fine branches that prevent passage of large bubbles present in the voids of the separator tends to be adjusted to a suitable range.

  In the step (F), an apparatus generally used in the operation in the step, such as a temperature control roll or a ventilation constant temperature bath, can be used.

[Embodiment 2: Laminated separator for non-aqueous electrolyte secondary battery]
The laminated separator for nonaqueous electrolyte secondary batteries according to Embodiment 2 of the present invention includes the separator for nonaqueous electrolyte secondary batteries according to Embodiment 1 of the present invention and an insulating porous layer. Therefore, the non-aqueous electrolyte secondary battery laminated separator according to Embodiment 2 of the present invention is a polyolefin porous film constituting the non-aqueous electrolyte secondary battery separator according to Embodiment 1 of the present invention described above. including.

[Insulating porous layer]
The insulating porous layer constituting the laminated separator for a non-aqueous electrolyte secondary battery according to one embodiment of the present invention is usually a resin layer containing a resin, preferably a heat-resistant layer or an adhesive layer. . The resin constituting the insulating porous layer is preferably insoluble in the battery electrolyte and is electrochemically stable in the range of use of the battery.

  A porous layer is laminated | stacked on the single side | surface or both surfaces of the separator for nonaqueous electrolyte secondary batteries as needed. When a porous layer is laminated on one side of the polyolefin porous film, the porous layer is preferably on the surface facing the positive electrode in the polyolefin porous film when a non-aqueous electrolyte secondary battery is used. Laminated, more preferably, on the surface in contact with the positive electrode.

  Examples of the resin constituting the porous layer include polyolefin, (meth) acrylate resin, fluorine-containing resin, polyamide resin, polyimide resin, polyester resin, rubbers, and a melting point or glass transition temperature of 180 ° C. or higher. Resin; Water-soluble polymer etc. are mentioned.

  Of the above-described resins, polyolefins, acrylate resins, fluorine-containing resins, polyamide resins, polyester resins, and water-soluble polymers are preferable. As the polyamide-based resin, a wholly aromatic polyamide (aramid resin) is preferable. As the polyester resin, polyarylate and liquid crystal polyester are preferable.

  The porous layer may contain fine particles. The fine particles in the present specification are organic fine particles or inorganic fine particles generally called a filler. Therefore, when the porous layer includes fine particles, the above-described resin contained in the porous layer has a function as a binder resin that binds the fine particles to each other and the fine particles and the porous film. The fine particles are preferably insulating fine particles.

  Examples of the organic fine particles contained in the porous layer include fine particles made of a resin.

  Specifically, as the inorganic fine particles contained in the porous layer, for example, calcium carbonate, talc, clay, kaolin, silica, hydrotalcite, diatomaceous earth, magnesium carbonate, barium carbonate, calcium sulfate, magnesium sulfate, barium sulfate, Examples include fillers made of inorganic substances such as aluminum hydroxide, boehmite, magnesium hydroxide, calcium oxide, magnesium oxide, titanium oxide, titanium nitride, alumina (aluminum oxide), aluminum nitride, mica, zeolite, and glass. These inorganic fine particles are insulating fine particles. Only one type of fine particles may be used, or two or more types may be used in combination.

  Among the above fine particles, fine particles made of an inorganic substance are preferable, and fine particles made of an inorganic oxide such as silica, calcium oxide, magnesium oxide, titanium oxide, alumina, mica, zeolite, aluminum hydroxide, or boehmite are more preferable, and silica Further, at least one fine particle selected from the group consisting of magnesium oxide, titanium oxide, aluminum hydroxide, boehmite and alumina is more preferable, and alumina is particularly preferable.

  The content of fine particles in the porous layer is preferably 1 to 99% by volume of the porous layer, and more preferably 5 to 95% by volume. By setting the content of the fine particles in the above range, voids formed by contact between the fine particles are less likely to be blocked by a resin or the like. Therefore, sufficient ion permeability can be obtained, and the basis weight per unit area can be set to an appropriate value.

  The fine particles may be used in combination of two or more different particles or specific surface areas.

  The thickness of the porous layer is preferably 0.5 to 15 μm and more preferably 2 to 10 μm per side of the laminated separator for a nonaqueous electrolyte secondary battery.

  If the thickness of the porous layer is less than 1 μm, internal short circuit due to battery damage or the like may not be sufficiently prevented. In addition, the amount of electrolytic solution retained in the porous layer may decrease. On the other hand, when the thickness of the porous layer exceeds 30 μm in total on both sides, the rate characteristics or the cycle characteristics may deteriorate.

Weight per unit area of the porous layer having a basis weight (per one side) is preferably from 1 to 20 g / ^{m 2,} and more preferably 4~10g / ^{m 2.}

The volume of the porous layer constituents contained per square meter porous layer (per one side) is preferably 0.5～20Cm ^3, more preferably 1 to 10 cm ^3,. 2 to More preferably, it is 7 cm ³ .

  The porosity of the porous layer is preferably 20 to 90% by volume, and more preferably 30 to 80% by volume so that sufficient ion permeability can be obtained. Moreover, the pore diameter of the pores of the porous layer is preferably 3 μm or less, and preferably 1 μm or less so that the laminated separator for a non-aqueous electrolyte secondary battery can obtain sufficient ion permeability. Is more preferable.

[Laminate]
A laminate that is a laminated separator for a nonaqueous electrolyte secondary battery according to Embodiment 2 of the present invention includes the separator for a nonaqueous electrolyte secondary battery and an insulating porous layer according to an embodiment of the present invention, Preferably, the non-aqueous electrolyte secondary battery separator according to one embodiment of the present invention has a configuration in which the above-described insulating porous layer is laminated on one side or both sides.

  The film thickness of the laminate according to an embodiment of the present invention is preferably 5.5 μm to 45 μm, and more preferably 6 μm to 25 μm.

The air permeability of the laminate according to an embodiment of the present invention is a Gurley value of 30 to 1000 sec / 100.
It is preferable that it is mL, and it is more preferable that it is 50-800 sec / 100mL.

  In addition to the polyolefin porous film and the insulating porous layer, the laminate according to an embodiment of the present invention may be a known porous film (porous film) such as a heat-resistant layer, an adhesive layer, or a protective layer, if necessary. May be included in a range not impairing the object of the present invention.

The laminated body which concerns on one Embodiment of this invention contains the separator for nonaqueous electrolyte secondary batteries whose magnitude | size of the inclination of the tangent in the area | region III of the said ultrasonic attenuation rate curve is a specific range as a base material. Therefore, the battery resistance after charging / discharging (especially after aging charge / discharge and after repeating charge / discharge cycles) of the non-aqueous electrolyte secondary battery including the laminate as a laminated separator for non-aqueous electrolyte secondary batteries is reduced. be able to.

[Method for producing porous layer and laminate]
As an insulating porous layer in one embodiment of the present invention and a manufacturing method of a layered product concerning one embodiment of the present invention, for example, the coating liquid mentioned below is used for nonaqueous electrolyte 2 concerning one embodiment of the present invention. The method of depositing an insulating porous layer by apply | coating to the surface of the polyolefin porous film with which the separator for secondary batteries is equipped and drying is mentioned.

  In addition, before apply | coating the said coating liquid to the surface of the polyolefin porous film with which the separator for nonaqueous electrolyte secondary batteries which concerns on one Embodiment of this invention is provided, the coating liquid of the said polyolefin porous film is apply | coated. A hydrophilic treatment can be performed on the surface as necessary.

  The coating liquid used in the method for producing a porous layer according to one embodiment of the present invention and the method for producing a laminate according to one embodiment of the present invention usually uses a resin that can be contained in the porous layer as a solvent. And can be prepared by dispersing fine particles that can be contained in the porous layer. Here, the solvent for dissolving the resin also serves as a dispersion medium for dispersing the fine particles. The resin may be made into an emulsion with a solvent.

  The solvent (dispersion medium) is not particularly limited as long as it does not adversely affect the porous polyolefin film, can dissolve the resin uniformly and stably, and can uniformly and stably disperse the fine particles. Specific examples of the solvent (dispersion medium) include water and organic solvents. Only one type of solvent may be used, or two or more types may be used in combination.

  The coating liquid may be formed by any method as long as the conditions such as the resin solid content (resin concentration) and the amount of fine particles necessary for obtaining a desired porous layer can be satisfied. Specific examples of the method for forming the coating liquid include a mechanical stirring method, an ultrasonic dispersion method, a high-pressure dispersion method, and a media dispersion method. In addition, the coating liquid may contain additives such as a dispersant, a plasticizer, a surfactant, and a pH adjuster as components other than the resin and fine particles as long as the object of the present invention is not impaired. . In addition, the addition amount of an additive should just be a range which does not impair the objective of this invention.

  The method for applying the coating liquid to the polyolefin porous film, that is, the method for forming the porous layer on the surface of the polyolefin porous film is not particularly limited. As a method for forming the porous layer, for example, a method in which the coating liquid is directly applied to the surface of the polyolefin porous film, and then the solvent (dispersion medium) is removed; the coating liquid is applied to a suitable support, and the solvent (Dispersion medium) is removed to form a porous layer, and then the porous layer and the polyolefin porous film are pressure-bonded, and then the support is peeled off; after the coating liquid is applied to a suitable support, Examples include a method in which a polyolefin porous film is pressure-bonded to the coated surface, and then the solvent (dispersion medium) is removed after peeling off the support.

  As a method for applying the coating liquid, a conventionally known method can be employed. Specific examples include a gravure coater method, a dip coater method, a bar coater method, and a die coater method.

  As a method for removing the solvent (dispersion medium), a drying method is generally used. Further, the solvent (dispersion medium) contained in the coating liquid may be replaced with another solvent before drying.

[Embodiment 3: Nonaqueous electrolyte secondary battery member, Embodiment 4: Nonaqueous electrolyte secondary battery]
A member for a non-aqueous electrolyte secondary battery according to Embodiment 3 of the present invention is a positive electrode, a separator for a non-aqueous electrolyte secondary battery according to Embodiment 1 of the present invention, or a non-electrode according to Embodiment 2 of the present invention. A laminated separator for a water electrolyte secondary battery and a negative electrode are arranged in this order.

  The nonaqueous electrolyte secondary battery according to Embodiment 4 of the present invention is a nonaqueous electrolyte secondary battery separator according to Embodiment 1 of the present invention or the nonaqueous electrolyte secondary battery according to Embodiment 2 of the present invention. Includes a laminated separator for a secondary battery.

  A nonaqueous electrolyte secondary battery according to an embodiment of the present invention is a nonaqueous secondary battery that obtains an electromotive force by, for example, lithium doping / dedoping, and includes a positive electrode and an embodiment of the present invention. A non-aqueous electrolyte secondary battery member in which a separator for a non-aqueous electrolyte secondary battery and a negative electrode are laminated in this order may be provided. A nonaqueous electrolyte secondary battery according to an embodiment of the present invention is a nonaqueous secondary battery that obtains an electromotive force by, for example, lithium doping / dedoping, and includes a positive electrode, a porous layer, A separator for a nonaqueous electrolyte secondary battery according to an embodiment of the invention and a negative electrode are laminated in this order, that is, a nonaqueous electrolyte secondary battery member, that is, a positive electrode, and an embodiment of the present invention It may be a lithium ion secondary battery provided with a nonaqueous electrolyte secondary battery member in which a nonaqueous electrolyte secondary battery laminated separator and a negative electrode are laminated in this order. The constituent elements of the nonaqueous electrolyte secondary battery other than the separator for the nonaqueous electrolyte secondary battery are not limited to the constituent elements described below.

  In the non-aqueous electrolyte secondary battery according to one embodiment of the present invention, the negative electrode and the positive electrode are usually provided in the separator for a non-aqueous electrolyte secondary battery according to one embodiment of the present invention or one embodiment of the present invention. A battery element in which an electrolyte is impregnated in a structure opposed to the laminated separator for a nonaqueous electrolyte secondary battery is enclosed in an exterior material. The nonaqueous electrolyte secondary battery is preferably a nonaqueous electrolyte secondary battery, particularly a lithium ion secondary battery. Doping means occlusion, support, adsorption, or insertion, and means a phenomenon in which lithium ions enter an active material of an electrode such as a positive electrode.

  A non-aqueous electrolyte secondary battery member according to an embodiment of the present invention is a non-aqueous electrolyte secondary battery separator according to an embodiment of the present invention or a non-aqueous electrolyte secondary battery according to an embodiment of the present invention. A laminated separator is provided. Therefore, when the non-aqueous electrolyte secondary battery member according to an embodiment of the present invention is incorporated in a non-aqueous electrolyte secondary battery, the non-aqueous electrolyte secondary battery member is charged and discharged (especially aging charge). The battery resistance after discharge and after repeating the charge / discharge cycle) can be reduced. A nonaqueous electrolyte secondary battery according to an embodiment of the present invention is a nonaqueous electrolyte secondary battery according to an embodiment of the present invention in which the magnitude of the tangential slope in the region III is adjusted to a specific range. A separator is provided. Therefore, the nonaqueous electrolyte secondary battery according to an embodiment of the present invention has an effect that the battery resistance after charge / discharge (particularly after aging charge / discharge and after repeating charge / discharge cycles) is low.

<Positive electrode>
The positive electrode in the non-aqueous electrolyte secondary battery member and non-aqueous electrolyte secondary battery according to an embodiment of the present invention is particularly limited as long as it is generally used as the positive electrode of the non-aqueous electrolyte secondary battery. However, for example, a positive electrode sheet having a structure in which an active material layer containing a positive electrode active material and a binder resin is formed on a current collector can be used. Note that the active material layer may further contain a conductive agent.

  Examples of the positive electrode active material include materials that can be doped / undoped with lithium ions. Specific examples of the material include lithium composite oxides containing at least one transition metal such as V, Mn, Fe, Co, and Ni.

Examples of the conductive material include carbonaceous materials such as natural graphite, artificial graphite, cokes, carbon black, pyrolytic carbons, carbon fibers, and organic polymer compound fired bodies.
Only one type of the conductive material may be used, or two or more types may be used in combination.

  Examples of the binder include fluorine resins such as polyvinylidene fluoride, acrylic resins, and styrene butadiene rubber. The binder also has a function as a thickener.

  Examples of the positive electrode current collector include conductors such as Al, Ni, and stainless steel. Among these, Al is more preferable because it is easily processed into a thin film and is inexpensive.

  As a method for producing a sheet-like positive electrode, for example, a method in which a positive electrode active material, a conductive material and a binder are pressure-molded on a positive electrode current collector; a positive electrode active material, a conductive material and a binder using an appropriate organic solvent are used. Examples include a method in which the paste is formed into a paste, and then the paste is applied to the positive electrode current collector, dried and then pressed to fix the positive electrode current collector.

<Negative electrode>
The negative electrode in the nonaqueous electrolyte secondary battery member and the nonaqueous electrolyte secondary battery according to one embodiment of the present invention is particularly limited as long as it is generally used as the negative electrode of the nonaqueous electrolyte secondary battery. However, for example, a negative electrode sheet having a structure in which an active material layer containing a negative electrode active material and a binder resin is formed on a current collector can be used. The active material layer may further contain a conductive additive.

  Examples of the negative electrode active material include materials that can be doped / undoped with lithium ions, lithium metal, and lithium alloys. Examples of the material include a carbonaceous material. Examples of the carbonaceous material include natural graphite, artificial graphite, coke, carbon black, and pyrolytic carbon.

  Examples of the negative electrode current collector include Cu, Ni, stainless steel, and the like. In particular, in a lithium ion secondary battery, Cu is more preferable because it is difficult to form an alloy with lithium and it can be easily processed into a thin film.

  As a method for producing a sheet-like negative electrode, for example, a method in which a negative electrode active material is pressure-molded on a negative electrode current collector; the negative electrode active material is made into a paste using an appropriate organic solvent, For example, a method of applying to an electric body, drying and pressurizing to adhere to a negative electrode current collector; The paste preferably contains the conductive aid and the binder.

<Non-aqueous electrolyte>
The non-aqueous electrolyte in the non-aqueous electrolyte secondary battery according to an embodiment of the present invention is not particularly limited as long as it is a non-aqueous electrolyte generally used in a non-aqueous electrolyte secondary battery. For example, a lithium salt A non-aqueous electrolyte solution obtained by dissolving in an organic solvent can be used. Examples of the lithium salt include LiClO ₄ , LiPF ₆ , LiAsF ₆ , LiSbF ₆ , LiBF ₄ , LiCF ₃ SO ₃ , LiN (CF ₃ SO ₂ ) ₂ , LiC (CF ₃ SO ₂ ) ₃ , Li ₂ B ₁₀ Cl ₁₀ , lower aliphatic carboxylic acid lithium salt, LiAlCl _{4 and the} like. The lithium salt may be used alone or in combination of two or more.

  Examples of the organic solvent constituting the non-aqueous electrolyte include carbonates, ethers, esters, nitriles, amides, carbamates and sulfur-containing compounds, and fluorine-containing groups in which these organic solvents are introduced. Examples include fluorine organic solvents. Only one kind of the organic solvent may be used, or two or more kinds may be used in combination.

<Nonaqueous Electrolyte Secondary Battery Member and Nonaqueous Electrolyte Secondary Battery Manufacturing Method>
Examples of the method for producing a member for a non-aqueous electrolyte secondary battery according to an embodiment of the present invention include the positive electrode, the separator for a non-aqueous electrolyte secondary battery according to an embodiment of the present invention, or one of the present invention. The method of arrange | positioning the laminated separator for nonaqueous electrolyte secondary batteries which concerns on embodiment, and a negative electrode in this order is mentioned.

  Moreover, as a manufacturing method of the non-aqueous electrolyte secondary battery according to an embodiment of the present invention, for example, after forming the non-aqueous electrolyte secondary battery member by the above method, the non-aqueous electrolyte secondary battery In one embodiment of the present invention, the nonaqueous electrolyte secondary battery member is placed in a container which is a housing of the container, and then the container is filled with the nonaqueous electrolyte and then sealed while decompressing. Such a non-aqueous electrolyte secondary battery can be manufactured.

  Hereinafter, although an example and a comparative example explain the present invention still in detail, the present invention is not limited to these examples.

[Measuring method]
The physical properties of the polyolefin porous films produced in the examples and comparative examples shown below, and the battery resistance after aging charge / discharge and after charge / discharge cycles of the nonaqueous electrolyte secondary battery were determined using the following methods. Measured.

[Film thickness]
The film thickness of the polyolefin porous film manufactured by the Example shown below and a comparative example was measured using the high precision digital length measuring machine (VL-50) by Mitutoyo Corporation.

[Weight weight]
From the polyolefin porous films produced in the following examples and comparative examples, a square having a side length of 8 cm was cut as a sample, and the weight W (g) of the sample was measured. And the following formula weight basis weight (g / m ² ) = W / (0.08 × 0.08)
The weight per unit area of the polyolefin porous film was calculated.

[Measurement of ultrasonic attenuation rate]
The ultrasonic attenuation rate was measured using a dynamic liquid permeability measuring device (PDA.C.02 manufactured by EMTEC).
(Module Standard). A specific method is described below (see FIG. 1).

  A non-aqueous electrolyte prepared by mixing at EC / EMC / DEC = 3/5/2 (volume ratio) was prepared. Subsequently, the non-aqueous electrolyte was added to the bathtub 1 attached to the dynamic liquid permeability measuring device until the reference line of the bathtub 1 was satisfied.

  Then, using the double-sided tape attached to the dynamic liquid permeability measuring device to the sample holder 2 attached to the dynamic liquid permeability measuring device, the sample attaching position provided on the sample holder 2 is as follows. Samples before measurement were prepared by pasting the polyolefin porous film (separator 3 for nonaqueous electrolyte secondary battery) produced in the examples and comparative examples shown.

  Subsequently, the pre-measurement sample is attached to the dynamic liquid permeability measurement device, and using the attached software of the dynamic liquid permeability measurement device, the measurement conditions are as follows: Algorithm: General, Measurement frequency: 2 MHz, Measurement diameter: The ultrasonic attenuation rate was measured by setting to 10 mm.

At that time, the measurement was started by pressing the test start button of the dynamic liquid permeability measuring apparatus. The time for pressing the test start button was t = 0 ms. When the test start button is pressed, the sample before measurement provided with the sample holder 2 by the constant speed motor begins to drop into the bathtub 1 filled with the nonaqueous electrolyte at a constant speed, and after the drop time (t = 6 ms) has elapsed. The measurement position of bathtub 1 has been reached. Thereafter, the measurement data of the first ultrasonic attenuation rate was measured at time: (t = 7 ms), and thereafter, the ultrasonic attenuation rate was measured at every measurement interval of 4 ms. Immediately after the start of measurement, the value of the minimum point appearing on the vertical axis of the measurement state monitoring graph on the computer was written, and the value of the minimum point was taken as the intensity of the ultrasonic attenuation rate at t = 7 ms. The minimum point is not described in units on the computer, but indicates the voltage value of the DC-DC converter. The unit of the ultrasonic attenuation rate measured by the above method is mV.

[Calculation of slope of ultrasonic attenuation rate curve in region III]
By measuring the ultrasonic attenuation rate, changes in the ultrasonic attenuation rate over time were plotted, and an ultrasonic attenuation rate curve as shown in FIG. 2 was created. In the region III of the ultrasonic attenuation rate curve, the time to reach the point (second inflection point) at which the ultrasonic attenuation rate changes from increasing to decreasing is defined as t = Dms, and the ultrasonic attenuation rate at t = Dms. And a tangent line using the least square method, and the time when the correlation coefficient of the least square method is closest to 0.985 is t = Ems, and t = Dms And the magnitude of the slope of the straight line connecting the ultrasonic attenuation rate at t = Ems. The magnitude of the calculated straight line slope was defined as the tangential slope magnitude c in the region III of the ultrasonic attenuation rate curve.

  Similarly, another ultrasonic attenuation rate curve was created with the intensity of the ultrasonic attenuation rate at the initial data measurement time (t = 7 ms) being 100%. Based on the other ultrasonic attenuation rate curve, the magnitude c ′ of the tangential slope in the region III of the other ultrasonic attenuation rate curve was calculated by the same method as the above-described calculation method.

[Measurement of battery resistance after aging charge / discharge and charge / discharge cycles]
<Degassing operation>
For non-aqueous electrolyte secondary battery, voltage range at 25 ° C .; 4.1 to 2.7 V, charging current value; 0.1 C CC-CV charging (end current condition 0.02 C), discharging current value 0 .1C initial charge / discharge was performed under the condition of CC discharge of 2C (the current value for discharging the rated capacity by 1 hour discharge capacity in 1 hour is 1C, the same applies hereinafter) (first charge / discharge process) ).

  Subsequently, in the secondary battery for non-aqueous electrolyte after the first charge / discharge, after cutting a blank portion (= gas accumulation portion) where the positive and negative electrode plates do not exist inside the laminate pouch leaving a re-seal portion, By applying a vacuum, excess gas components generated by the first charge / discharge were removed, and the laminate pouch of the secondary battery for non-aqueous electrolyte was pressure-bonded and sealed again (gas venting step).

<Measurement of battery resistance after aging charge / discharge>
With respect to the non-aqueous electrolyte secondary battery subjected to the above degassing operation, a voltage range at 25 ° C .; 4.1 to 2.7 V, a charging current value; 0.2 C CC-CV charging (end current condition 0. 02C), and three cycles of aging charge / discharge were performed under the condition of CC discharge with a discharge current value of 0.2C.

Next, IR drop after discharge 10 s in the first cycle of aging charge / discharge was measured. That is, the battery resistance was calculated by dividing by a current value of 4.1 mA (= 0.2 C) using a voltage difference (IR drop) obtained by subtracting the voltage of discharge 0s from the voltage of discharge 10s. The calculated battery resistance, and a battery resistance R ₁ after aging discharge. R ₁ represents the battery resistance after 10 seconds of discharge after one cycle of aging charge / discharge.

<Measurement of battery resistance after charge / discharge cycle>
The non-aqueous electrolyte secondary battery subjected to the above aging charge / discharge at 55 ° C., voltage range; 4.2 to 2.7 V, charge current value; 1 C CC-CV charge (end current condition) 0.02C), discharge current value; 20 cycles of charge / discharge were performed with charge / discharge being performed as one cycle under the condition of CC discharge of 10C. In the same manner as the measurement of the battery resistance after aging charge / discharge, the IR drop after 10 seconds of discharge at the 20th cycle was measured, and the battery resistance of the nonaqueous electrolyte secondary battery was calculated. The calculated battery resistance, and a battery resistance R ₂ after the charge and discharge cycles.

[Example 1]
18 parts by weight of ultrahigh molecular weight polyethylene powder (Hi-Zex Million 145M, manufactured by Mitsui Chemicals, Inc.) and 2 parts by weight of hydrogenated petroleum resin (melting point 164 ° C., softening point 125 ° C.) were prepared. These powders were pulverized and mixed with a blender until the particle diameters of the powders were the same to obtain a mixture. The above mixture was added to a biaxial kneader from a quantitative feeder and melt-kneaded to obtain a melt-kneaded product.

  Further, at the time of the melt kneading, 80 parts by weight of liquid paraffin was side fed while being pressurized to a biaxial kneader with a pump, and melt kneaded together. At this time, the temperature was set so that the average temperature immediately before liquid paraffin charging (segment barrel 1) and the liquid paraffin charging portion (segment barrel 2) was 173 ° C. Thereafter, the melt-kneaded product was extruded through a gear pump from a T die set at 210 ° C. into a sheet shape to obtain a sheet-shaped polyolefin resin composition.

  The above-mentioned sheet-like polyolefin resin composition was stretched 4.5 times in the MD direction and then stretched 6.0 times in the TD direction. The value obtained by dividing the draw ratio in the MD direction by the draw ratio in the TD direction (hereinafter referred to as the draw ratio) was 0.75. The stretched polyolefin resin composition described above was washed with a washing liquid (heptane). Then, after drying at room temperature with respect to the above-mentioned washed polyolefin resin composition, it heat-fixed over 15 minutes at the temperature of 132 degreeC, and produced the polyolefin porous film. The produced polyolefin porous film is designated as polyolefin porous film 1. The polyolefin porous film 1 had a film thickness of 13 μm and a porosity of 32%.

[Example 2]
A polyolefin porous film was produced in the same manner as in Example 1 except that heat setting was performed at a temperature of 120 ° C. for 1 minute. The produced polyolefin porous film is designated as polyolefin porous film 2. The polyolefin porous film 2 had a film thickness of 18 μm and a porosity of 56%.

[Example 3]
Using hydrogenated petroleum resin (melting point 131 ° C, softening point 90 ° C), set the average temperature immediately before liquid paraffin charging (segment barrel 1) and the liquid paraffin charging part (segment barrel 2) to be 168 ° C. Except that the film was stretched 4.2 times in the MD direction, 6.0 times in the TD direction, and a stretch ratio of 0.70, and heat setting was performed at a temperature of 133 ° C. for 15 minutes. A polyolefin porous film was prepared by a simple method. The produced polyolefin porous film is designated as polyolefin porous film 3. The film thickness of the polyolefin porous film 3 was 13 μm, and the porosity was 35%.

[Example 4]
Using hydrogenated petroleum resin (melting point 131 ° C, softening point 90 ° C), set the average temperature immediately before liquid paraffin charging (segment barrel 1) and the liquid paraffin charging part (segment barrel 2) to be 168 ° C. Except that the film was stretched 4.2 times in the MD direction, 6.0 times in the TD direction, and a stretch ratio of 0.70, and heat setting was performed at a temperature of 100 ° C. for 8 minutes. A polyolefin porous film was prepared by a simple method. The produced polyolefin porous film is referred to as a polyolefin porous film 4. Polyolefin porous film 4
The film thickness was 22 μm, and the porosity was 60%.

[Comparative Example 1]
Using 20 parts by weight of ultra high molecular weight polyethylene powder (Hi-Zex Million 145M, manufactured by Mitsui Chemicals), without adding hydrogenated petroleum resin (melting point 164 ° C., softening point 125 ° C.), and immediately before adding liquid paraffin ( The average temperature of the segment barrel 1) and the liquid paraffin charging part (segment barrel 2) is set to 165 ° C., and is 3.2 times in the MD direction, 6.0 times in the TD direction, and a draw ratio of 0.53. A polyolefin porous film was produced in the same manner as in Example 1 except that the film was stretched and heat-set at a temperature of 133 ° C. for 15 minutes. The produced polyolefin porous film is referred to as polyolefin porous film 5. The film thickness of the polyolefin porous film 5 was 13 μm, and the porosity was 37%.

[Comparative Example 2]
68% by weight of ultra high molecular weight polyethylene powder (GUR2024, manufactured by Ticona), 32% by weight of polyethylene wax (FNP-0115, manufactured by Nippon Seiki Co., Ltd.) having a weight average molecular weight of 1000, and the total of the ultra high molecular weight polyethylene and polyethylene wax. As 100 parts by weight, 0.4 parts by weight of an antioxidant (Irg1010, manufactured by Ciba Specialty Chemicals), 0.1 part by weight (P168, manufactured by Ciba Specialty Chemicals), 1.3 parts by weight of sodium stearate After adding calcium carbonate (manufactured by Maruo Calcium Co., Ltd.) having an average particle size of 0.1 μm so as to be 38% by volume with respect to the total volume, and mixing these with a Henschel mixer as a powder, a twin-screw kneader And kneaded to obtain a polyolefin resin composition. The polyolefin resin composition was rolled with a pair of rolls having a surface temperature of 150 ° C., and then stretched 1.5 times in the MD direction to prepare a sheet. Calcium carbonate was removed from the sheet by immersing the sheet in an aqueous hydrochloric acid solution (hydrochloric acid 4 mol / L, nonionic surfactant 0.5% by weight). Subsequently, the sheet from which the calcium carbonate had been removed was stretched at a stretching temperature of 105 ° C. to 6.2 times in the TD direction and a stretching ratio of 0.24 to produce a polyolefin porous film. The produced polyolefin porous film is referred to as a polyolefin porous film 6. The polyolefin porous film 6 had a film thickness of 16 μm and a porosity of 65%.

[Manufacture of non-aqueous electrolyte secondary batteries]
The polyolefin porous films 1 to 6 produced in Examples 1 to 4 and Comparative Examples 1 and 2 were used as separators for non-aqueous electrolyte secondary batteries. A battery was produced.

(Preparation of positive electrode)
A commercially available positive electrode manufactured by applying LiNi _0.5 Mn _0.3 Co _0.2 O ₂ / conductive material / PVDF (weight ratio 92/5/3) to an aluminum foil was used. Cut off the aluminum foil so that the size of the portion where the positive electrode active material layer is formed is 45 mm × 30 mm and the portion where the width is 13 mm and the positive electrode active material layer is not formed remains on the positive electrode. A positive electrode was obtained. The thickness of the positive electrode active material layer was 58 μm, the density was 2.50 g / cm ³ , and the positive electrode capacity was 174 mAh / g.

(Preparation of negative electrode)
A commercially available negative electrode produced by applying graphite / styrene-1,3-butadiene copolymer / sodium carboxymethylcellulose (weight ratio 98/1/1) to a copper foil was used. Cut the copper foil so that the negative electrode active material layer has a size of 50 mm × 35 mm and the outer periphery has a width of 13 mm and no negative electrode active material layer formed on the negative electrode. A negative electrode was obtained. The thickness of the negative electrode active material layer was 49 μm, the density was 1.40 g / cm ³ , and the negative electrode capacity was 372 mAh / g.

(Assembly of non-aqueous electrolyte secondary battery)
In the laminate pouch, the positive electrode, the polyolefin porous film as the non-aqueous electrolyte secondary battery separator, and the negative electrode were laminated (arranged) in this order to obtain a non-aqueous electrolyte secondary battery member. At this time, the positive electrode and the negative electrode were disposed so that the entire main surface of the positive electrode active material layer of the positive electrode was included in the range of the main surface of the negative electrode active material layer of the negative electrode (overlaid on the main surface).

Subsequently, the non-aqueous electrolyte secondary battery member was put in a bag in which an aluminum layer and a heat seal layer were laminated, and 0.25 mL of the non-aqueous electrolyte was put in this bag. The non-aqueous electrolyte is an electrolyte at 25 ° C. in which LiPF ₆ having a concentration of 1.0 mol / liter is dissolved in a mixed solvent of ethyl methyl carbonate, diethyl carbonate and ethylene carbonate in a volume ratio of 50:20:30. It was. And the non-aqueous-electrolyte secondary battery was produced by heat-sealing the said bag, decompressing the inside of a bag. The design capacity of the non-aqueous electrolyte secondary battery 1 was 20.5 mAh. The nonaqueous electrolyte secondary batteries manufactured using the polyolefin porous films 1 to 6 as the polyolefin porous film are referred to as nonaqueous electrolyte secondary batteries 1 to 6, respectively.

[result]
“Magnitude of slope c in region III of ultrasonic attenuation rate curve” and “region III of ultrasonic attenuation rate curve” of polyolefin porous films 1 to 6 produced in Examples 1 to 4 and Comparative Examples 1 and 2 Table 1 below shows the magnitude of the inclination c ′ ”. Moreover, “after 1 cycle of aging charge / discharge” of the non-aqueous electrolyte secondary batteries 1 to 6 produced using the polyolefin porous films 1 to 6 produced in Examples 1 to 4 and Comparative Examples 1 and 2, respectively. Table 2 below shows “battery resistance: R ₁ ” and “battery resistance after charge / discharge cycle: R ₂ ”.

[Conclusion]
In the polyolefin porous films 1 to 4 produced in Examples 1 to 4, the magnitude of the slope c in the region III of the ultrasonic attenuation curve is 3.5 mV / s or more and 14 mV / s or less. On the other hand, in the polyolefin porous films 5 and 6 manufactured in Comparative Examples 1 and 2, the magnitude of the inclination c in the region III of the ultrasonic attenuation curve is out of the above range.

  After one cycle of aging charge / discharge of a nonaqueous electrolyte secondary battery incorporating a separator for a nonaqueous electrolyte secondary battery including the polyolefin porous films 5 and 6 produced in Comparative Examples 1 and 2 from the description in Table 2 The battery resistance exceeded 1.31Ω, and the battery resistance after the charge / discharge cycle exceeded 1.20Ω. On the other hand, the battery resistance after one cycle of aging charge / discharge of the nonaqueous electrolyte secondary battery incorporating the separator for nonaqueous electrolyte secondary batteries including the polyolefin porous films 1 to 4 is less than 1.31Ω. Yes, the battery resistance after the charge / discharge cycle was less than 1.20 Ω, which was a result that both were lower than those of Comparative Examples 1 and 2.

  A separator for a non-aqueous electrolyte secondary battery according to an embodiment of the present invention is a battery after aging charge / discharge and after a charge / discharge cycle of a non-aqueous electrolyte secondary battery including the separator for a non-aqueous electrolyte secondary battery. Resistance can be reduced. Therefore, the separator for nonaqueous electrolyte secondary batteries according to an embodiment of the present invention can be suitably used in various industries that handle nonaqueous electrolyte secondary batteries.

1 Bath 2 Sample holder 3 Nonaqueous electrolyte secondary battery separator

Claims (4)

A separator for a non-aqueous electrolyte secondary battery including a polyolefin porous film,
The non-aqueous electrolyte solution 2 has a tangential slope of region III in the ultrasonic attenuation rate curve of the separator for a non-aqueous electrolyte secondary battery immersed in the electrolyte solution of 3.5 mV / s to 14 mV / s. Secondary battery separator.
(Here, the region III is an ultrasonic attenuation rate curve showing a time change of the ultrasonic attenuation rate with respect to 2 MHz ultrasonic waves of the separator for a non-aqueous electrolyte secondary battery immersed in the electrolytic solution. The area after the inflection point of 2 is shown.)   A laminated separator for a nonaqueous electrolyte secondary battery comprising the separator for a nonaqueous electrolyte secondary battery according to claim 1 and an insulating porous layer.   The non-aqueous electrolyte secondary battery separator according to claim 1 or the non-aqueous electrolyte secondary battery laminated separator according to claim 2 and the negative electrode are arranged in this order. A member for a water electrolyte secondary battery.   A nonaqueous electrolyte secondary battery comprising the separator for a nonaqueous electrolyte secondary battery according to claim 1 or the laminated separator for a nonaqueous electrolyte secondary battery according to claim 2.

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