JP5476844B2 - Porous film, battery separator and battery - Google Patents

Description

The present invention relates to a porous film, a battery separator, and a battery.

The porous film is used for various applications such as sanitary materials, medical materials, and battery separators. In particular, when a porous film is used as a battery separator such as a lithium ion secondary battery, high piercing strength is required.

As a porous film excellent in piercing strength, a high molecular weight polyolefin having a weight average molecular weight of 5 × 10 ⁵ or more, a thermoplastic resin having a weight average molecular weight of 2 × 10 ⁴ or less, and fine particles are kneaded and formed into a sheet shape Then, a porous film obtained by stretching the sheet is known (see Patent Document 1). In such a porous film, a high molecular weight polyolefin can be easily processed without using an organic solvent in the production process, and the resulting porous film has excellent puncture strength.

A laminated porous film in which a porous heat-resistant layer is laminated on a porous film made of a thermoplastic polymer is also known as a battery separator (see Patent Document 2). The battery using the laminated porous film as a separator can prevent the positive electrode and the negative electrode from coming into contact with the heat-resistant layer even when the porous film melts when abnormal heat generation occurs due to overcharge, etc. Excellent safety.

As a method for producing such a laminated porous film, a solution containing a heat-resistant resin is applied on the porous film and the solvent is volatilized to form a heat-resistant layer, or the solution is applied on the porous film. Then, a method of depositing a heat resistant resin by exposure to a poor solvent is known. Such a method is simple and excellent in productivity. However, the laminated porous film obtained by such a method has been required to be further improved in terms of the adhesive strength between the heat-resistant layer and the porous film.

JP 2002-69221 A JP 2000-30686 A

The object of the present invention is, when a heat resistant layer is laminated on a porous film, a porous film in which the heat resistant layer is difficult to peel off, a laminated porous film in which a porous film and a porous heat resistant layer are laminated, a battery separator, And providing a battery.

That is, the present invention relates to [1] to [4].
[1] A porous film obtained by using a resin composition containing an ultrahigh molecular weight polyolefin and a polyolefin wax having a weight average molecular weight of 3000 or less, and substantially free of components that melt at 60 ° C. or less .
[2] A porous film in which the resin composition in the above [1] contains 5 to 50% by weight of polyolefin wax (however, the weight of the resin composition is 100%).
[3] A laminated porous film in which a porous heat-resistant layer is laminated on at least one surface of the porous film according to [1] or [2].
[4] The porous film according to [1] or [2], which is a battery separator, or the laminated porous film according to [3].
[5] A battery comprising the battery separator according to [4].

  According to the present invention, when a heat-resistant layer is laminated on a porous film, the heat-resistant layer is hardly peeled off, a laminated porous film in which a porous film and a porous heat-resistant layer are laminated, a battery separator, And a battery can be provided.

  The present invention relates to a porous film obtained by using a resin composition containing an ultrahigh molecular weight polyolefin and a polyolefin wax having a weight average molecular weight of 3000 or less, and is substantially free of a component that melts at 60 ° C. or less It is a film.

The ultra-high molecular weight polyolefin in the present invention is a polyolefin having a weight average molecular weight of 5 × 10 ⁵ or more, and is preferably a polyolefin having a weight average molecular weight of 10 × 10 ⁵ or more from the viewpoint of the strength of the porous film. From the viewpoint of moldability, the weight average molecular weight of the ultrahigh molecular weight polyolefin is usually 50 × 10 ⁵ or less, and preferably 40 × 10 ⁵ or less. Examples of the ultrahigh molecular weight polyolefin include a high molecular weight homopolymer or copolymer obtained by polymerizing ethylene, propylene, 1-butene, 4-methyl-1-pentene, 1-hexene and the like. Of these, ultra high molecular weight polyethylene mainly composed of monomer units derived from ethylene is preferred.

The polyolefin wax in the present invention is a polyolefin wax having a weight average molecular weight of 3000 or less. The weight average molecular weight of the polyolefin wax is preferably 500-2500. Polyolefin waxes include ethylene polymers, polyethylene polymers such as ethylene-α-olefin copolymers, polypropylene polymers such as propylene homopolymers, propylene-α-olefin copolymers, 4-methylpentene- 1 polymer, poly (butene-1), ethylene-vinyl acetate copolymer and the like. It is preferable to select a polyolefin wax having excellent compatibility with the ultrahigh molecular weight polyolefin. For example, when the ultrahigh molecular weight polyolefin is ultrahigh molecular weight polyethylene, an ethylene homopolymer or an ethylene-α-olefin copolymer is used. It is preferable to use polyethylene wax.

  The weight average molecular weight of the ultrahigh molecular weight polyolefin or polyolefin wax can be generally determined by GPC measurement.

  In the present invention, a porous film is produced using a resin composition containing the above-described ultrahigh molecular weight polyolefin and polyolefin wax. When the weight of the resin composition is 100% by weight, the proportion of the polyolefin wax is preferably 5 to 50% by weight, and more preferably 10 to 40% by weight. Further, the amount of the ultrahigh molecular weight polyolefin contained in the resin composition is preferably 50 to 95% by weight, and more preferably 60 to 90% by weight. The resin composition having such a composition is excellent in processability, promotes crystallization of ultrahigh molecular weight polyolefin, and can obtain a porous film excellent in strength.

The porous film of the present invention is a porous film obtained using a resin composition containing the above-described ultrahigh molecular weight polyolefin and a polyolefin wax having a weight average molecular weight of 3000 or less, and substantially contains components that melt at 60 ° C. or less. Not included. Such a porous film is a film in which, when a heat resistant layer is laminated on the porous film, the heat resistant layer is hardly peeled off. The reason for this is not clear, but if there is substantially no component that melts at 60 ° C. or lower, it may be due to heat applied during processing or contact with an organic solvent when laminating the heat-resistant layer on the porous film by the method described below. Since the resin composition is less likely to swell or melt, the surface becomes a dense porous film, and the contact area with the heat resistant layer is widened. Therefore, it is considered that the adhesion between the porous film and the heat resistant layer is enhanced.
Whether or not the porous film contains a component that melts at 60 ° C. can be confirmed by differential scanning calorimetry (DSC).

  The porous film of the present invention can be obtained by using a material that does not substantially contain a component that melts at 60 ° C. That is, it melts at 60 ° C. as a material to be included in the porous film when an ultra-high molecular weight polyolefin or polyolefin wax included in the resin composition used for manufacturing the porous film is produced. By using a material substantially free of components, the porous film of the present invention can be obtained.

  The resin composition used for the production of the porous film of the present invention may contain components other than the ultrahigh molecular weight polyolefin and the polyolefin wax having a weight average molecular weight of 3000 or less. For example, the porous film of the present invention can be obtained by forming a sheet using a resin composition containing a filler in addition to ultrahigh molecular weight polyolefin and polyolefin wax and then stretching the film uniaxially or biaxially. Moreover, a porous film can be obtained also by removing a filler from the said sheet | seat and extending | stretching, or removing a filler after extending | stretching the said sheet | seat.

  As the filler, inorganic or organic fine particles generally called a filler can be used. Inorganic fine particles include calcium carbonate, talc, clay, kaolin, silica, hydrotalcite, diatomaceous earth, magnesium carbonate, barium carbonate, calcium sulfate, magnesium sulfate, barium sulfate, aluminum hydroxide, magnesium hydroxide, calcium oxide, oxidation Fine particles such as magnesium, titanium oxide, alumina, mica, zeolite, glass powder, and zinc oxide are used. Among these, fine particles of calcium carbonate and barium sulfate with low moisture are particularly preferable. As the organic fine particles, known resin fine particles are used. As the resin, a polymer obtained by polymerizing monomers such as styrene, acrylonitrile, methyl methacrylate, ethyl methacrylate, glycidyl methacrylate, methyl acrylate alone or in combination of two or more kinds. Polycondensation resins such as coalescence, melamine and urea are preferred.

  The filler may be removed before or after the sheet is stretched. In that case, it is preferable that the filler is water-soluble because it can be easily removed with an aqueous solution such as neutral, acidic or alkaline. Examples of the water-soluble filler include talc, clay, kaolin, diatomaceous earth, calcium carbonate, magnesium carbonate, barium carbonate, magnesium sulfate, calcium oxide, calcium oxide, magnesium hydroxide, calcium hydroxide, and zinc oxide among the aforementioned fine particles. And silica. Among these, calcium carbonate is preferable.

The average particle size of the filler is preferably 0.01 to 3 μm, more preferably 0.02 to 1 μm, and most preferably 0.05 to 0.5 μm. When the average particle size is 3 μm or less, a film having better piercing strength can be obtained. When the average particle size is 0.01 μm or more, it becomes easy to highly disperse in the ultrahigh molecular weight polyolefin and the polyolefin wax. It becomes easy to open holes.

In order to facilitate dispersion in the ultrahigh molecular weight polyolefin and polyolefin wax, the filler facilitates interfacial delamination with the ultra high molecular weight polyolefin and polyolefin wax when the sheet is stretched to make it porous. In order to prevent absorption, it is preferable to use a surface-treated one. Examples of the surface treatment agent include higher fatty acids such as stearic acid and lauric acid, and metal salts thereof.

  When a resin composition containing a filler is used, the filler content in the resin composition is such that the total volume of 100 when the total volume of the ultrahigh molecular weight polyolefin and polyolefin wax contained in the resin composition is 100 parts by volume. Preferably it is 15-150 volume parts with respect to a volume part, More preferably, it is 25-100 volume parts. If it is 15 parts by volume or more, it can be sufficiently opened by stretching to obtain a good porous film, and if it is 150 parts by volume or less, a resin ratio is high, so that a porous film having excellent puncture strength is obtained. be able to.

  In addition, the resin composition used in the present invention contains additives (antistatic agents, plasticizers, lubricants, antioxidants, nucleating agents, etc.) that are generally used as long as they do not impair the purpose of the present invention. May be added.

  The above-described ultrahigh molecular weight polyolefin, polyolefin wax, and, if necessary, a filler, other additives, and other resins are kneaded to produce a resin composition. The kneading is preferably performed in a kneading apparatus having a high shearing force. Specific examples include a roll, a Banbury mixer, a single screw extruder, and a twin screw extruder.

  The method for producing a sheet using the resin composition is not particularly limited, and examples thereof include inflation processing, calendar processing, T-die extrusion processing, and Skyf method. Since a sheet with higher film thickness accuracy can be obtained, it is preferable to produce the sheet by the following method.

  A preferable production method of the sheet is a method of rolling the resin composition using a pair of rotational molding tools adjusted to a surface temperature higher than the melting point of the ultrahigh molecular weight polyolefin contained in the resin composition. The surface temperature of the rotary forming tool is preferably (melting point + 5) ° C. or higher. The upper limit of the surface temperature is preferably (melting point + 30) ° C. or less, and more preferably (melting point + 20) ° C. or less. Examples of the pair of rotary forming tools include a roll and a belt. The peripheral speeds of the two rotary forming tools do not necessarily have to be exactly the same peripheral speed, and the difference between them may be about ± 5% or less. By producing a porous film using a sheet obtained by such a method, a porous film excellent in strength, ion permeation, air permeability and the like can be obtained. Moreover, you may use what laminated | stacked the sheet | seat of the single layer obtained by the above methods for manufacture of a porous film.

  When the resin composition is roll-formed with a pair of rotational molding tools, the resin composition discharged in a strand form from an extruder may be directly introduced between the pair of rotational molding tools, and the resin composition once pelletized May be used.

  The method of stretching the sheet obtained by molding the resin composition to form a porous film is not particularly limited, but can be produced by stretching using a known device such as a tenter, roll, or autograph. . The stretching may be uniaxial or biaxial, and the stretching may be performed in one step or in multiple steps. In order to cause interfacial peeling between the resin and the filler, the draw ratio is preferably 2 to 12 times, and more preferably 4 to 10 times. The stretching temperature is usually performed at a temperature not lower than the softening point and not higher than the melting point of the ultrahigh molecular weight polyolefin, and is preferably performed at 80 ° C to 120 ° C. By stretching at such a temperature, the film hardly breaks during stretching and the ultra-high molecular weight polyolefin hardly melts, so that the holes generated by the interfacial peeling between the resin and the filler are difficult to close. In addition, after stretching, a heat setting treatment may be performed as necessary to stabilize the shape of the holes.

  After removing at least part of the filler from the sheet obtained by molding the resin composition, the porous film may be produced by stretching. Or after extending | stretching the sheet | seat obtained by shape | molding a resin composition, you may remove at least one part filler and manufacture a porous film. Examples of the method for removing the filler include a method of immersing the sheet or the stretched film in a liquid capable of dissolving the filler.

  In the present invention, a porous heat-resistant layer can be laminated on at least one surface of the porous film obtained by the method as described above. The laminated porous film having such a heat-resistant layer is excellent in film thickness uniformity, heat resistance, strength, and ion permeability, and when a battery is used as a separator, when abnormal heat generation occurs due to overcharge, Even if the porous film is melted, the heat-resistant layer is preferable because it prevents the positive electrode and the negative electrode from contacting each other and is excellent in safety.

  The heat-resistant resin constituting the heat-resistant layer is preferably a polymer containing a nitrogen atom in the main chain, and particularly preferably contains an aromatic ring from the viewpoint of heat resistance. For example, aromatic polyaramid (hereinafter sometimes referred to as “aramid”), aromatic polyimide (hereinafter sometimes referred to as “polyimide”), aromatic polyamideimide, and the like can be given. Examples of aramids include meta-oriented aromatic polyamides and para-oriented aromatic polyamides (hereinafter sometimes referred to as “para-aramids”), and it is easy to form a porous heat-resistant layer having a uniform film thickness and excellent air permeability. To para-aramid.

  Para-aramid is obtained by condensation polymerization of a para-oriented aromatic diamine and a para-oriented aromatic dicarboxylic acid halide, and the amide bond is in the para position of the aromatic ring or an oriented position equivalent thereto (for example, 4,4′-biphenylene). , 1,5-naphthalene, 2,6-naphthalene, and the like, which are substantially composed of repeating units bonded in the opposite direction (orientation positions extending coaxially or in parallel). Specifically, poly (paraphenylene terephthalamide), poly (parabenzamide), poly (4,4′-benzanilide terephthalamide), poly (paraphenylene-4,4′-biphenylenedicarboxylic acid amide), poly ( (Paraphenylene 2,6-naphthalene dicarboxylic acid amide), poly (2-chloro-paraphenylene terephthalamide), paraphenylene terephthalamide / 2,6-dichloroparaphenylene terephthalamide copolymer, etc. Para-aramid having a similar structure is exemplified.

When providing the heat-resistant layer, a coating solution obtained by dissolving a heat-resistant resin in a solvent is usually used. When the heat-resistant resin is para-aramid, a polar amide solvent or a polar urea solvent can be used as the solvent. Specifically, N, N-dimethylformamide, N, N-dimethylacetamide, N-methyl Examples include, but are not limited to, -2-pyrrolidone and tetramethylurea.
From the viewpoint of coatability, the heat resistant resin is preferably a heat resistant resin having an intrinsic viscosity of 1.0 to 2.8 dl / g, and more preferably a heat resistant resin having an intrinsic viscosity of 1.7 to 2.5 dl / g. . The intrinsic viscosity here is a value measured by dissolving the heat-resistant resin once deposited and making it into a heat-resistant resin sulfuric acid solution. From the viewpoint of coating properties, the heat-resistant resin concentration in the coating solution is preferably 0.5 to 10% by weight.

When para-aramid is used as the heat-resistant resin, it is preferable to add an alkali metal or alkaline earth metal chloride during the para-aramid polymerization for the purpose of improving the solubility of para-aramid in a solvent. Specific examples include, but are not limited to lithium chloride or calcium chloride. The amount of the chloride added to the polymerization system is preferably 0.5 to 6.0 mol, more preferably 1.0 to 4.0 mol, per 1.0 mol of the amide group produced by condensation polymerization. If the chloride is 0.5 mol or more, the resulting para-aramid is sufficiently soluble, and if it is 6.0 mol or less, the chloride does not remain dissolved in the solvent. In general, the alkali metal or alkaline earth metal chloride is often 2% by weight or more and the solubility of para-aramid is often sufficient. At 10% by weight or less, the alkali metal or alkaline earth metal chloride is polar. In many cases, it is completely dissolved without being dissolved in a polar organic solvent such as an amide solvent or a polar urea solvent.

  The polyimide used in the present invention is preferably a wholly aromatic polyimide produced by condensation polymerization of an aromatic dianhydride and a diamine. Specific examples of the dianhydride include pyromellitic dianhydride, 2,2′-bis (3,4-dicarboxyphenylphenyl) hexafluoropropane, 3,3 ′, 4,4′-biphenyltetra. Examples thereof include carboxylic dianhydrides. Specific examples of the diamine include oxydianiline, paraphenylenediamine, benzophenonediamine, 3,3′-methylenedianiline, 3,3′-diaminobenzophenone, 3,3′-diaminodiphenylsulfone, 1,5-naphthalene. Although diamine etc. are mentioned, this invention is not limited to these. In the present invention, a polyimide soluble in a solvent can be suitably used. An example of such a polyimide is a polyimide that is a condensation polymer of 3,3 ′, 4,4′-diphenylsulfonetetracarboxylic dianhydride and an aromatic diamine. As a polar organic solvent for dissolving polyimide, dimethyl sulfoxide, cresol, o-chlorophenol, and the like can be suitably used in addition to those exemplified as a solvent for dissolving aramid.

In the present invention, the coating liquid used for forming the heat-resistant layer particularly preferably contains inorganic fine particles. By forming a heat-resistant layer using a coating solution in which inorganic fine particles are added to a solution having an arbitrary heat-resistant resin concentration, it is possible to form a heat-resistant layer having a uniform film thickness and a fine porosity. The air permeability can be controlled by the amount of inorganic fine particles added. The inorganic fine particles in the present invention preferably have an average primary particle size of 1.0 μm or less, more preferably 0.5 μm or less, from the viewpoint of the strength of the porous film and the smoothness of the heat-resistant layer surface. More preferably, it is 0.1 μm or less.
The content of the inorganic fine particles is preferably 1% by weight to 95% by weight or less in the porous film, and more preferably 5% by weight to 50% by weight. When the content is 1% by weight or more, sufficient porosity is obtained, so that the ion permeability is excellent. When the content is 95% by weight or less, sufficient film strength is obtained, so that handling is excellent. The shape of the inorganic fine particles to be used is not particularly limited, and can be spherical or random.

  The inorganic fine particles used when forming the heat-resistant layer are preferably ceramic powder. Examples of the ceramic powder include ceramic powders made of electrically insulating metal oxides, metal nitrides, metal carbides, and the like. For example, powders such as alumina, silica, titanium dioxide, and zirconium oxide are preferably used. The ceramic powders may be used alone, or two or more kinds thereof may be mixed, and the same or different ceramic powders having different particle sizes may be arbitrarily mixed and used.

As a method of laminating a heat-resistant layer on a porous film formed from a resin composition containing an ultra-high molecular weight polyolefin and a polyolefin wax, a method of separately producing a heat-resistant layer and laminating the porous film later, Although the method of apply | coating the coating liquid containing a ceramic powder and a heat resistant resin to an at least single side | surface and forming a heat resistant layer etc. are mentioned, The latter method is preferable from a viewpoint of productivity. Specifically, the latter method includes a method including the following steps.
(A) In a polar organic solvent solution containing 100 parts by weight of a heat resistant resin, a slurry-like coating liquid in which 1 to 500 parts by weight of ceramic powder is dispersed with respect to 100 parts by weight of the heat resistant resin is prepared. (B) The coating liquid is porous. Coating is performed on at least one surface of the quality film to form a coating film.
(C) The heat resistant resin is deposited from the coating film by means of humidification, solvent removal, or immersion in a solvent that does not dissolve the heat resistant resin, and then dried as necessary.
The coating liquid is preferably applied continuously by a coating apparatus described in JP-A-2001-316006 and a method described in JP-A-2001-23602.

  Moreover, a heat resistant layer can also be laminated | stacked on both surfaces of a porous film by immersing a porous film in the coating liquid containing a heat resistant resin, and drying.

  The porous film of the present invention is excellent in permeability at the use temperature and can be quickly shut down at a low temperature when the use temperature is exceeded, and is suitable as a separator for non-aqueous batteries. Moreover, the laminated porous film obtained by laminating the heat-resistant layer on the porous film of the present invention is excellent in heat resistance, strength and ion permeability, and is preferably used as a separator for non-aqueous batteries, particularly a separator for lithium secondary batteries. Can do.

When the battery separator of the present invention includes the porous film of the present invention, the porosity of the porous film is 30 to 80% by volume from the viewpoints of electrolyte retention, film strength, and shutdown performance. More preferably, it is 40-70 volume%. In addition, from the viewpoint of shutdown property, battery short circuit prevention during winding, and high battery capacity, the thickness of the porous film is preferably 5 to 50 μm, more preferably 10 to 50 μm, and still more preferably 10 to 10 μm. 30 μm. The pore diameter of the porous film is preferably 0.1 μm or less, and more preferably 0.08 μm or less. By reducing the pore diameter, a porous film having a small membrane resistance value is obtained even with the same air permeability.

When the battery separator of the present invention includes the laminated porous film of the present invention, among the laminated porous films, preferred porosity and pore diameter of the porous film are the same as those of the porous film. However, the film thickness is preferably 5 to 50 μm, more preferably 10 to 50 μm, and still more preferably 10 to 30 μm as the whole laminated porous film. Among the laminated porous films, the porosity of the heat-resistant layer is preferably 30 to 80% by volume, more preferably 40 to 70% by volume, from the viewpoint of the amount of electrolyte retained and the strength. The film thickness of the heat-resistant layer is preferably 0.5 to 10 μm, more preferably 1 to 5 μm, from the viewpoint of suppressing shrinkage during heating and load characteristics when a battery is formed.

The battery of the present invention includes the battery separator of the present invention. Below, when the battery of this invention is nonaqueous electrolyte secondary batteries, such as a lithium battery, components other than the battery separator are demonstrated in detail.

As the non-aqueous electrolyte solution, for example, a non-aqueous electrolyte solution in which a lithium salt is dissolved in an organic solvent can be used. Examples of lithium salts include LiClO ₄ , LiPF ₆ , LiAsF ₆ , LiSbF ₆ , LiBF ₄ , LiCF ₃ SO ₃ , LiN (SO ₂ CF ₃ ) ₂ , LiC (SO ₂ CF ₃ ) ₃ , Li ₂ B ₁₀ Cl ₁₀ , One or a mixture of two or more of lower aliphatic carboxylic acid lithium salts, LiAlCl _{4 and the} like can be mentioned. The lithium salt is selected from the group consisting of LiPF ₆ containing fluorine, LiAsF ₆ , LiSbF ₆ , LiBF ₄ , LiCF ₃ SO ₃ , LiN (CF ₃ SO ₂ ) ₂ , and LiC (CF ₃ SO ₂ ) ₃ among these. It is preferable to use one containing at least one selected from the above.

Examples of the organic solvent used in the nonaqueous electrolyte solution include propylene carbonate, ethylene carbonate, dimethyl carbonate, diethyl carbonate, ethyl methyl carbonate, 4-trifluoromethyl-1,3-dioxolan-2-one, 1,2-di ( Carbonates such as methoxycarbonyloxy) ethane; 1,2-dimethoxyethane, 1,3-dimethoxypropane, pentafluoropropyl methyl ether, 2,2,3,3-tetrafluoropropyl difluoromethyl ether, tetrahydrofuran, 2-methyl Ethers such as tetrahydrofuran; esters such as methyl formate, methyl acetate and γ-butyrolactone; nitriles such as acetonitrile and butyronitrile; N, N-dimethylformamide, N, N-dimethylacetate Amides such as amide; Carbamates such as 3-methyl-2-oxazolidone; Sulfur-containing compounds such as sulfolane, dimethyl sulfoxide and 1,3-propane sultone, or those obtained by introducing a fluorine substituent into the above organic solvent Usually, a mixture of two or more of these is used.

Among these, a mixed solvent containing carbonates is preferable, and a mixed solvent of cyclic carbonate and acyclic carbonate or cyclic carbonate and ether is more preferable. The mixed solvent of cyclic carbonate and non-cyclic carbonate has a wide operating temperature range, excellent load characteristics, and is hardly decomposable even when a graphite material such as natural graphite or artificial graphite is used as the negative electrode active material. In addition, a mixed solvent containing ethylene carbonate, dimethyl carbonate and ethyl methyl carbonate is preferable. As the positive electrode sheet, a sheet in which a mixture containing a positive electrode active material, a conductive material, and a binder is supported on a current collector is usually used. Specifically, as the positive electrode active material, a material containing a material that can be doped / undoped with lithium ions, a carbonaceous material as a conductive material, and a thermoplastic resin as a binder can be used. Examples of the material that can be doped / undoped with lithium ions include lithium composite oxides containing at least one transition metal such as V, Mn, Fe, Co, and Ni. Among these, in view of high average discharge potential, lithium based on a layered lithium composite oxide based on an α-NaFeO2 type structure such as lithium nickelate and lithium cobaltate and a spinel type structure such as lithium manganese spinel is preferable. A composite oxide is mentioned.

The lithium composite oxide may contain various additive elements, particularly at least selected from the group consisting of Ti, V, Cr, Mn, Fe, Co, Cu, Ag, Mg, Al, Ga, In, and Sn. Composite nickel acid containing a metal such that the at least one metal is 0.1 to 20 mol% with respect to the sum of the number of moles of one metal and the number of moles of Ni in lithium nickelate Lithium is preferable because cycle characteristics in use at high capacity are improved.

As the thermoplastic resin as the binder, polyvinylidene fluoride, vinylidene fluoride copolymer, polytetrafluoroethylene, tetrafluoroethylene-hexafluoropropylene copolymer, tetrafluoroethylene-perfluoroalkyl vinyl ether Copolymer, ethylene-tetrafluoroethylene copolymer, vinylidene fluoride-hexafluoropropylene-tetrafluoroethylene copolymer, thermoplastic polyimide, polyethylene, polypropylene and the like.

Examples of the carbonaceous material as the conductive agent include natural graphite, artificial graphite, cokes, and carbon black. As the conductive material, each may be used alone, or for example, a composite conductive material system in which artificial graphite and carbon black are mixed and used may be selected.

As the negative electrode sheet, for example, a material capable of doping and dedoping lithium ions, lithium metal, or a lithium alloy can be used. Materials that can be doped / undoped with lithium ions include carbonaceous materials such as natural graphite, artificial graphite, cokes, carbon black, pyrolytic carbons, carbon fibers, and fired organic polymer compounds, and lower potential than the positive electrode. And chalcogen compounds such as oxides and sulfides for doping and dedoping lithium ions. As a carbonaceous material, a carbonaceous material mainly composed of graphite materials such as natural graphite and artificial graphite, because it has a high potential flatness and a low average discharge potential, so that a large energy density can be obtained when combined with a positive electrode. Is preferred.

As the negative electrode current collector, Cu, Ni, stainless steel, or the like can be used. In particular, in a lithium secondary battery, Cu is preferable because it is difficult to form an alloy with lithium and it can be easily processed into a thin film. As a method of supporting the mixture containing the negative electrode active material on the negative electrode current collector, a method of pressure molding, or a method of pasting into a paste using a solvent or the like and applying pressure to the current collector by pressing after drying Is mentioned.

The shape of the battery of the present invention is not particularly limited, and may be any of a paper type, a coin type, a cylindrical type, a rectangular shape, and the like.

  Hereinafter, the present invention will be described more specifically with reference to examples and comparative examples. However, the present invention is not limited to the following examples.

(1) DSC measurement Using a SSC / 5200 manufactured by Seiko Instruments Inc., the DSC measurement was performed at a heating rate of 10 ° C / min.

(2) Bond strength measurement
Synthesis of para-aramid (poly (paraphenylene terephthalamide)) Production of poly (paraphenylene terephthalamide) using a 3 liter separable flask with stirring blade, thermometer, nitrogen inlet tube and powder addition port went. The flask was sufficiently dried, charged with 2200 g of N-methyl-2-pyrrolidone (NMP), added with 151.07 g of calcium chloride powder vacuum-dried at 200 ° C. for 2 hours, heated to 100 ° C. and completely dissolved. . After returning to room temperature, 68.23 g of paraphenylenediamine was added and completely dissolved. While maintaining this solution at 20 ° C. ± 2 ° C., 124.97 g of terephthalic acid dichloride was added in 10 divided portions every about 5 minutes. Thereafter, the solution was aged for 1 hour while maintaining the temperature at 20 ° C. ± 2 ° C. with stirring. It filtered with the 1500 mesh stainless steel wire mesh. The resulting solution had a para-aramid concentration of 6%.
Preparation of coating liquid 100 g of the previously polymerized para-aramid solution was weighed into a flask, 300 g of NMP was added, and a solution having a para-aramid concentration of 1.5% by weight was prepared and stirred for 60 minutes. 6 g of alumina C (manufactured by Nippon Aerosil Co., Ltd.) and 6 g of advanced alumina AA-03 (manufactured by Sumitomo Chemical Co., Ltd.) were mixed with the above-mentioned solution having a para-aramid concentration of 1.5% by weight and stirred for 240 minutes. The obtained solution was filtered through a 1000 mesh wire mesh, then 0.73 g of calcium oxide was added, and the mixture was neutralized by stirring for 240 minutes, and defoamed under reduced pressure to obtain a coating solution on the slurry.
Measurement of adhesive strength After applying the obtained coating liquid on the porous film with a bar coater so as to have a thickness of 130 μm, it was placed in an oven at 50 ° C. and 70% RH for 15 seconds, and then applied onto the porous film. Aramid was precipitated. A weight was placed on a 2 cm square SUS plate having one 1.5R protrusion and slid onto the aramid layer on which the protrusion was deposited, and the weight of the largest weight that the aramid layer was not peeled was measured. . The greater the weight of the weight, the higher the bond strength between the aramid layer and the porous film.

Example 1
70% by weight of ultrahigh molecular weight polyethylene powder (340M, manufactured by Mitsui Chemicals), 30% by weight of polyethylene wax having a weight average molecular weight of 1000 (FNP-0115, manufactured by Nippon Seiki Co., Ltd.), 100 of this ultrahigh molecular weight polyethylene and polyethylene wax Antioxidant (Irg1010, manufactured by Ciba Specialty Chemicals) 0.4 wt%, (P168, manufactured by Ciba Specialty Chemicals) 0.1 wt%, sodium stearate 1.3 wt%, based on parts by weight After adding calcium carbonate (manufactured by Maruo Calcium Co., Ltd.) having an average pore 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. to prepare a sheet having a thickness of about 60 μm. This sheet is immersed in an aqueous hydrochloric acid solution (hydrochloric acid 4 mol / L, nonionic surfactant 0.5 wt%) to remove calcium carbonate, and subsequently stretched 5.8 times at 105 ° C. to obtain a porous film (A) was obtained.
When the DSC measurement of the porous film (A) was performed, it was confirmed that there was no component that melted at 60 ° C.
According to the method described in “Adhesion strength measurement” of (2) above, an aramid layer was laminated on the porous film (A) and the adhesion strength was measured.

Comparative Example 1
A porous film (B) was obtained in the same manner as in Example 1 except that high wax 110P having a weight average molecular weight of 1000 manufactured by Mitsui Chemicals was used as the polyethylene wax.
When the DSC measurement of the porous film (B) was performed, it was confirmed that there was a component that melted at 60 ° C. or less.
When an aramid layer was laminated on the porous film (B) in the same manner as in Example 1 and the adhesive strength was measured, it was 5 g.

Claims (5)

A resin composition comprising an ultra-high molecular weight polyolefin and a polyolefin wax having a weight average molecular weight of 3000 or less , wherein the resin wax has a proportion of 5 to 50% by weight when the weight of the resin composition is 100% by weight. A porous film obtained using the composition, which is substantially free from components that melt at 60 ° C. or lower. A laminated porous film in which a porous heat-resistant layer is laminated on at least one surface of the porous film according to claim 1 . The porous film according to claim 1, which is a battery separator. The laminated porous film according to claim 2 , which is a battery separator. Battery comprising the battery separator according to claim 3 or 4.