JP2005285740A - Porous membrane, its manufacturing method, and lithium ion secondary battery using it - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide an inexpensive separator having satisfactory shut-down characteristics and melt-down characteristics and superior insulation properties. <P>SOLUTION: When glass transition temperature is 70°C or higher, logalithmic viscosity is 0.5 dl/g or higher, and the gross repeating structure unit is 100 mol%, this porous membrane includes a polyamide imide resin layer containing Formula (I) of 20 mol% or higher, and membrane thickness of the gross porous membrane is 5 to 100 μm. The porous membrane is provided as a separator between a positive electrode and a negative electrode capable of absorbing and discharging lithium ions in this lithium ion secondary battery. <P>COPYRIGHT: (C)2006,JPO&NCIPI

Description

  The present invention relates to a polyamide-imide porous membrane that exhibits excellent shutdown temperature characteristics and high meltdown temperature characteristics as a separator for lithium ion secondary batteries that are required to improve safety, a method for producing the same, and lithium using the same The present invention relates to an ion secondary battery.

  In recent years, with the development of electronic portable devices, batteries with high energy density and high electromotive force have been developed. Among them, nonaqueous electrolyte batteries, particularly lithium ion secondary batteries, have been vigorously developed from the viewpoint of high electromotive force. One of the problems with such non-aqueous electrolyte batteries is the danger of using flammable organic solvents. When both electrodes of the battery are short-circuited and a decomposition reaction of the battery contents occurs, the contents are ejected due to a rapid temperature rise inside the battery. In order to solve such problems, there are currently attachment of a safety valve and provision of a shutdown function by a separator containing a meltable component.

  However, the safety valve is not an essential protective measure against a short circuit, but only relieves a sudden pressure increase inside the battery.

  On the other hand, the shutdown function of the separator uses a porous film made of a heat-meltable material. When the temperature inside the battery reaches a certain temperature due to a short circuit or the like, By blocking, the ionic conductivity is hindered and the battery reaction that causes heat generation is suppressed. As such a separator, a porous membrane of an olefin polymer material disclosed in Patent Documents 1 to 3 is disclosed. However, when such a heat-meltable material is used, even if the shutdown function works due to heat rise, if there is a further temperature rise, the film itself melts and the isolation between the electrodes, which is the original function, is impaired. End up. This is a phenomenon called meltdown, which is not preferable for a battery. It has been proposed to widen the range of the shutdown temperature as a remedy for such problems. For example, as disclosed in Patent Documents 4 to 7 and the like, it is a technique of laminating and coating a heat-meltable material on a porous film or a nonwoven fabric substrate. However, these preparation methods may be complicated and an insulation property at the time of shutdown is not necessarily obtained.

Japanese Patent No. 2642206 JP-A-6-212006 Japanese Patent Laid-Open No. 8-138643 Japanese Patent Publication No. 4-1692 JP-A-60-52 JP 61-232560 A Japanese Patent Laid-Open No. 10-6453

  The present invention has been made in view of such circumstances, and an object of the present invention is to provide an inexpensive separator that has excellent shutdown characteristics and melt-down characteristics, which are superior to conventional porous membrane separators, and is excellent in insulation. .

  As a result of intensive studies to achieve the above object, the present invention is excellent in safety and cycle durability by using a porous polyamideimide resin film alone or in combination with other materials as a separator. It was found that a lithium ion secondary battery was obtained. That is, this invention is the following porous membrane, its manufacturing method, and a lithium ion secondary battery using the same.

(1) A polyamide-imide resin layer having a glass transition temperature of 70 ° C. or higher, a logarithmic viscosity of 0.5 dl / g or higher, and a total repeating structural unit of 100 mol% and containing 20 mol% or more of the following structural formula (I) A porous film having a total film thickness of 5 to 100 μm.

(2) A part of the acid component of the polyamideimide resin is at least one selected from the group consisting of dimer acid, polyalkylene glycol, polyester, and butadiene rubber containing any of carboxyl group, hydroxyl group and amino group at the terminal. The porous membrane according to (1), which is a substituted copolymerized polyamideimide resin.

(3) A composite porous membrane according to (1) or (2), wherein a polyamideimide resin layer and a polyolefin-based porous membrane are combined.

(4) The porous membrane according to any one of (1) to (3), which has an air permeability of 1 to 2000 sec / 100 cc Air.

(5) A lithium ion secondary battery in which the porous film according to any one of (1) to (4) is interposed as a separator between a positive electrode and a negative electrode capable of inserting and extracting lithium ions.

(6) After applying or immersing the polyamideimide resin solution described in (1) or (2) on the base material, it is mixed with the solvent in which the polyamideimide resin is dissolved. A method for producing a porous membrane that is charged into a solution and solidified.

(7) After applying or immersing the polyamideimide resin solution described in (1) or (2) on one or both surfaces of the polyolefin-based porous membrane, it is mixed with the solvent in which the polyamideimide resin is dissolved. On the other hand, a method for producing a composite porous membrane, which is charged into a poor solvent solution and solidified.

  The present invention provides lithium ion excellent in balance between shutdown characteristics and meltdown characteristics by using a polyamideimide resin porous film having a specific structure or a composite porous film in which a polyamideimide resin porous film and a polyolefin film are laminated. A separator for a secondary battery can be provided.

  The present invention will be described in detail below. The polyamideimide resin used in the present invention contains the following structural formula (I) as an essential component.

  The structure of the formula (I) preferably has 20 mol% or more, more preferably 30 mol% or more, and further preferably 40 mol% or more when the total repeating structural unit of the polyamideimide resin is 100 mol%. . An upper limit is not specifically limited, 100 mol% may be sufficient. When the ratio of the formula (I) is less than 20 mol%, the resistance of the lithium ion secondary battery to the electrolytic solution is deteriorated, which may adversely affect the battery characteristics.

  The production method of the polyamide-imide resin used in the present invention is an isocyanate method produced from an acid component and an isocyanate (amine) component, or an acid chloride method produced from an acid chloride (acid component) and an amine, and produced from an acid component and an amine component. However, the diisocyanate method is preferred from the viewpoint of production cost.

  Although the acid component used for the synthesis of the polyamideimide resin contains trimellitic anhydride (chloride) as an essential component, a part of it can be replaced with other polybasic acid or its anhydride. For example, tetracarboxylic acids such as pyromellitic acid, biphenyltetracarboxylic acid, biphenylsulfonetetracarboxylic acid, benzophenonetetracarboxylic acid, biphenylethertetracarboxylic acid, ethylene glycol bistrimellitate, propylene glycol bistrimellitate and their anhydrides, Aliphatic dicarboxylic acids such as oxalic acid, adipic acid, malonic acid, sebacic acid, azelaic acid, dodecanedicarboxylic acid, dicarboxypolybutadiene, dicarboxypoly (acrylonitrile-butadiene), dicarboxypoly (styrene-butadiene), 1,4 -Cyclohexanedicarboxylic acid, 1,3-cyclohexanedicarboxylic acid, 4,4'-dicyclohexylmethanedicarboxylic acid, alicyclic dicarboxylic acids such as dimer acid, terephthalic acid, Le acid, diphenyl sulfone dicarboxylic acid, diphenylether dicarboxylic acid, and aromatic dicarboxylic acids such as naphthalene dicarboxylic acid. Among these, dicarboxypolybutadiene, dicarboxypoly (acrylonitrilebutadiene) and dicarboxypoly (styrene-butadiene) having a molecular weight of 1000 or more are preferable from the standpoint of shutdown characteristics.

  In addition, a urethane group can be introduced into the molecule by replacing part of the trimellitic acid compound with glycol. Examples of glycols include alkylene glycols such as ethylene glycol, propylene glycol, tetramethylene glycol, neopentyl glycol, and hexanediol, polyalkylene glycols such as polyethylene glycol, polypropylene glycol, and polytetramethylene glycol, and one or more of the above dicarboxylic acids. And polyesters having terminal hydroxyl groups synthesized from one or two or more of the above-mentioned glycols. Among these, polyethylene glycol and polyesters having terminal hydroxyl groups are preferred because of the shutdown effect. Moreover, these number average molecular weights are preferably 500 or more, and more preferably 1000 or more. The upper limit is not particularly limited, but is preferably less than 8000.

  It is also desirable to replace part of the acid component with at least one selected from the group consisting of dimer acid, polyalkylene ether, polyester and butadiene rubber containing any of carboxyl group, hydroxyl group and amino group at the end. It is preferable to replace 1 to 60 mol% of the components.

  As a diamine (diisocyanate) component used for the synthesis of the polyamideimide resin of the present invention, naphthalenediamine or this diisocyanate is an essential component, but other components include aliphatic diamines such as ethylenediamine, propylenediamine, hexamethylenediamine, and the like. These diisocyanates, 1,4-cyclohexanediamine, 1,3-cyclohexanediamine, isophoronediamine, alicyclic diamines such as 4,4′-dicyclohexylmethanediamine, and these diisocyanates, phenylenediamine, 4,4′-diaminodiphenylmethane 4,4′-diaminodiphenyl ether, 4,4′-diaminodiphenylsulfone, benzidine, xylylenediamine, tolylenediamine and other aromatic diamines and their diiso Aneto and the like, reactivity among these, cost, 4,4'-diaminodiphenylmethane from the point of electrolyte solution resistance, tolylenediamine, tolidine and its diisocyanates are preferred.

  The polyamideimide resin used in the present invention is stirred while heating at 60 to 200 ° C. in a polar solvent such as N, N′-dimethylformamide, N, N′-dimethylacetamide, N-methyl-2-pyrrolidone, and γ-butyrolactone. By doing so, it can be easily manufactured. In this case, amines such as triethylamine and diethylenetriamine, alkali metal salts such as sodium fluoride, potassium fluoride, cesium fluoride, sodium methoxide, and the like can be used as a catalyst as necessary.

  The polyamideimide resin of the present invention preferably has a glass transition temperature of 70 ° C. or higher and a logarithmic viscosity of 0.5 dl / g or higher. When the glass transition temperature is 70 ° C. or lower, there is a shutdown effect, but the meltdown temperature is lowered, and when used for a separator, the positive electrode and the negative electrode may be short-circuited. On the other hand, when the logarithmic viscosity is 0.5 dl / g or less, the resin becomes brittle and the mechanical properties of the porous film may be deteriorated. As a result, the porous film is likely to crack when the porous film is processed or the battery is assembled, which may cause a short circuit between the positive electrode and the negative electrode. On the other hand, the upper limit is preferably less than 2.0 dl / g in consideration of processability and solvent solubility.

  Next, a method for producing a polyamideimide porous membrane will be described. The production of the porous membrane of the present invention is not particularly limited, but after coating the polyamideimide polymerization solution on a substrate such as a polyester film to a predetermined thickness, or extruding the polymerization solution from a slit die into a film, The polyamidoimide resin is mixed with a dissolving solvent, but it is preferable that the polyamidoimide resin is put into a poor solvent and solidified. In addition, the poor solvent said here shall not be able to melt | dissolve this polyamidoimide resin in 25weight% at a 5 weight% density | concentration.

  Since the solvent for dissolving the polyamide-imide resin is mainly amide solvents such as N-methyl-2-pyrrolidone, dimethylacetamide, N, N-dimethylformamide as described above, the substantial coagulation bath is mainly water. Into a solution. The water used here is preferably one having few ionic impurities, and it is preferable to use water from which ions are intentionally removed, such as ion-exchanged water. The ionic impurities are preferably 500 ppm or less for each ion, more preferably 200 ppm or less, and most preferably 100 ppm or less.

This coagulation bath can be mixed with other solvents miscible with water in order to adjust the coagulation rate, the pore size of the porous membrane and its distribution. Examples of such solvents include alcohols such as methanol, ethanol, propyl alcohol, ethylene glycol, propylene glycol, diethylene glycol, and polyethylene glycol, ketones such as acetone and methyl ethyl ketone, N, N-dimethylformamide, N, N-dimethylacetamide, Examples thereof include amide solvents such as N-methyl-2-pyrrolidone, and among these, glycols such as ethylene glycol and polyethylene glycol are preferable from the viewpoint of uniformity in the porous film having a pore size. Although there is no restriction | limiting in the addition amount, Preferably it is 5 parts to 500 parts with respect to 100 parts of water, More preferably, it is 10 parts to 400 parts, Most preferably, it is 20 parts to 300 parts.
Further, the coagulation tank may be a single tank, but it may be a multi-tank in order to adjust the coagulation rate, the pore diameter of the porous membrane and its distribution. At this time, it is preferable to change the concentration of the additive to water in each tank.

  In addition, an additive may be used in the polyamideimide resin solution to adjust the coagulation rate, the pore size of the porous membrane, and the distribution thereof. For example, alcohols such as methanol, ethanol, propyl alcohol, ethylene glycol, propylene glycol, diethylene glycol, and polyethylene glycol; ketones such as acetone and methyl ethyl ketone; and water-soluble polymers such as polyethylene glycol and polyvinyl pyrrolidone. Although there is no restriction | limiting in addition amount, Preferably it is 5 to 300 parts with respect to 100 parts of resin solutions, More preferably, it is 10 parts to 200 parts, Most preferably, it is 20 parts to 100 parts.

  The polyamideimide porous membrane may be a single layer or a laminate, but the total film thickness is 5 to 100 μm, preferably 10 to 70 μm, and more preferably 15 to 50 μm. If the film thickness is 5 μm or less, the film becomes weak and may break. Conversely, when the film thickness exceeds 100 μm, the cycle characteristics may deteriorate. The porosity of the polyamideimide porous membrane is preferably 30 to 90%. More preferably, it is 40 to 70%. When the porosity is 30% or less, the electric resistance of the film becomes high and it becomes difficult to flow a large current. On the other hand, if it is 90% or more, the film strength becomes weak. The air permeability, which is a measure of the pore diameter, is preferably 1 to 2000 sec / 100 cc Air measured by a method based on JIS-P8117. More preferably, it is 50-1500 sec / 100 cc Air, More preferably, it is 100-1000 sec / 100 cc Air. When the air permeability is less than 1 sec / 100 cc Air, the film strength is weak, and when it exceeds 2000 sec / 100 cc Air, the cycle characteristics may be deteriorated.

  The polyamideimide porous membrane thus produced exhibits excellent shutdown characteristics and meltdown characteristics even when used alone as a separator. In particular, the effect is remarkable in the case of a porous film made of a polyamideimide resin in which a butadiene rubber having a number average molecular weight of 1000 or more, polyalkylene glycol, polyester, or the like is copolymerized in a block shape. The upper limit of the number average molecular weight is preferably less than 8000 considering the glass transition temperature of the polyamideimide resin.

  Another feature of the present invention is that a polyamide-imide porous membrane can be used in combination with a polyolefin-based porous membrane. The polyolefin-based porous membrane is a polyethylene or polypropylene film produced by, for example, the stretch opening method or the phase separation method described in 7th Polymer Material Forum (1998) Abstract 1 BIL09. When the polyamide-imide porous membrane and the polyolefin porous membrane are laminated, the polyamide-imide porous membrane is A, and the polyolefin-based porous membrane is B. A / B, A / B / A or B / A / B It becomes the composition of.

The production of these composite porous membranes is not particularly limited, but the following method is preferred.
(1) A polyamide-imide porous membrane and a polyolefin porous membrane are simply stacked.
(2) Using a polyolefin porous membrane as a support, impregnating or coating a polyamideimide resin solution on one side or both sides thereof, putting the solution in a coagulation bath in the same manner as described above, and coagulating it.
(3) Combine (1) and (2) above.

  In the case of these composite porous membranes, the total film thickness is 10 to 100 μm, preferably 15 to 70 μm. The porosity is preferably 30 to 80% and the air permeability is preferably 1 to 2000 sec / 100 cc Air.

  The lithium ion secondary battery using the polyamideimide porous membrane of the present invention configured as described above as a separator exhibits the same battery performance as before, and obtains a safe battery excellent in shutdown characteristics and meltdown characteristics. Can do. The lithium ion secondary battery according to the present invention can be produced according to a conventional method except that the porous membrane of the present invention is used as a separator.

  That is, a material containing lithium can be used as the positive electrode active material, a material that can store and release lithium as ions can be used as the negative electrode, and an organic solvent solution of an electrolyte composed of a compound containing lithium and fluorine can be used as the electrolytic solution.

  Specifically, lithium metal oxides such as lithium cobaltate and lithium manganate that can insert and remove lithium ions can be used as the positive electrode active material. A known active carbon, various cokes, carbon black, a binder, a solvent, and the like are blended into the positive electrode active material as a conductive agent, and this dispersion is applied to a current collector such as aluminum and dried to form a positive electrode material. Can do.

  Coke, graphite, amorphous carbon, etc. are used as the negative electrode active material, and these are applied to a current collector such as a copper foil with a dispersion composed of a binder and an organic solvent, and dried to form a negative electrode material. it can.

Examples of the electrolyte used in the electrolytic solution include LiClO ₄ , LiAsF ₆ , LiPF ₄ , LiBF ₄ , LiBr, LiCF ₃ SO ₃ , and the like, and examples of the organic solvent include propylene carbonate, ethylene carbonate, γ-butyrolactone, dimethyl One or more of carbonate, ethyl methyl carbonate, 1,2-dimethoxyethane, 1,2-diethoxyethane, tetrahydrofuran and the like are used.

EXAMPLES Hereinafter, although an Example demonstrates this invention further in detail, this invention is not restrict | limited by these Examples.
In addition, the measured value in an Example was measured with the following method.

Logarithmic viscosity: A solution obtained by dissolving 0.5 g of polyamideimide resin in 100 ml of N-methyl-2-pyrrolidone was kept at 30 ° C. and measured using an Ubbelohde viscosity tube.

Glass transition temperature: The inflection point of the loss elastic modulus of dynamic viscoelasticity measured by applying a vibration of a frequency of 110 Hz to a polyamideimide film having a measurement width of 4 mm and a length of 15 mm, using a DVE-V4 rheospectr made by Rheology. The glass transition temperature was taken.

Film thickness: The polyamideimide porous film was measured with a SONY μ-meter.

Porosity: The average film thickness (At) and weight (Aw) of about 25 μm film (A) prepared by casting and drying from a polyamideimide resin solution were measured and coagulated in water from the same polyamideimide resin solution. The porosity was calculated from the average film thickness (Bt) of the porous film (B) thus prepared and the weight (Bw) of 10 cm □ by the following formula.
Porosity = [1- (Bw / Bt) / (Aw / At)] × 100 (%)

Shutdown temperature characteristics: A porous membrane filled with 1 mol / l of lithium tetrafluoroborate dissolved in propylene carbonate was used and measured at an AC frequency of 1 kHz, an AC amplitude of 100 mV, and a heating rate of 2 ° C./min. The temperature at which the rise in impedance value due to temperature rise once becomes 100 Ωcm ² is the shutdown start temperature, and the temperature at which the impedance value exceeds 1 kΩcm ² , then rises and decreases again to 1 kΩcm ² is the meltdown temperature. It was.

[Example 1]
Trimellitic anhydride 1 mol, naphthalene diisocyanate 0.99 mol, potassium fluoride 0.02 mol in a four-necked flask equipped with a thermometer, a cooling tube, and a nitrogen gas introduction tube so that the solid content concentration becomes 20% Was mixed with N-methyl-2-pyrrolidone, stirred at 120 ° C. for 5 hours, and diluted with N-methyl-2-pyrrolidone so that the solid content concentration was 15% to synthesize a polyamideimide resin. The obtained polyamideimide resin had a logarithmic viscosity of 1.12 dl / g and a glass transition temperature of 350 ° C. The structural formula (I) component was 100 mol% in all repeating units.
A varnish containing 20 parts of polyethylene glycol # 400 in 100 parts of the above polyamideimide resin solution was applied to one side of a polyolefin porous membrane (25 μm) manufactured by Tonen Chemical Co., Ltd. so as to have a dry film thickness of 1 μm, and immersed in water. Coagulated, washed and dried. The composite porous membrane had a thickness of 26 μm, an air permeability of 340 sec / 100 cc, a shutdown temperature of 120 ° C., and a meltdown of 200 ° C. or higher. Using this composite porous membrane as a separator, positive electrode using lithium cobaltate as a positive electrode active material, acetylene black as a conductive agent, polyvinylidene fluoride as a binder, negative electrode active material mixed with graphite and amorphous carbon, and polyvinylidene fluoride A coin-type battery was made using Sollite (manufactured by Mitsubishi Chemical Corp.) as a negative electrode with a binder and electrolyte as an electrolytic solution, and battery characteristics were evaluated. As a result, compared with a commercially available separator (polyolefin porous membrane manufactured by Tonen Chemical Co., Ltd .: 25 μm), the discharge capacity and cycle characteristics were almost the same.

[Example 2]
A polyamide-imide resin was synthesized under the same conditions as in Example 1 except that the isocyanate component of Example 1 was changed to 0.5 mol of naphthalene diisocyanate and 0.49 mol of 4,4′-diphenylmethane diisocyanate. The obtained polyamideimide resin had a logarithmic viscosity of 1.08 dl / g and a glass transition temperature of 320 ° C. The structural formula (I) component was 50 mol% in all repeating units. A composite porous membrane was prepared from this polyamideimide resin solution by the same method as in Example 1. The composite porous membrane had a thickness of 27 μm, an air permeability of 460 sec / 100 cc Air, a shutdown temperature of 122 ° C., and a meltdown temperature of 200 ° C. or higher.

[Example 3]
Example 1 except that the acid component of Example 1 was 0.9 mol of trimellitic anhydride and 0.1 mol of poly (acrylonitrile-butadiene) copolymer of dicarboxylic acids at both ends (Hiker CTBN1300 × 13 manufactured by Ube Industries). 1 was synthesized under the same conditions as in 1. The obtained polyamideimide resin had a logarithmic viscosity of 0.73 dl / g and a glass transition temperature of 175 ° C. The structural formula (I) component was 90 mol% in all repeating units. A composite porous membrane was prepared from this polyamideimide resin solution by the same method as in Example 1. The composite porous membrane had a thickness of 28 μm, an air permeability of 360 sec / 100 cc Air, a shutdown temperature of 121 ° C., and a meltdown temperature of 200 ° C. or higher.

[Example 4]
Using the same apparatus as Example 1, 0.93 mol of trimellitic anhydride, 0.07 mol of polycaprolactone (Placcel 220 manufactured by Daicel Chemical Industries, Ltd., molecular weight 2000), 0.5 mol of naphthalene diisocyanate, diphenylmethane-4,4′- 0.49 mol of diisocyanate and 0.02 mol of potassium fluoride were charged together with N-methyl-2-pyrrolidone so that the solid content concentration was 20%, and reacted at 120 ° C. for about 5 hours. The obtained polyamideimide resin had a logarithmic viscosity of 0.82 dl / g and a glass transition temperature of 230 ° C. Structural formula (I) component was 47 mol% in all repeating units. A porous membrane was prepared from this polyamideimide resin solution in the same manner as in Example 1. This porous film had a thickness of 27 μm, an air permeability of 340 sec / 100 cc Air, a shutdown temperature of 122 ° C., and a meltdown temperature of 200 ° C. or higher.

[Example 5]
A solution obtained by blending 100 parts of the polyamideimide resin solution of Example 3 with 20 parts of ethylene glycol on a 100 μm polyester film, dipping in water to solidify, washing with water and drying, a polyamideimide porous film having a film thickness of 28 μm Got. This porous film had a porosity of 63%, an air permeability of 6.5 sec / 100 cc Air, a shutdown temperature of 185 ° C., and a meltdown temperature of 200 ° C. or higher. Battery performance such as discharge capacity and cycle durability of a coin battery using this polyamideimide porous membrane as a separator in the same configuration as in Example 1 showed the same characteristics as the polyolefin porous membrane single separator.

[Example 6]
After immersing a polyolefin porous membrane (25 μm) manufactured by Tonen Chemical in a varnish in which 20 parts of polyethylene glycol # 400 was blended with 100 parts of the polyamideimide resin solution of Example 1, the dry film thicknesses were measured on both sides of the polyolefin porous membrane. It is scraped off with a squeeze roll so as to be 1 μm, put into a coagulation bath having a water / polyethylene glycol (molecular weight 400) ratio of 70/30, coagulated, washed and dried, and a composite porous membrane of 3 layers having a thickness of 27 μm Got. The composite porous membrane had a shutdown temperature of 120 ° C. and a meltdown temperature of 200 ° C. or higher. The battery performance such as the discharge capacity and cycle durability of the coin battery prepared by using the composite porous membrane as a separator and having the same structure as in Example 1 showed the same characteristics as the polyolefin porous membrane single separator.

[Example 7]
Discharge capacity and cycle endurance of a coin battery in which a composite membrane obtained by laminating a polyolefin porous membrane on the polyamideimide porous membrane side of the polyamideimide / polyolefin composite porous membrane prepared in Example 6 under the same conditions as in Example 1 The battery performance such as the property showed almost the same characteristics as the polyolefin porous membrane single separator.

[Comparative Example 1]
A polyamideimide resin was synthesized under the same conditions as in Example 1 except that TMA was 1.08 mol in Example 1. The obtained polyamideimide resin had a logarithmic viscosity of 0.31 dl / g and a glass transition temperature of 350 ° C. The structural formula (I) component was 100 mol% in all repeating units. A porous membrane using this polyamideimide resin is fragile because of its low molecular weight, and is not suitable as a separator.

[Comparative Example 2]
Polyamide under the same conditions as in Example 1 except that the acid component was 0.15 mol trimellitic anhydride, 0.85 mol dimer acid, 0.5 mol naphthalene diisocyanate, and 0.49 mol 4,4'-diphenylmethane diisocyanate. An imide resin was synthesized. The obtained polyamideimide resin had a logarithmic viscosity of 0.64 dl / g and a glass transition temperature of 60 ° C. The structural formula (I) component was 8 mol% in all repeating units. Using this polyamideimide resin solution, a porous membrane was prepared in the same manner as in Example 5. The porous film had a thickness of 26 μm, a porosity of 63%, and an air permeability of 3.4 sec / 100 cc Air. The shutdown temperature was as low as 75 ° C. and the meltdown temperature was as low as 95 ° C. Safety was insufficient.

[Comparative Example 3]
Using the same apparatus as in Example 1, 1 mol of trimellitic anhydride, 0.05 mol of naphthalene diisocyanate, 0.95 mol of hexamethylene diisocyanate, and 0.02 mol of potassium fluoride were adjusted to a solid content concentration of 50%. After charging with butyrolactone and reacting at 120 ° C. for 1 hour and 190 ° C. for 5 hours, a polyamideimide resin was synthesized by diluting with N-methyl-2-pyrrolidone at a solid concentration of 25%. The obtained polyamideimide resin had a logarithmic viscosity of 0.52 dl / g and a glass transition temperature of 130 ° C. The structural formula (I) component was 5 mol% in all repeating units.
A composite porous membrane was prepared from this polyamideimide resin solution by the same method as in Example 1. The composite porous membrane had a film thickness of 27 μm, an air permeability of 460 sec / 100 cc Air, a shutdown temperature of 122 ° C., and a meltdown temperature of 153 ° C., and the safety as a separator was insufficient. Moreover, although the coin battery was produced with the same structure as Example 1, since the polyamide-imide resin swelled in electrolyte solution, it was unsuitable as a separator.

  The present invention provides lithium ion excellent in balance between shutdown characteristics and meltdown characteristics by using a polyamideimide resin porous film having a specific structure or a composite porous film in which a polyamideimide resin porous film and a polyolefin film are laminated. A separator for a secondary battery can be provided.

Claims (7)

Including a polyamide-imide resin layer having a glass transition temperature of 70 ° C. or higher, a logarithmic viscosity of 0.5 dl / g or higher, and a total repeating structural unit of 100 mol%, containing 20 mol% or more of the following structural formula (I). A porous film having a total film thickness of 5 to 100 μm.

  Part of the acid component of the polyamide-imide resin was replaced with at least one of the group consisting of dimer acid, polyalkylene glycol, polyester, and butadiene rubber containing any of carboxyl, hydroxyl and amino groups at the terminal. The porous film according to claim 1, which is a copolymerized polyamideimide resin.   The composite porous membrane according to claim 1 or 2, wherein a polyamide-imide resin layer and a polyolefin-based porous membrane are combined.   The porous membrane according to any one of claims 1 to 3, which has an air permeability of 1 to 2000 sec / 100 cc Air.   A lithium ion secondary battery comprising the porous film according to claim 1 interposed as a separator between a positive electrode and a negative electrode capable of inserting and extracting lithium ions.   After applying or immersing the polyamideimide resin solution according to claim 1 or 2 on a substrate, the polyamideimide resin solution is mixed with a solvent in which the polyamideimide resin is dissolved, but is added to a poor solvent for the polyamideimide resin. A method for producing a porous membrane to be solidified.   After applying or immersing the polyamideimide resin solution according to claim 1 or 2 on one or both surfaces of the polyolefin-based porous membrane, it is mixed with a solvent in which the polyamideimide resin is dissolved. A method for producing a composite porous membrane that is charged into a solution and solidified.