JP2006164873A - Non-aqueous electrolytic solution secondary battery - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a non-aqueous electrolytic solution in which an injection property of the electrolytic solution in a manufacturing process is high, which is superior in a high-temperature storage property, and of which the safety is high by improving electrolytic solution retaining force. <P>SOLUTION: A separator is composed of at least three layers of a heat-resistant porous resin layer, a porous polyethylene layer, and a porous polypropylene layer, and by arranging so that a positive electrode be opposed to the porous polypropylene layer and a negative electrode be opposed to the heat-resistant porous resin layer, a void balance in an electrode group is improved. <P>COPYRIGHT: (C)2006,JPO&NCIPI

Description

  The present invention relates to a separator for a non-aqueous electrolyte secondary battery, and more particularly to a separator structure that can achieve safety, performance, and productivity.

  A non-aqueous electrolyte secondary battery represented by a lithium ion secondary battery has an advantage of high energy density, but has a problem in safety in an abnormal state. For this reason, the porous polyolefin separator used is not only for electrically insulating the positive and negative electrodes during normal operation, but also when the battery temperature rises significantly due to excess current due to an external short circuit, the separator softens and becomes clogged. The conductivity is lost and the battery function is stopped (hereinafter referred to as shutdown). However, when the temperature of the battery rises even after shutdown, the separator melts and the positive and negative electrodes are short-circuited (hereinafter referred to as meltdown). The shutdown and the meltdown are in a contradictory relationship. For example, when the heat melting property is increased to enhance the shutdown, there is a problem that the meltdown temperature is lowered.

In order to solve this problem, many separators made of composite films having different functions have been proposed. As an example, a composite film consisting of a heat-resistant porous layer made of polyimide, polyamideimide, aramid, etc. and a shutdown layer made of polyethylene or the like is constructed, and the heat-resistant porous layer is arranged on the positive electrode side to overheat the positive electrode active material. Corresponding methods (for example, Patent Document 1) and conversely methods (for example, Patent Document 2) that are arranged on the negative electrode side and cope with the deterioration of the function of this layer over time have been proposed.
Japanese Patent Laid-Open No. 2000-100408 JP 2001-266949 A

  However, the heat-resistant porous layer tends to have a low porosity in the manufacturing process (stretching process, etc.) of the separator. On the other hand, the positive electrode is often designed to have a low porosity (high density) from the viewpoint of increasing the capacity and ensuring electronic conductivity. Therefore, when the heat-resistant porous layer and the high-density positive electrode are combined as in Patent Document 1, the electrolyte holding power on the positive electrode side is extremely lowered, and the productivity is lowered when the electrolyte is injected in the manufacturing process. It was.

  Further, when the heat-resistant porous layer is opposed to the negative electrode side as in Patent Document 2, the problem as in Patent Document 1 can be avoided, but general polyethylene as a shutdown layer is exposed to a high temperature under the charging potential of the positive electrode. Therefore, when polyethylene is disposed on the positive electrode side, the high-temperature storage characteristics tend to decrease. As a countermeasure, when polypropylene is used instead of polyethylene, there is a problem that the overheat safety is insufficient because the shutdown temperature is high.

  The present invention has been made in view of these problems, and an object of the present invention is to provide a highly safe non-aqueous electrolyte secondary battery that has high electrolyte solution retention and excellent high-temperature storage characteristics. .

  In order to solve the above-described problems, the non-aqueous electrolyte secondary battery of the present invention has a separator comprising at least three layers of a heat-resistant porous resin layer, a porous polyethylene layer and a porous polypropylene layer, and a positive electrode being a porous polypropylene layer. And the negative electrode is opposed to the heat resistant porous resin layer.

  By disposing the heat-resistant porous resin layer with a relatively low porosity on the negative electrode side with a relatively high porosity, the electrolyte holding power of the positive and negative electrodes and the separator becomes uniform, so the productivity of the electrolyte injection process is improved. improves. In addition, by disposing a porous polypropylene layer at a location exposed to the positive electrode potential and disposing a porous polyethylene layer inside thereof, the shutdown function can be exhibited at a desired temperature while improving the high-temperature storage characteristics.

  The present invention solves various problems that conventional separators have, so it is possible to provide a non-aqueous electrolyte secondary battery excellent in high-temperature storage characteristics and safety with high productivity. It becomes.

  Hereinafter, the best mode for carrying out the present invention will be described in detail.

  The gist of the present invention is that the separator disposed between the positive and negative electrodes is composed of at least three layers of a heat-resistant porous resin layer, a porous polyethylene layer and a porous polypropylene layer, and a porous propylene layer on the positive electrode side, A heat-resistant porous resin layer is disposed on the negative electrode side.

  As the heat-resistant porous resin disposed on the negative electrode side, a heat-resistant resin having a heat distortion temperature of 260 ° C. or higher obtained by measuring the deflection temperature under load at 1.82 MPa, test method ASTM-D648 of the American Society for Testing Materials is used. It is desirable. Here, heat resistance means that the glass transition point and melting point are sufficiently high, and the thermal decomposition starting temperature accompanied by chemical change is sufficiently high. Temperature is used. It can be said that the higher the heat distortion temperature, the easier it is to maintain the separator shape even when heat shrinkage occurs. When this heat distortion temperature is 260 ° C. or higher, sufficiently high thermal stability can be exhibited even when the battery temperature further rises due to heat storage during battery overheating (usually about 180 ° C.). Examples of such heat-resistant porous resin include aramid, polyamideimide, polyimide, polyphenylene sulfide, polyetherimide, polyethylene terephthalate, polyarylate, polyether nitrile, polyether ether ketone, polybenzimidazole and the like. Among these, aramid, polyamideimide, and polyimide are preferable from the viewpoint of forming a porous resin layer having extremely high electrolytic solution holding power and heat resistance.

  This heat-resistant porous resin layer needs to be disposed on the negative electrode side. When this low porosity layer is disposed so as to face the positive electrode (designed to have a low porosity), the void distribution of the electrode group consisting of the positive and negative electrodes and the separator becomes non-uniform. That is, since the positive electrode side generally has few voids and the negative electrode side generally has many voids, the electrolyte solution is impregnated on the positive electrode side when the electrolyte solution is injected, so that the entire electrode group is impregnated with the electrolyte solution. It will take time.

  The thickness of the heat-resistant porous resin layer is not particularly limited, but is preferably 1 to 16 μm and more preferably 2 to 10 μm from the viewpoint of ensuring internal short circuit safety and electric capacity. When the thickness is less than 1 μm, the heat-resistant porous resin layer has a low effect of suppressing heat shrinkage of the porous polyethylene layer and the porous polypropylene layer in a high temperature environment. On the other hand, when the thickness exceeds 16 μm, the impedance increases due to the influence of the heat-resistant porous resin layer having a low porosity (low ion conductivity), and the charge / discharge characteristics are slightly decreased. Furthermore, the porosity of the heat-resistant porous resin layer is preferably 20 to 70% from the viewpoint that lithium ions can sufficiently move.

Of the remaining two layers (the porous polyethylene layer and the porous polypropylene layer), the porous polypropylene layer is preferably disposed on the positive electrode side. While the porous polyethylene layer has an appropriate shutdown temperature and high safety, it is inferior in stability under the positive electrode charging potential. Therefore, when exposed to a high temperature for a long time, it is considered that decomposition accompanied by consumption of the electrolytic solution occurs. Therefore, by disposing a porous polypropylene layer on the positive electrode side and providing a porous polyethylene layer on the inside thereof, the shutdown function can be exhibited without impairing the high-temperature storage characteristics. The pore diameters of these porous polyethylene layer and porous polypropylene layer are preferably 0.01 to 10 μm from the viewpoint of achieving both ion conductivity and mechanical strength.

  The total thickness of the separator composed of at least three layers of the above-mentioned heat resistant porous resin layer, porous polyethylene layer and porous polypropylene layer is not particularly limited, but comprehensively considers various safety, battery characteristics, and battery design capacity. In consideration, it is preferably 5 to 35 μm.

  These laminated structures can be realized by forming a heat-resistant porous resin layer on a base material using the porous polyethylene layer and the porous polypropylene layer as the base material. For example, when aramid is used as the heat-resistant porous resin, it can be prepared by dissolving it in a polar solvent such as N-methylpyrrolidone (hereinafter abbreviated as NMP) and then applying it onto the substrate. Here, by adding an inorganic oxide filler to the aramid solution, a coating layer having extremely high heat resistance can be formed. As the inorganic oxide filler, for example, an inorganic porous material such as alumina, zeolite, silicon nitride, or silicon carbide is preferably selected.

  When polyimide is used as the heat-resistant porous resin, it is prepared by casting a polyamic acid solution, which is a precursor, and then creating a porous thin film by stretching, and then integrating the substrate with a heat roll or the like. it can. Here, the porosity of the heat resistant porous resin layer can be controlled by changing the stretching process conditions.

  For positive electrodes, lithium cobaltate and its modified products (such as those obtained by eutectic aluminum or magnesium), lithium nickelate and its modified products (such as those in which nickel is partially substituted with cobalt or manganese), manganese Examples thereof include composite oxides such as lithium acid and modified products thereof. As the binder, polytetrafluoroethylene, modified acrylonitrile rubber particles (such as BM-500B (trade name) manufactured by Nippon Zeon Co., Ltd.), carboxymethylcellulose (hereinafter abbreviated as CMC) having a thickening effect, polyethylene oxide, soluble modification It may be combined with acrylonitrile rubber (such as BM-720H (trade name) manufactured by Nippon Zeon Co., Ltd.), and is a single polyvinylidene fluoride (hereinafter abbreviated as PVDF) having both binding properties and thickening and its The modified products may be used alone or in combination. As the conductive agent, acetylene black, ketjen black, and various graphites may be used alone or in combination.

  For the negative electrode, various natural graphites and silicon-based composite materials such as artificial graphite and silicide, lithium alloys containing at least one selected from tin, aluminum, zinc, and magnesium, and various alloy composition materials can be used as the active material. As the binder, various resin materials such as PVDF and modified products thereof can be used. From the viewpoint of improving the overcharge safety as described above, for example, a styrene-butadiene copolymer (hereinafter abbreviated as SBR). It is more preferable to use a mixed water-soluble binder between the modified product and a cellulose resin such as CMC.

For the electrolytic solution, it is possible to use various lithium compounds such as LiPF ₆ and LiBF ₄ as a salt. Further, ethylene carbonate (EC), dimethyl carbonate (DMC), diethyl carbonate (DEC), and ethyl methyl carbonate (EMC) can be used alone or in combination as a solvent. In order to form a good film on the positive and negative electrodes, vinylene carbonate (VC), cyclohexylbenzene (CHB), and modified products thereof can be used.

EXAMPLES Hereinafter, although this invention is demonstrated concretely based on an Example, the content described here is only the illustration of this invention, and this invention is not limited to these.

Example 1
(A) Production of positive electrode 3 kg of lithium cobaltate as a positive electrode active material, 1 kg of “# 1320 (trade name)” (NMP solution containing 12% by weight of PVDF) manufactured by Kureha Chemical Co., Ltd. as a positive electrode binder, Acetylene black 90 g as an agent and an appropriate amount of NMP were stirred with a double-arm kneader to prepare a positive electrode mixture paint. This paint was applied to both sides of a 15 μm thick aluminum foil as a positive electrode current collector, excluding the connecting portion of the positive electrode lead, and the dried coating film was rolled with a roller to obtain an active material layer density (active material weight / A positive electrode mixture layer having a mixture layer volume) of 3.3 g / cm ³ was formed. Under the present circumstances, the thickness of the electrode plate which consists of aluminum foil and a positive mix layer was controlled to 160 micrometers. Thereafter, the electrode plate was slit to a width that could be inserted into a cylindrical battery (diameter 18 mm, length 65 mm) battery can to obtain a positive electrode hoop.
(B) Production of Negative Electrode 3 kg of artificial graphite as the negative electrode active material and “BM-400B (trade name)” manufactured by Nippon Zeon Co., Ltd. as the negative electrode binder (40% by weight of a modified styrene-butadiene copolymer) An aqueous dispersion containing 75 g, 30 g of CMC as a thickener, and an appropriate amount of water were stirred with a double-arm kneader to prepare a negative electrode mixture paint. This paint was applied to both sides of a 10 μm thick copper foil as a negative electrode current collector, excluding the negative electrode lead connection portion, and the dried coating film was rolled with a roller to obtain an active material layer density (active material weight / A negative electrode mixture layer having a mixture layer volume) of 1.4 g / cm ³ was formed. Under the present circumstances, the thickness of the electrode plate which consists of copper foil and a negative mix layer was controlled to 180 micrometers. Thereafter, the electrode plate was slit to a width that could be inserted into the battery can of the cylindrical battery described above to obtain a negative electrode hoop.
(C) Production of separator A porous polyethylene thin film having a thickness of 8 μm and a porous polypropylene thin film having a thickness of 8 μm were overlapped and rolled with a hot roll to obtain a porous polyethylene-porous polypropylene laminated film. Further, as the heat-resistant porous resin layer, a layer made of an aramid resin (thermal deformation temperature (test method ASTM-D648, deflection temperature under load at 1.82 MPa): 320 ° C. or higher) was formed on the substrate.

The method for forming the aramid resin layer is shown below. 6.5 parts by weight of dry anhydrous calcium chloride was added to 100 parts by weight of NMP and heated in a reaction vessel to completely dissolve. After this calcium chloride-added NMP solution was returned to room temperature, 3.2 parts by weight of paraphenylenediamine was added and completely dissolved. Thereafter, the reaction vessel was placed in a constant temperature bath at 20 ° C., 5.8 parts by weight of terephthalic acid dichloride was added dropwise over 1 hour, and polyparaphenylene terephthalamide (hereinafter abbreviated as PPTA) was synthesized by a polymerization reaction. Then, it was left for 1 hour in a thermostatic chamber, replaced with a vacuum chamber after the reaction was completed, and degassed by stirring for 30 minutes under reduced pressure. The obtained polymerization solution was further diluted with a calcium chloride-added NMP solution to prepare an NMP solution of an aramid resin having a PPTA concentration of 1.4% by weight. The NMP solution of the aramid resin thus obtained was coated thinly with a bar coater with the coated surface as the porous polyethylene layer side, dried with hot air at 80 ° C. (wind speed 0.5 m / sec), and laminated. A membrane was obtained. Thereafter, the laminated film was sufficiently washed with pure water to remove the calcium chloride, and the aramid resin layer was made porous and dried. Thereby, an aramid-porous polyethylene-porous polypropylene laminated film having a total thickness of 20 μm was produced.
(D) Preparation of non-aqueous electrolyte After dissolving LiPF ₆ at a concentration of 1 mol / L in a mixture of non-aqueous solvent containing EC, DMC and EMC at a volume ratio of 2: 3: 3, VC was non-aqueous electrolyzed. A non-aqueous electrolyte was prepared by adding 3 parts by weight per 100 parts by weight of the liquid.
(E) Production of Battery A cylindrical battery was produced in the following manner using the above-described positive and negative electrodes, separator, and non-aqueous electrolyte. First, the positive electrode and the negative electrode were each cut to a predetermined length, and one end of the positive electrode lead was connected to the positive electrode lead connection portion, and one end of the negative electrode lead was connected to the negative electrode lead connection portion. Thereafter, the positive and negative electrodes were arranged and wound so that the aramid resin in the laminated separator was on the negative electrode side and the porous polypropylene was on the positive electrode side, and a cylindrical electrode group with the outermost periphery covered with the separator was formed. This electrode group was sandwiched between an upper insulating ring and a lower insulating ring and accommodated in a battery can. Next, 5 g of the above non-aqueous electrolyte solution was poured into the battery can, and then the pressure was reduced to 133 Pa. The electrode group surface was left until no electrolyte residue was observed, and the electrode group was impregnated with the electrolyte solution.

  After that, the positive electrode lead is welded to the back surface of the battery lid and the negative electrode lead is welded to the inner bottom surface of the battery can. Finally, the opening of the battery can is closed with the battery lid having the insulating packing on the periphery. Type lithium ion secondary battery was produced. This is referred to as the battery of Example 1.

(Example 2)
With respect to the porous polyethylene-porous polypropylene laminated film (separator precursor) of Example 1, as a heat-resistant porous resin layer, a deflection temperature under load (thermal deformation temperature) with a polyimide resin (test method ASTM-D648 (1.82 MPa)) ): 360 ° C. or higher).

  The formation method of a polyimide resin layer is shown below. After casting the precursor polyamic acid solution, a porous thin film was prepared by stretching. This thin film was heated to 300 ° C. to perform dehydration imidation to obtain a porous layer made of a polyimide resin having a thickness of 6 μm. Thereafter, the polyimide resin layer was superposed on the porous polyethylene layer side and rolled with a hot roll at 80 ° C. to produce a laminated film, and a polyimide-porous polyethylene-porous polypropylene laminated film having a total thickness of 22 μm was obtained. . The battery manufactured in the same manner as in Example 1 is referred to as the battery of Example 2.

(Example 3)
With respect to the porous polyethylene-porous polypropylene laminated film (separator precursor) of Example 1, as a heat-resistant porous resin layer, a deflection temperature under load (thermal deformation) with a polyamide-imide resin (test method ASTM-D648 (1.82 MPa)) Temperature): 278 ° C. or higher).

  The method for forming the polyamideimide resin layer is shown below. Trimellitic anhydride monochloride and diamine were mixed in an NMP solvent at room temperature to obtain an NMP solution of polyamic acid. This polyamic acid NMP solution is coated on the porous polyethylene layer side thinly with a bar coater, and after removing the solvent by washing with water, it becomes polyamidoimide with hot air at 80 ° C. (wind speed 0.5 m / sec). Thus, dehydration and ring closure were carried out to obtain a polyamideimide-porous polyethylene-porous propylene film layer having a total thickness of 20 μm. The battery manufactured in the same manner as in Example 1 is referred to as the battery of Example 3.

Example 4
A battery produced in the same manner as in Example 1 except that 250 parts by weight of alumina particles having an average particle size of 0.1 μm was added to 100 parts by weight of aramid resin solid content in the aramid resin-NMP solution used in Example 1, The battery of Example 4 is assumed.

(Example 5)
In Example 1, while a laminated film composed of two layers of porous polyethylene and porous polypropylene was used as a separator precursor, a porous polypropylene film having a thickness of 6 μm was superimposed on both sides of a porous polyethylene film having a thickness of 6 μm, A battery produced in the same manner as in Example 1 except that a laminated film composed of three layers of porous polypropylene-porous polyethylene-porous polypropylene having a thickness of 18 μm was produced by rolling with a hot roll, and this was used as a separator precursor. Is the battery of Example 5.

(Example 6)
For the porous polyethylene-porous polypropylene laminate film (separator precursor) of Example 1, polyphenylene sulfide resin was used as the heat-resistant porous resin layer.

  The formation method of a polyphenylene sulfide resin layer is shown below. 1-chloronaphthalene and polyphenylene sulfide short fiber ("Torcon" manufactured by Toray Industries, Inc. (single yarn fineness 0.9 denier, fiber length 6 mm, deflection temperature under load test method ASTM-D648 (1.82 MPa) ( Thermal deformation temperature): 260 ° C. or higher)) was dissolved at 280 ° C., and a well-stirred solution with addition of alumina having a median diameter of 0.3 μm as a filler was applied onto a glass plate at 210 ° C. with a bar coater, A drying treatment was performed in a drying furnace at 250 ° C. for 3 hours to obtain a brown film. The brown film was washed sequentially with N, N, -dimethylformamide and methanol, and then washed with pure water to obtain a porous film. Thereafter, the polyimide resin layer was superposed on the porous polyethylene layer side and rolled with a hot roll at 80 ° C. to obtain a polyphenylene sulfide-porous polyethylene-porous polypropylene laminated film having a total thickness of 23 μm. A battery manufactured in the same manner as in Example 1 is referred to as the battery of Example 6.

(Example 7)
With respect to the porous polyethylene-porous polypropylene laminated film (separator precursor) of Example 1, as a heat-resistant porous resin layer, a deflection temperature under load (heat at a test method ASTM-D648 (1.82 MPa)) Deformation temperature): 190 ° C. or higher) was used.

  The method for forming the polyetherimide resin layer is shown below. 2,2,3,3-Tetracarboxydiphenylene ether dianhydride and diamine were mixed in NMP solvent at room temperature to prepare a solution. This NMP solution is coated on the porous polyethylene layer side, thinly coated with a bar coater, solvent removed by washing with water, and dehydrated to become polyetherimide with hot air at 120 ° C. (wind speed 0.5 m / sec). Thus, a polyetherimide-porous polyethylene-porous polypropylene film layer having a total thickness of 20 μm was obtained. A battery manufactured in the same manner as in Example 1 is referred to as the battery of Example 7.

(Example 8)
With respect to the porous polyethylene-porous polypropylene laminate film (separator precursor) of Example 1, as a heat-resistant porous resin layer, a deflection temperature under load (thermal deformation) with a polyarylate resin (test method ASTM-D648 (1.82 MPa)) Temperature): 175 ° C. or higher).

  The method for forming the polyarylate resin layer is shown below. Biaryphenol A dissolved in an alkaline aqueous solution and tele / iso mixed phthalic acid chloride dissolved using a halogenated hydrocarbon as an organic solvent were reacted at room temperature to synthesize polyarylate in the organic solvent phase. Using this polyarylate-dispersed halogenated hydrocarbon solution, the coated surface is the porous polyethylene layer side, thinly coated with a bar coater, and after removing the solvent with a toluene washing solution, heated to 80 ° C. with hot air (wind speed 0.5 m / sec) And dried to obtain a polyarylate-porous polyethylene-porous polypropylene laminate film layer having a total thickness of 20 μm. A battery manufactured in the same manner as in Example 1 is referred to as the battery of Example 8.

(Comparative Example 1)
A battery produced in the same manner as in Example 1 except that a porous polyethylene film having a thickness of 20 μm was used as a separator is referred to as a battery of Comparative Example 1.

(Comparative Example 2)
An NMP solution of an aramid resin similar to that in Example 1 was prepared and applied onto a porous polyethylene film having a thickness of 16 μm, and a composite film having a thickness of 20 μm was prepared to form a separator. This battery is referred to as the battery of Comparative Example 2.

(Comparative Example 3)
A battery produced in the same manner as in Comparative Example 2 except that the separator produced in Comparative Example 2 was placed on the opposite side of the positive and negative electrodes and wound was used as the battery of Comparative Example 3.

(Comparative Example 4)
A battery produced in the same manner as in Comparative Example 3 except that the polyolefin film in Comparative Example 3 was changed from polyethylene to polypropylene was referred to as the battery of Comparative Example 4.

(Comparative Example 5)
A battery produced in the same manner as in Example 1 except that the separator produced in Example 1 was placed on the opposite side of the positive and negative electrodes and wound was used as the battery of Comparative Example 5.

(Comparative Example 6)
A battery produced in the same manner as in Example 1 except that an aramid resin NMP solution similar to that in Example 1 was applied to both surfaces of a 12 μm thick porous polyethylene thin film to produce a 20 μm composite film as a separator. Is the battery of Comparative Example 6.

  The following evaluation was performed with respect to the obtained battery.

(I) Electrolyte solution injection time In the battery manufacturing process, after injecting the non-aqueous electrolyte into the battery can, the standing time required until no electrolyte residue was observed on the surface of the electrode group was recorded.

(Ii) Heating safety test Preliminary charge / discharge was performed twice according to the following conditions (1) and (2), and the battery was stored in a charged state in a 45 ° C environment for 7 days. Then, the following charging / discharging was performed in a 20 degreeC environment.

(1) Constant current discharge: 400 mA (end voltage 3 V)
(2) Constant current charge: 1400 mA (end voltage 4.2 V)
(3) Constant voltage charging: 4.2 V (end current 100 mA)
(4) Constant current discharge: 2000 mA (final voltage 3 V)
(5) Constant current charging: 1400 mA (end voltage 4.2 V)
(6) Constant voltage charging: 4.2 V (end current 100 mA)
After (6), each battery was placed in a tank at 150 ° C., and the maximum temperature reached on the battery surface was measured.

(Iii) External short circuit test After performing (1) to (6) in (ii) above, each battery was externally short-circuited with an external circuit resistance of 50 mΩ, and the maximum temperature reached on the battery surface was measured.

(Iv) High-temperature storage test After performing (1) to (6) in (ii) above, each battery was placed in a 100 ° C bath and stored for 4 hours. Thereafter, constant current discharge was performed at 2000 mA, and the discharge capacity was determined as a ratio with the capacity of (4) before storage.

  The evaluation results of the test battery produced as described above are shown in (Table 1).

Regarding the time for injecting the electrolytic solution, the case where the aramid which is a heat-resistant porous resin is arranged on the positive electrode side (Comparative Examples 2, 5 and 6) requires 10 minutes or more and takes a long time. In the example and the comparative example, the injection time is shortened. Among them, the heat-resistant porous resin is aramid (Example 1), polyimide (Example 2), and polyamideimide (Example 3) exhibiting an electrolyte solution impregnation comparable to that of a polyethylene single-layer separator (Comparative Example 1). .

  Regarding the heating test, the polyethylene single-layer separator (Comparative Example 1) has low heat resistance, and thus cannot be prevented from overheating, whereas in other Examples and Comparative Examples using the heat-resistant porous resin layer, overheating is not possible. Suppressed. This effect is considered due to the fact that the heat-resistant porous resin layer suppresses the thermal contraction of the separator and suppresses the short circuit between the positive and negative electrodes even at high temperatures. In particular, Examples 1 to 6 using a heat-resistant porous resin (aramid, polyimide, polyamideimide, polyphenylene sulfide) having a heat deformation temperature of 260 ° C. or higher use polyetherimide and polyarylate having a heat deformation temperature of less than 260 ° C. The maximum temperature is kept lower than if it were.

  Regarding the external short circuit test, the sample without the porous polyethylene layer (Comparative Example 4) was overheated due to the delay of the shutdown operation, whereas the other examples and comparative examples having the porous polyethylene layer were overheated. It has been found that the shutdown effect of the porous polyethylene layer is high.

  Regarding recovery characteristics after storage at 100 ° C. for 4 hours, which is a high temperature storage test, the recovery rate of the porous polyethylene layer arranged on the positive electrode side (Comparative Examples 1 and 3) is low, whereas the porous polyethylene layer is on the positive electrode side. In other examples and comparative examples which are not arranged in the above, a high recovery rate is shown. As described above, since the porous polyethylene layer is inferior in stability under the positive electrode charging potential, it is considered that decomposition accompanying consumption of the electrolytic solution occurs when the porous polyethylene layer is exposed to a high temperature for a long time.

  Considering all the above results, the separator of the present invention has a heat resistant porous resin layer, a porous polyethylene layer and a porous polypropylene layer as essential elements, a porous propylene layer on the positive electrode side, and a heat resistance on the negative electrode side. It turns out that it is necessary to arrange | position a porous resin layer.

Further, in order to investigate the influence of the thickness of the heat resistant porous resin layer, a similar prototype battery was prepared for the separator having the heat resistant porous resin layer thickness of 2, 4, 8, 10 μm in Example 1, and the same evaluation was performed. When it did, it turned out that the outstanding battery which can satisfy | fill all the evaluation results of productivity based on heating test safety | security, external short circuit safety | security, high temperature storage characteristics, and electrolyte solution impregnation property is obtained.

In the lithium ion secondary battery using an electrolytic solution composed of a flammable organic non-aqueous solvent, the characteristics can be maintained while improving the safety, and therefore, the present invention is effective in general application of the battery system.

Claims (3)

A non-aqueous electrolyte secondary battery comprising a positive electrode, a negative electrode, a non-aqueous electrolyte, and a separator, wherein the separator is at least three layers of a heat-resistant porous resin layer, a porous polyethylene layer, and a porous polypropylene layer Are stacked,
The non-aqueous electrolyte secondary battery, wherein the positive electrode faces the porous polypropylene layer, and the negative electrode faces the heat-resistant porous resin layer.   The heat-resistant porous layer is made of a heat-resistant resin having a heat deformation temperature of 260 ° C. or higher obtained by measuring the deflection temperature under load at 1.82 MPa, test method ASTM-D648 of the American Society for Testing Materials. The nonaqueous electrolyte secondary battery according to claim 1. The non-aqueous electrolyte secondary battery according to claim 2, wherein the heat-resistant resin is made of any one of polyimide, aramid, and polyamideimide.