JP5017764B2 - Nonaqueous electrolyte secondary battery separator and nonaqueous electrolyte secondary battery using the same - Google Patents

Description

  The present invention relates to a separator for a non-aqueous electrolyte secondary battery and a non-aqueous electrolyte secondary battery using the same.

  Specifically, the present invention reduces the number of specific impurities contained in the separator containing the inorganic filler, thereby suppressing the formation of micro short circuits and corrosion of the current collector caused by these impurities, and the cycle characteristics. The present invention relates to a separator for a non-aqueous electrolyte secondary battery that realizes a secondary battery with excellent battery performance, and a non-aqueous electrolyte secondary battery using this separator.

Lithium secondary batteries, which are non-aqueous electrolyte secondary batteries having high energy density and light weight with the reduction in weight and size of electrical products, are used in a wide range of fields. A lithium secondary battery has a positive electrode in which an active material layer containing a positive electrode active material such as a lithium compound typified by lithium cobaltate is formed on a current collector, and occlusion / release of lithium typified by graphite. A non-aqueous solution in which an active material layer containing a negative electrode active material such as a carbon material is formed on a current collector and an electrolyte such as a lithium salt such as LiPF ₆ dissolved in a normal aprotic non-aqueous solvent It is mainly composed of an electrolytic solution and a separator made of a polymer porous membrane.

  Separators used in lithium secondary batteries are required to satisfy requirements such as not impeding ion conduction between both electrodes, being able to hold an electrolytic solution, and having resistance to an electrolytic solution. A porous polymer membrane made of polypropylene or polypropylene is used.

Conventionally, as a method for producing a polymer porous membrane, for example, the following methods are known as known techniques.
(1) An extraction method in which a plasticizer that can be easily extracted and removed in a subsequent process is added to a polymer material, and then molded, and then the plasticizer is removed with a suitable solvent to make it porous (Japanese Patent Laid-Open No. 7-029563) .
(2) A stretching method in which after forming a crystalline polymer material, a structurally weak amorphous portion is selectively stretched to form micropores (Japanese Patent Laid-Open No. 7-304110).
(3) An interfacial exfoliation method in which an inorganic filler is added to a polymer material, molding is performed, and the interface between the polymer material and the inorganic filler is exfoliated by a subsequent stretching operation to form micropores (Japanese Patent Laid-Open No. 7-149937) ).

  As a method for obtaining a polymer porous membrane, the extraction method (1) described above requires treatment of a large amount of waste liquid, and has problems in both environmental and economic aspects. Further, it is difficult to obtain a uniform film due to the contraction of the film generated in the extraction process, and there is a problem in productivity such as yield. The stretching method (2) requires a long-time heat treatment for controlling the structure of the crystalline phase and the amorphous phase before stretching, which is problematic in terms of productivity.

On the other hand, the interfacial peeling method (3) has no waste liquid and is excellent in both environmental and economic aspects. In addition, since the interface between the polymer material and the inorganic filler can be easily peeled off by a stretching operation, a polymer porous membrane can be obtained without the need for pretreatment such as heat treatment. It is an excellent method.
JP 7-029563 A JP-A-7-304110 JP-A-7-149937

  However, when the polymer porous membrane obtained by the interfacial exfoliation method of (3) is applied as a separator for a secondary battery, it often causes a decrease in battery performance, particularly cycle characteristics at high temperatures. It has been difficult to put a conventional polymer porous membrane by the method into practical use as a separator for a secondary battery.

  Therefore, the present invention is a case where a separator composed of a porous polymer membrane obtained by an interface peeling method excellent in environment, economy, and productivity is applied to a non-aqueous electrolyte secondary battery, An object is to realize a non-aqueous electrolyte secondary battery excellent in battery performance such as cycle characteristics.

The separator for a non-aqueous electrolyte secondary battery according to the present invention (invention 1) is a separator for a non-aqueous electrolyte secondary battery composed of a polymer porous membrane containing an inorganic filler, and the polymer porous The material film is a thermoplastic resin film containing 40 to 300 parts by weight of an inorganic filler with respect to 100 parts by weight of the thermoplastic resin film, the halogen element contained in the separator is 10 ppm or less, and the iron element is 100 ppm or less. It is characterized by being.

The separator for a non-aqueous electrolyte secondary battery of the present invention (Claim 2) is a separator for a non-aqueous electrolyte secondary battery composed of a porous polymer membrane containing an inorganic filler, and the polymer porous The material film is a thermoplastic resin film containing 40 to 300 parts by weight of an inorganic filler with respect to 100 parts by weight of the thermoplastic resin film, the chlorine element contained in the separator is 10 ppm or less, and the iron element is 100 ppm or less. It is characterized by being.

The non-aqueous electrolyte secondary battery of the present invention (Claim 6 ) includes a positive electrode capable of inserting and extracting lithium ions, a negative electrode capable of inserting and extracting lithium ions, an electrolytic solution containing an electrolyte in a non-aqueous solvent, and In the non-aqueous electrolyte secondary battery having a separator, the separator according to the present invention is used as the separator.

  In the porous polymer membrane obtained by the interfacial exfoliation method, the present inventors pay attention to the influence of impurities that are mainly entrained in the inorganic filler and mixed in the film because the inorganic filler remains in the film as it is. As a result of extensive studies, the inventors have found that by suppressing the specific impurities contained in the separator to a predetermined amount or less, it is possible to suppress a decrease in battery performance, in particular, a decrease in cycle characteristics at high temperatures, and the present invention has been achieved.

  That is, as shown in Comparative Example 2 to be described later, since many of the industrially manufactured inorganic fillers used in the conventional interfacial peeling method are prepared using natural quarrying as a raw material, halogen elements, iron elements As a result, the polymer porous film manufactured by the conventional interface peeling method contains a halogen element or an iron element as impurities. The present inventors pay attention to the impurity elements in the separator that have been inevitably brought along with the inorganic filler, and consider the effects caused by the inclusion of these in the separator. Of the impurities, it has been found that particularly halogen elements and iron elements adversely affect battery performance.

  The details of the mechanism by which the halogen element and iron element contained in the separator cause a decrease in battery performance are not clear, but for iron element, first, when Fe elutes from the separator into the electrolyte, it is deposited on the negative electrode surface. As a result, it is considered that a small short circuit is formed, resulting in a decrease in charge / discharge efficiency and deterioration in cycle characteristics. As for the halogen element, if the halogen element is eluted from the separator into the electrolytic solution, corrosion of the outer can of the battery or the current collector is promoted, which may lead to a decrease in battery performance.

  The halogen element and the iron element contained in the polymer porous membrane constituting the separator are mostly contained in the inorganic filler and are inevitably brought in. Therefore, the separator of the present invention is an interface peeling method. The present invention is preferably applied to a separator composed of a porous polymer membrane containing an inorganic filler manufactured by the method described above, but the present invention is a battery that is caused by impurities eluted from the separator into the electrolyte as described above. Therefore, it is effective not only for separators made of polymer porous membranes manufactured by the interfacial peeling method but also for separators made of polymer porous membranes manufactured by other methods. Needless to say.

  As is apparent from the results of Examples and Comparative Examples described later, according to the present invention, the non-aqueous electrolyte solution is composed of a porous polymer membrane containing an inorganic filler and has a low content of halogen elements and iron elements. The separator for a secondary battery provides a non-aqueous electrolyte secondary battery that is excellent in battery performance, in particular, cycle characteristics at high temperatures, and has stable performance.

  Hereinafter, embodiments of the present invention will be described in detail.

[Impurity content of separator of the present invention]
The separator for a non-aqueous electrolyte secondary battery of the present invention is a separator composed of a polymer porous membrane containing an inorganic filler, and the halogen element or chlorine element contained in the separator is 10 ppm or less, and The iron element is 100 ppm or less.

  The content of halogen element and iron element in the separator can be quantified by the following method, and in the examples and comparative examples described later, the separator is configured by the following methods (i) and (ii). Halogen and iron elements in the polymer porous membrane were quantified.

(i) Determination of halogen element in separator 25 ml of pure water is added to 2 g of a sample (polymer porous membrane constituting the separator) and subjected to ultrasonic extraction for 15 minutes. For the ultrasonic extraction, for example, an ultrasonic cleaner “UT-104 SILENT SONIC” manufactured by Sharp Corporation (medium output) can be used. Thereafter, the extract is filtered, and the halogen element is quantified by ion chromatography using the filtrate as a measurement solution.

(ii) Determination of iron element in the separator 10 ml of 36% EL hydrochloric acid manufactured by Mitsubishi Chemical Corporation and 20 ml of pure water are added to 5 g of the sample (polymer porous membrane constituting the separator), and boiling extraction is performed for 30 minutes. . Thereafter, the extract is filtered, and Fe is quantified with an ICP emission spectrometer using the filtrate as a measurement solution.

  In the separator of the present invention, the upper limit of the content of halogen element, particularly chlorine element, in the separator thus measured is 10 ppm or less, preferably 8 ppm or less, more preferably 5 ppm or less. If the content of halogen elements, particularly chlorine elements, exceeds this upper limit, corrosion of battery cans and current collectors is likely to be accelerated by halogen elements such as Cl eluted in the electrolytic solution, leading to deterioration of battery performance. .

  In the separator of the present invention, the upper limit of the iron element content in the separator thus measured is 100 ppm or less, preferably 80 ppm or less, more preferably 70 ppm or less. When the content of the chlorine element exceeds this upper limit value, Fe eluted in the electrolytic solution is deposited on the negative electrode surface and a minute short circuit is likely to be formed, resulting in a decrease in charge / discharge efficiency and cycle characteristic deterioration.

  The lower limit of the content of the halogen element and the iron element in the separator is not particularly limited, but excessively lowering the content of the halogen element and the iron element includes the inclusion of the halogen element and the iron element in the separator as described later. While the number of steps such as refining the inorganic filler to reduce the amount increases and the production of the polymer porous membrane becomes difficult, the content of halogen element and iron element has the above upper limit. If lower, battery performance can be ensured, so the lower limit for the content of halogen elements, especially chlorine element in the separator is about 5 ppm, and the lower limit for the content of iron elements is about 50 ppm. Is done.

[Constituent Components and Physical Properties of the Separator of the Present Invention]
As the base resin for the polymer porous membrane constituting the separator of the present invention, a thermoplastic resin is usually used. The thermoplastic resin is not particularly limited as long as the inorganic filler described later can be uniformly dispersed. For example, polyolefin resin, fluororesin, styrene resin such as polystyrene, ABS resin, vinyl chloride resin. , Vinyl acetate resin, acrylic resin, polyamide resin, acetal resin, polycarbonate resin and the like. Among these, polyolefin resin is particularly preferable because of its excellent balance of heat resistance, solvent resistance, and flexibility. Examples of the polyolefin resin include monoolefin polymers such as ethylene, propylene, 1-butene, 1-hexene, 1-octene or 1-decene, ethylene, propylene, 1-butene, 1-hexene, 1-octene or The main component is a copolymer of 1-decene and another monomer such as 4-methyl-1-pentene or vinyl acetate. Specifically, low-density polyethylene, linear low-density polyethylene, Examples thereof include high-density polyethylene, polypropylene, crystalline ethylene-propylene block copolymer, polybutene, and ethylene-vinyl acetate copolymer. In the present invention, it is preferable to use high density polyethylene or polypropylene among the polyolefin resins. The above thermoplastic resins such as polyolefin resins may be used alone or in combination of two or more.

  The weight average molecular weight of such a thermoplastic resin is such that the lower limit is usually 50,000 or more, especially 100,000 or more, and the upper limit is usually 500,000 or less, preferably 400,000 or less, more preferably 300,000 or less, especially 200,000 or less. I just need it. When this upper limit is exceeded, melt molding becomes difficult because the melt viscosity of the resin increases in addition to the decrease in fluidity due to the addition of filler. Further, even when a molded product is obtained, the filler is not evenly dispersed in the resin, and pore formation due to interfacial peeling becomes nonuniform, which is not preferable. Below this lower limit, the mechanical strength decreases, which is not preferable.

  The kind of the inorganic filler contained in the polymer porous membrane according to the present invention is particularly limited as long as the content of the halogen element and the iron element in the separator can be suppressed to not more than the values limited in the present invention. However, general inorganic fillers can be used, but those having low reactivity with the electrolyte, particularly those having the property of not decomposing the carbonate-based organic electrolyte used in the lithium secondary battery are preferable. Examples of such inorganic fillers include sparingly water-soluble sulfates and aluminas. For example, barium sulfate and alumina are preferably used, and barium sulfate is particularly preferably used. “Slightly water-soluble” as used herein means that the solubility in water at 25 ° C. is 5 mg / l or less.

In general, carbonates such as calcium carbonate, titanium oxide, silica, and the like that are often used as fillers are not preferable because they cause decomposition of the non-aqueous electrolyte components of the lithium secondary battery, as will be described later. Here, decomposition of the organic electrolyte component is a ratio of 0.5 g of filler per 1 ml of electrolyte in an electrolyte solution composed of a mixed nonaqueous solvent solution of EC / EMC = 3: 7 (volume ratio) of 1M LiPF ₆ It is defined that the concentration of lithium ions in the electrolytic solution after being added at 85 ° C. and held for 72 hours is reduced to 0.75 mmol / g or less. The amount of lithium ions is measured by ion chromatography. In addition, it is necessary to put electrolyte solution in an airtight container so that it may not contact external air during 72 hours holding | maintenance. This is because decomposition of the electrolyte component proceeds by reacting with moisture in the air.

The table below shows the results of holding various fillers added to the electrolyte solution (1M LiPF ₆ / (EC + EMC) (3: 7, volume ratio)) under the above conditions. Compared with the ionic composition of the electrolytic solution to which no filler was added, barium sulfate and alumina showed almost no change in composition, indicating that they are suitable as inorganic fillers in the present invention. On the other hand, carbonates such as calcium carbonate and lithium carbonate, or silica and titanium oxide show a significant decrease in lithium ions and an increase in fluorine ions due to the generation of hydrofluoric acid, indicating that they are not preferred as the inorganic filler in the present invention.

  As the particle size of the inorganic filler, the lower limit of the average particle size is usually 0.1 μm or more, preferably 0.3 μm or more, more preferably 0.5 μm or more, and the upper limit is usually 10 μm or less, preferably 5 μm or less, more preferably. Is 2 μm or less. If the average particle diameter exceeds 10 μm, the diameter of the holes formed by stretching becomes too large, which is not preferable because it causes stretching breakage and a decrease in film strength. On the other hand, if the average particle size is smaller than 0.1 μm, the filler tends to aggregate, so that it is difficult to uniformly disperse the filler in the base resin.

  In this invention, if it is an inorganic filler which adapts to the said conditions, 1 type can also be used independently and 2 or more types can also be mixed and used.

  The blending amount of the inorganic filler in the polymer porous membrane according to the present invention is such that the lower limit is usually 40 parts by weight or more, preferably 50 parts by weight or more, more preferably 60 parts by weight or more, relative to 100 parts by weight of the thermoplastic resin. Preferably, it is 100 parts by weight or more, and the upper limit is usually 300 parts by weight or less, preferably 200 parts by weight or less, more preferably 150 parts by weight or less with respect to 100 parts by weight of the thermoplastic resin. When the blending amount of the inorganic filler with respect to 100 parts by weight of the thermoplastic resin in the polymer porous membrane is less than 40 parts by weight, it is difficult to form a communication hole, and it becomes difficult to express a function as a separator. On the other hand, if it exceeds 300 parts by weight, not only the viscosity at the time of film forming becomes high and the processability is inferior, but also the film breaks during stretching for making it porous, which is not preferable. In the present invention, since the inorganic filler blended in the production of the porous film remains in the substantially shaped porous film, the blending amount range of the inorganic filler is within the range of the porous film. It becomes an inorganic filler content range.

  As the inorganic filler, one that has been surface-treated with a surface treatment agent in order to enhance dispersibility in the thermoplastic resin can also be used. As the surface treatment, when the thermoplastic resin is a polyolefin resin, for example, a treatment with a fatty acid such as stearic acid or a metal salt thereof, polysiloxane, or a silane coupling agent can be given.

  At the time of molding the porous polymer membrane according to the present invention, a low molecular weight compound having compatibility with the thermoplastic resin may be added. This low molecular weight compound enters between the molecules of the thermoplastic resin, lowers the interaction between molecules and inhibits crystallization, and as a result, improves the stretchability of the resin composition during sheet molding. In addition, the low molecular weight compound moderately increases the interfacial adhesive force between the thermoplastic resin and the inorganic filler, prevents the pores from becoming coarse due to stretching, and increases the interfacial adhesive force between the thermoplastic resin and the inorganic filler. It has the effect | action which prevents the drop-off | omission of the inorganic filler from a film.

  As this low molecular weight compound, those having a molecular weight of 200 to 3000 are suitably used, and those having a molecular weight of 200 to 1000 are more preferably used. When the molecular weight of the low molecular weight compound exceeds 3000, the low molecular weight compound is difficult to enter between the molecules of the thermoplastic resin, so that the effect of improving stretchability is insufficient. On the other hand, when the molecular weight is less than 200, the compatibility is improved, but so-called blooming, in which a low molecular weight compound is precipitated on the surface of the polymer porous membrane, is likely to occur, and the membrane properties are easily deteriorated and blocking is not preferable.

  As the low molecular weight compound, when the thermoplastic resin is a polyolefin resin, an aliphatic hydrocarbon or glyceride is preferably used. In particular, when the polyolefin resin is polyethylene, liquid paraffin or low melting point wax is preferably used.

  In the resin composition as a film forming material for the polymer porous membrane according to the present invention, the lower molecular weight compound is added at a lower limit of usually 1 part by weight or more, preferably 5 parts by weight with respect to 100 parts by weight of the thermoplastic resin. The upper limit is usually 20 parts by weight or less, preferably 15 parts by weight or less, relative to 100 parts by weight of the thermoplastic resin. When the blending amount of the low molecular weight compound is less than 1 part by weight with respect to 100 parts by weight of the thermoplastic resin, the above effect by blending the low molecular weight compound cannot be sufficiently obtained, and when it exceeds 20 parts by weight, the thermoplasticity The interaction between the molecules of the resin is reduced too much and sufficient strength cannot be obtained. In addition, smoke generation occurs during sheet forming, and slipping occurs at the screw portion, making it difficult to form a stable sheet.

  If necessary, other additives such as a heat stabilizer can be added to the resin composition as a film forming material for the polymer porous membrane according to the present invention. The additive is not particularly limited as long as it is a known additive. The compounding quantity of these additives is 0.05-1 weight% normally with respect to the whole quantity of a resin composition.

  The porosity of the polymer porous membrane according to the present invention is usually 30% or more, preferably 40% or more, more preferably 50% or more as the lower limit of the porosity of the polymer porous membrane, and usually 80 as the upper limit. % Or less, preferably 70% or less, more preferably 65% or less, and particularly preferably 60% or less. If the porosity is less than 30%, the ion permeability is not sufficient, and the function as a separator cannot be achieved. On the other hand, if the porosity exceeds 80%, the actual strength of the film is lowered, which is not preferable because breakage or short-circuiting due to the active material and short-circuiting occur during battery production.

The porosity of the polymer porous membrane is a value calculated by the following calculation formula.
Porosity Pv (%) = 100 × (1−w / [ρ · S · t])
S: Area of polymer porous membrane t: Thickness of polymer porous membrane w: Weight of polymer porous membrane ρ: True specific gravity of polymer porous membrane

If the blend weight of the component i (resin, filler, etc.) constituting the polymer porous membrane is Wi and the specific gravity is ρi, the true specific gravity ρ can be obtained by the following formula (where Σ is the sum of all components) Represents the sum).
ρ = ΣWi / Σ (Wi / ρi)

  The upper limit value of the thickness of the polymer porous membrane according to the present invention is usually 100 μm or less, particularly 50 μm or less, preferably 40 μm or less, and the lower limit value is usually 5 μm or more, preferably 10 μm or more. If the thickness is less than 5 μm, the actual strength is low, and therefore, it is not preferable because breakage at the time of producing the battery, punch-through due to the active material, and short circuit occur. Moreover, since the electrical resistance of a separator will become high when thickness exceeds 100 micrometers, the capacity | capacitance of a battery falls and it is unpreferable. By setting the thickness in the range of 5 to 100 μm, a separator having good ion permeability can be obtained.

  Further, the porous polymer membrane according to the present invention has a lower limit value of Gurley permeability of 20 seconds / 100 cc or more, particularly 100 seconds / 100 cc or more, and an upper limit value of 500 seconds / 100 cc or less, particularly 300 seconds / 100 cc or less. It is preferable that When the Gurley permeability is below this lower limit, the porosity is often too high or the thickness is too thin, and as described above, the actual strength of the film is low, and breakage during battery creation and penetration by active material A short circuit occurs, which is not preferable. When the upper limit is exceeded, ion permeability is not sufficient, and the function as a separator cannot be achieved, which is not preferable. The Gurley air permeability is measured according to JIS P8117, and indicates the number of seconds that 100 cc of air passes through the membrane at a pressure of 1.22 kPa.

[Manufacturing method of separator]
Next, a method for producing a separator of the present invention will be described. Prior to that, a general method for producing a separator made of a polymer porous membrane containing an inorganic filler will be described.

<General separator manufacturing method>
The method for producing the porous polymer membrane containing the inorganic filler is not particularly limited, and examples include the following extraction method (1), stretching method (2), and interfacial peeling method (3). Interfacial peeling method.
(1) Extraction method: Melting a resin composition obtained by mixing a polymer material, an inorganic filler, and a plasticizer that can be removed by solvent extraction in a later step, and forming this into a film by a molding method such as extrusion molding Then, it is made porous by treating it with a solvent to remove the plasticizer.
(2) Stretching method: A resin composition obtained by mixing a crystalline polymer material with an inorganic filler is melted, formed into a film by a molding method such as extrusion, and then structurally stretched. Micropores are formed by cutting weak amorphous parts.
(3) Interfacial peeling method: A resin composition obtained by mixing a polymer material with an inorganic filler is melted, formed into a film by a molding method such as extrusion molding, and then stretched to obtain a polymer material. Fine pores are formed by peeling the interface with the inorganic filler.

  Among the above production methods, in the extraction method, it is difficult to selectively contain an inorganic filler on the polymer material side during molding, and the inorganic filler contained in the plasticizer portion is removed together with the plasticizer during extraction. Therefore, it is not efficient as compared with the interface peeling method. In addition, in the stretching method, when an inorganic filler is contained in the polymer material, pores are formed by stretching at the interface between the polymer material and the inorganic filler in addition to the amorphous portion, so that it is essentially not different from the interface peeling method. Therefore, in the present invention, it is preferable to employ the interfacial peeling method.

  The production of the polymer porous membrane is more specifically performed by the following method.

  First, a resin composition is prepared by blending a predetermined amount of an inorganic filler, a thermoplastic resin, and additives such as a low molecular weight compound and an antioxidant that are added as necessary, and melt-kneading. Here, the resin composition may be preliminarily mixed with a Henschel mixer or the like, and thereafter prepared using a commonly used single screw extruder, twin screw extruder, mixing roll, twin screw kneader, or the like, or The pre-kneading may be omitted and the resin composition may be directly prepared with the above extruder or the like.

  Next, the resin composition is formed into a sheet. Sheet forming can be performed by a T-die method using a commonly used T-die or an inflation method using a circular die.

  Next, the formed sheet is stretched. For the stretching, longitudinal uniaxial stretching for stretching in the sheet take-up direction (MD), transverse uniaxial stretching for stretching in the transverse direction (TD) with a tenter stretching machine, etc., uniaxial stretching to MD, followed by TD with a tenter stretching machine, etc. There is a sequential biaxial stretching method in which stretching is performed, or a simultaneous biaxial stretching method in which the longitudinal direction and the transverse direction are simultaneously stretched. The uniaxial stretching can be performed by roll stretching. The stretching can be performed at any temperature at which the resin composition constituting the sheet can be easily stretched to a predetermined stretching ratio, and the resin composition does not melt and block the pores to lose the connectivity. However, it is preferably stretched in the temperature range of the melting point of the resin—70 ° C. to the melting point of the resin—5 ° C. The stretching ratio is arbitrarily set according to the required pore diameter and strength, but preferably, stretching is performed at least 1.2 times in a uniaxial direction.

<The manufacturing method of the separator of this invention>
Next, a method for producing the separator of the present invention having a halogen element content or a chlorine element content of 10 ppm or less and an iron element content of 100 ppm or less will be described.

  Specifically, the polymer porous membrane constituting the separator of the present invention is produced by the same method as the conventional general polymer porous membrane described above. In order to make the halogen element or chlorine element content in the separator to be produced 10 ppm or less and the iron element content 100 ppm or less, it is contained in the raw material for producing the polymer porous film in the polymer porous film. Impurities introduced into the polymer porous film and impurities mixed in the polymer porous film in the polymer porous film manufacturing process are reduced by the following method.

[1] A porous polymer membrane is produced using an inorganic filler with a reduced content of halogen elements and iron elements.

  As described above, since inorganic fillers are usually produced using natural ore as a raw material, inevitably impurities such as iron and halogen elements are inevitable, for example, several hundred ppm for iron and several tens of ppm for halogen elements. Mixed in. For this reason, about the manufactured inorganic filler, the above-mentioned impurities are reduced through processes, such as refining and water washing. Alternatively, the amount of impurities in the inorganic filler is reduced by incorporating chemical synthesis into the manufacturing process of the inorganic filler. When chemical synthesis is incorporated, a process in which a halide is generated during the synthesis is not preferable because a large amount of halogen element remains in the final product.

  In the case of washing the inorganic filler produced using natural ore as a raw material, for example, it is possible to employ a method of stirring in high water at about 20 to 100 ° C. In this case, chemicals not containing halogen elements such as sulfuric acid and nitric acid and iron may be added to the cleaning water to enhance the cleaning effect. The acid concentration of the washing water is preferably 1 to 20% by weight. When washing with water to which a chemical is added, it is preferable to finish and wash with pure water at the end.

  In addition, as a method for purifying an inorganic filler produced using natural ore as a raw material, for example, a method of separating pulverized ore in air or water based on a difference in specific gravity can be employed.

  In addition, in the case of incorporating a chemical synthesis step, for example, in the case of a barium sulfate filler, it is produced by reacting barium sulfide obtained by reducing and firing barite as a raw material ore with sodium sulfate or sulfuric acid. can do. Moreover, if it is an alumina filler, it can also manufacture by adding sodium hydroxide to bauxite which is a raw material ore to make sodium aluminate, hydrolyzing it and precipitating aluminum hydroxide, and baking this at high temperature.

  Inorganic fillers thus contain halogen element or chlorine element content and iron element content in separators made of polymer porous membranes that are manufactured by incorporating water washing or purification, or by incorporating chemical synthesis process. The impurity content is reduced so that the amount is not more than the upper limit value defined in the present invention.

  Therefore, the impurity content of the inorganic filler varies depending on the amount of the inorganic filler added to the polymer porous membrane, and when the amount of the inorganic filler is small, the impurity content of the inorganic filler may be relatively large. Moreover, when there are many inorganic filler compounding quantities, it is necessary to reduce the impurity content of an inorganic filler as much as possible.

  In the present invention, the inorganic filler compounding amount described above, that is, 40 to 300 parts by weight, preferably 60 to 200 parts by weight, more preferably 100 to 150 parts by weight with respect to 100 parts by weight of the thermoplastic resin. The upper limit of the halogen element or chlorine element content of the inorganic filler is usually 30 ppm or less, preferably 20 ppm or less, more preferably 15 ppm or less, and the upper limit of the iron element content is usually 300 ppm or less, preferably 200 ppm or less, more preferably 100 ppm. It is preferable to reduce the impurity content so as to be as follows. The lower limit of the impurity content of the inorganic filler is about 7 ppm for the halogen element or chlorine element and about 70 ppm for the iron element for the same reason as the lower limit of the impurity content in the separator.

  The halogen element and iron element concentration in the inorganic filler can be quantified by the following method in the same manner as the impurity concentration in the separator (polymer porous membrane) described above. And in the comparative example, the halogen element and the iron element in the inorganic filler were quantified by the following methods (iii) and (iv).

(iii) Determination of halogen element in inorganic filler To 2 g of sample (inorganic filler), 25 ml of pure water is added and ultrasonically extracted for 15 minutes. For the ultrasonic extraction, for example, an ultrasonic cleaner “UT-104 SILENT SONIC” manufactured by Sharp Corporation (medium output) can be used. Thereafter, the extract is filtered, and the halogen element is quantified by ion chromatography using the filtrate as a measurement solution.

(iv) Determination of iron element in inorganic filler To 5 g of a sample (inorganic filler), 10 ml of 36% EL hydrochloric acid manufactured by Mitsubishi Chemical Corporation and 20 ml of pure water are added, followed by boiling extraction for 30 minutes. Thereafter, the extract is filtered, and Fe is quantified with an ICP emission spectrometer using the filtrate as a measurement solution.

  The impurity content in the inorganic filler contained in the separator can also be measured by the same method as described above. In this case, the matrix resin of the polymer porous membrane constituting the separator is baked at a high temperature, the inorganic filler is separated from the collected ash, and the same quantification as described above may be performed.

[2] As the base resin for the polymer porous membrane, a resin having a reduced content of halogen element and iron element is used.

  The thermoplastic resin used as the base resin of the polymer porous membrane may contain about 4 to 5 ppm of chlorine element derived from the catalyst in the polymerization reaction step.

  Therefore, during the production of thermoplastic resins, for example, by increasing the catalyst activity, increasing the reaction time, or increasing the reaction temperature, polymerization is performed with a small amount of catalyst used, and the amount of catalyst remaining in the thermoplastic resin is reduced. Thus, impurities derived from the catalyst are reduced.

  In the production of the separator of the present invention, any of the above-mentioned methods [1] and [2] for reducing impurities may be employed, and both may be employed to produce a polymer porous membrane. Since the halogen element and iron element therein are mainly derived from the inorganic filler, it is preferable to employ at least the impurity reduction method of [1] above.

[Non-aqueous electrolyte secondary battery]
Next, the non-aqueous electrolyte secondary battery of the present invention using the above-described separator for a non-aqueous electrolyte secondary battery of the present invention will be described. The non-aqueous electrolyte secondary battery of the present invention includes a positive electrode capable of inserting and extracting lithium ions, a negative electrode capable of inserting and extracting lithium ions, an electrolytic solution containing an electrolyte in a non-aqueous solvent, and a separator.

  As the non-aqueous solvent of the electrolyte used in the non-aqueous electrolyte secondary battery of the present invention, any known solvent can be used as the solvent for the non-aqueous electrolyte secondary battery. For example, alkylene carbonates such as ethylene carbonate, propylene carbonate, butylene carbonate; dialkyl carbonates such as dimethyl carbonate, diethyl carbonate, di-n-propyl carbonate, and ethyl methyl carbonate (the alkyl group of the dialkyl carbonate is an alkyl having 1 to 4 carbon atoms) A cyclic ether such as tetrahydrofuran and 2-methyltetrahydrofuran; a chain ether such as dimethoxyethane and dimethoxymethane; a cyclic carboxylic acid ester such as γ-butyrolactone and γ-valerolactone; methyl acetate, methyl propionate and propion Examples thereof include chain carboxylic acid esters such as ethyl acid. These may be used alone or in combination of two or more.

Arbitrary things can be used as lithium salt which is a solute of nonaqueous system electrolyte. For example, inorganic lithium salts such as LiClO ₄ , LiPF ₆ and LiBF ₄ ; LiCF ₃ SO ₃ , LiN (CF ₃ SO ₂ ) ₂ , LiN (C ₂ F ₅ SO ₂ ) ₂ , LiN (CF ₃ SO ₂ ) (C _{4 F 9 SO 2), LiC} (CF 3 SO 2) 3, LiPF 4 (CF 3) 2, LiPF 4 (C 2 F 5) 2, LiPF 4 (CF 3 SO 2) 2, LiPF 4 (C 2 F _{5 SO 2) 2, LiBF 2} (CF 3) 2, LiBF 2 (C 2 F 5) 2, LiBF 2 (CF 3 SO 2) 2 and _{LiBF 2 (C 2 F 5 SO} 2) 2 , etc. the fluorine-containing organic Examples include lithium salts. Of these, LiPF ₆ , LiBF ₄ , LiCF ₃ SO ₃ , LiN (CF ₃ SO ₂ ) ₂ or LiN (C ₂ F ₅ SO ₂ ) ₂ , particularly LiPF ₆ or LiBF ₄ are preferred. In addition, about lithium salt, 1 type may be used independently and 2 or more types may be used together.

  The lower limit of the concentration of these lithium salts in the non-aqueous electrolyte is usually 0.5 mol / l or more, especially 0.75 mol / l or more, and the upper limit is usually 2 mol / l or less, especially 1.5 mol / l. l or less. When the concentration of the lithium salt exceeds this upper limit value, the viscosity of the nonaqueous electrolytic solution increases and the electrical conductivity also decreases. Moreover, since electrical conductivity will become low if less than a lower limit, it is preferable to prepare a non-aqueous electrolyte within the said concentration range.

  The non-aqueous electrolyte solution according to the present invention has other useful components as required, for example, conventionally known overcharge inhibitors, dehydrating agents, deoxidizing agents, capacity maintenance characteristics and cycle characteristics after high-temperature storage. You may contain various additives, such as an auxiliary agent for improving.

  Auxiliaries for improving capacity maintenance characteristics and cycle characteristics after high temperature storage include carbonate compounds such as vinylene carbonate, fluoroethylene carbonate, trifluoropropylene carbonate, phenylethylene carbonate and erythritan carbonate; succinic anhydride, anhydrous glutar Carboxylic acid anhydrides such as acid, maleic anhydride, citraconic anhydride, glutaconic anhydride, itaconic anhydride, diglycolic anhydride, cyclohexanedicarboxylic anhydride, cyclopentanetetracarboxylic dianhydride, phenylsuccinic anhydride; Sulfur containing ethylene sulfite, 1,3-propane sultone, 1,4-butane sultone, methyl methanesulfonate, busulfan, sulfolane, sulfolene, dimethyl sulfone, tetramethylthiuram monosulfide, etc. Compound; Nitrogen-containing compound such as 1-methyl-2-pyrrolidinone, 1-methyl-2-piperidone, 3-methyl-2-oxazolidinone, 1,3-dimethyl-2-imidazolidinone, N-methylsuccinimide; Examples thereof include hydrocarbon compounds such as heptane, octane, and cycloheptane. When the non-aqueous electrolyte contains these auxiliaries, the concentration is usually 0.1 to 5% by weight.

  As the positive electrode, a material in which an active material layer containing a positive electrode active material and a binder is usually formed on a current collector is used.

  Examples of the positive electrode active material include materials capable of inserting and extracting lithium, such as lithium transition metal composite oxide materials such as lithium cobalt oxide, lithium nickel oxide, and lithium manganese oxide. These may be used individually by 1 type, or may use multiple types together.

  The binder is not particularly limited as long as it is a material that is stable with respect to the solvent and electrolyte used during electrode production and other materials used during battery use. Specific examples thereof include polyvinylidene fluoride, polytetrafluoroethylene, fluorinated polyvinylidene fluoride, EPDM (ethylene-propylene-diene terpolymer), SBR (styrene-butadiene rubber), NBR (acrylonitrile-butadiene rubber), Examples thereof include fluororubber, polyvinyl acetate, polymethyl methacrylate, polyethylene, and nitrocellulose. These may be used individually by 1 type, or may use multiple types together.

  As for the ratio of the binder in the positive electrode active material layer, the lower limit is usually 0.1% by weight or more, preferably 1% by weight or more, more preferably 5% by weight or more, and the upper limit is usually 80% by weight or less, preferably 60% by weight or less, more preferably 40% by weight or less, and still more preferably 10% by weight or less. If the proportion of the binder is small, the active material cannot be sufficiently retained, so that the mechanical strength of the positive electrode is insufficient, and the battery performance such as cycle characteristics may be deteriorated. On the contrary, if the amount is too large, the battery capacity and conductivity are lowered. It will be.

  The positive electrode active material layer usually contains a conductive agent in order to increase conductivity. Examples of the conductive agent include carbonaceous materials such as graphite fine particles such as natural graphite and artificial graphite, carbon black such as acetylene black, and amorphous carbon fine particles such as needle coke. These may be used individually by 1 type, or may use multiple types together. The ratio of the conductive agent in the positive electrode active material layer is such that the lower limit is usually 0.01% by weight or more, preferably 0.1% by weight or more, more preferably 1% by weight or more, and the upper limit is usually 50% by weight or less. , Preferably 30% by weight or less, more preferably 15% by weight or less. If the proportion of the conductive agent is small, the conductivity may be insufficient, and conversely if too large, the battery capacity may be reduced.

  In addition, the positive electrode active material layer can contain additives for a normal active material layer such as a thickener.

  The thickener is not particularly limited as long as it is a material that is stable with respect to the solvent and electrolyte used during electrode production and other materials used during battery use. Specific examples thereof include carboxymethyl cellulose, methyl cellulose, hydroxymethyl cellulose, ethyl cellulose, polyvinyl alcohol, oxidized starch, phosphorylated starch, and casein. These may be used individually by 1 type, or may use multiple types together.

  Aluminum, stainless steel, nickel-plated steel or the like is used for the current collector of the positive electrode.

  The positive electrode can be formed by applying a slurry obtained by slurrying the above-described positive electrode active material, a binder, a conductive agent, and other additives added as necessary with a solvent onto a current collector, and drying the positive electrode active material. . As the solvent used for slurrying, an organic solvent that dissolves the binder is usually used. For example, N-methylpyrrolidone, dimethylformamide, dimethylacetamide, methyl ethyl ketone, cyclohexanone, methyl acetate, methyl acrylate, diethyltriamine, NN-dimethylaminopropylamine, ethylene oxide, tetrahydrofuran and the like are used, but not limited thereto. These may be used individually by 1 type, or may use multiple types together. Moreover, a dispersing agent, a thickener, etc. can be added to water, and an active material can also be slurried with latex, such as SBR.

  Thus, the thickness of the positive electrode active material layer formed is about 10-200 micrometers normally. The active material layer obtained by coating and drying is preferably consolidated by a roller press or the like in order to increase the packing density of the active material.

  As the negative electrode, a material in which an active material layer containing a negative electrode active material and a binder is usually formed on a current collector is used.

  As a negative electrode active material, a carbonaceous material capable of occluding / releasing lithium such as organic pyrolysate, artificial graphite and natural graphite under various pyrolysis conditions; capable of occluding / releasing lithium such as tin oxide and silicon oxide Metal oxide material; lithium metal; various lithium alloys can be used. These negative electrode active materials may be used individually by 1 type, and may mix and use 2 or more types.

  The binder is not particularly limited as long as it is a material that is stable with respect to the solvent and electrolyte used during electrode production and other materials used during battery use. Specific examples thereof include polyvinylidene fluoride, polytetrafluoroethylene, styrene / butadiene rubber, isoprene rubber, and butadiene rubber. These may be used individually by 1 type, or may use multiple types together.

  The ratio of the binder in the negative electrode active material layer is such that the lower limit is usually 0.1% by weight or more, preferably 1% by weight or more, more preferably 5% by weight or more, and the upper limit is usually 80% by weight or less. Preferably it is 60 weight% or less, More preferably, it is 40 weight% or less, More preferably, it is 10 weight% or less. If the ratio of the binder is small, the active material cannot be sufficiently retained, so that the negative electrode mechanical strength may be insufficient, and the battery performance such as cycle characteristics may be deteriorated. become.

  The negative electrode active material layer usually contains a conductive agent in order to increase conductivity. Examples of the conductive agent include carbonaceous materials such as graphite fine particles such as natural graphite and artificial graphite, carbon black such as acetylene black, and amorphous carbon fine particles such as needle coke. These may be used individually by 1 type, or may use multiple types together. As for the ratio of the conductive agent in the negative electrode active material layer, the lower limit is usually 0.01% by weight or more, preferably 0.1% by weight or more, more preferably 1% by weight or more, and the upper limit is usually 50% by weight or less. , Preferably 30% by weight or less, more preferably 15% by weight or less. If the proportion of the conductive agent is small, the conductivity may be insufficient, and conversely if too large, the battery capacity may be reduced.

  In addition, the negative electrode active material layer may contain additives for a normal active material layer such as a thickener.

  The thickener is not particularly limited as long as it is a material that is stable with respect to the solvent and electrolyte used during electrode production and other materials used during battery use. Specific examples thereof include carboxymethyl cellulose, methyl cellulose, hydroxymethyl cellulose, ethyl cellulose, polyvinyl alcohol, oxidized starch, phosphorylated starch, and casein. These may be used individually by 1 type, or may use multiple types together.

  Copper, nickel, stainless steel, nickel-plated steel, or the like is used for the negative electrode current collector.

  The negative electrode can be formed by applying a slurry obtained by slurrying the above-described negative electrode active material, a binder, a conductive agent, and other additives added as necessary with a solvent onto a current collector, and then drying the negative electrode active material. .

  As the solvent for forming a slurry, an organic solvent that dissolves the binder is usually used. For example, N-methylpyrrolidone, dimethylformamide, dimethylacetamide, methyl ethyl ketone, cyclohexanone, methyl acetate, methyl acrylate, diethyltriamine, NN-dimethylaminopropylamine, ethylene oxide, tetrahydrofuran and the like are used, but not limited thereto. These may be used individually by 1 type, or may use multiple types together. Moreover, a dispersing agent, a thickener, etc. can be added to water, and an active material can also be slurried with latex, such as SBR.

  Thus, the thickness of the negative electrode active material layer formed is about 10-200 micrometers normally. The active material layer obtained by coating and drying is preferably consolidated by a roller press or the like in order to increase the packing density of the active material.

  The lithium secondary battery of the present invention is manufactured by assembling the positive electrode, the negative electrode, the non-aqueous electrolyte, and the separator of the present invention into an appropriate shape. Furthermore, other components such as an outer case can be used as necessary.

  The battery shape is not particularly limited, and can be appropriately selected from various commonly used shapes according to the application. Examples of commonly used shapes include a cylinder type with a sheet electrode and separator spiral, an inside-out cylinder type with a combination of pellet electrode and separator, a coin type with a stack of pellet electrode and separator, and a sheet Examples include a laminate type in which electrodes and separators are laminated. The method for assembling the battery is not particularly limited, and can be appropriately selected from various commonly used methods according to the shape of the target battery.

  The general embodiment of the lithium secondary battery of the present invention has been described above. However, the lithium secondary battery of the present invention is not limited to the above embodiment, and various modifications can be made without departing from the gist thereof. Can be implemented.

  The use of the lithium secondary battery of the present invention is not particularly limited, and can be used for various known uses. Specific examples include notebook computers, pen input computers, mobile computers, electronic book players, mobile phones, mobile faxes, mobile copy, mobile printers, headphone stereos, video movies, LCD TVs, handy cleaners, portable CDs, minidiscs, and transceivers. , Electronic notebooks, calculators, memory cards, portable tape recorders, radios, backup power supplies, motors, lighting equipment, toys, gaming devices, small devices such as watches, strobes and cameras, and large devices such as electric vehicles and hybrid vehicles Can be mentioned.

  EXAMPLES Hereinafter, the present invention will be described more specifically with reference to examples and comparative examples. However, the present invention is not limited to these examples as long as the gist thereof is not exceeded.

[Example 1]
<Manufacture of polymer porous membrane>
High density polyethylene [“HI-ZEX7000FP” manufactured by Mitsui Chemicals, Inc., weight average molecular weight: 200,000, density: 0.956 g / cm ³ , melt flow rate: 0.04 g / 10 min], 100 parts by weight, soft polypropylene [Idemitsu Petrochemical "PER R110E", weight average molecular weight: 330,000, 15.6 parts by weight, hydrogenated castor oil [HY-CASTOR OIL, molecular weight 938, manufactured by Toyokuni Oil Co., Ltd., 9.4 parts by weight, barium sulfate [硫酸] “B-55” manufactured by Kagaku Co., Ltd., average particle size 0.66 μm] 187.5 parts by weight was blended and melt-kneaded, and the resulting resin composition was subjected to inflation molding at a temperature of 210 ° C. to obtain a raw sheet. The thickness of the original fabric sheet was 105 μm on average. Next, the obtained raw sheet was sequentially stretched at 70 ° C. in the sheet longitudinal direction (MD) by 1.31 times, and then at 110 ° C. in the width direction (TD) by 2.95 times to obtain a film thickness of 25 μm, A porous polymer membrane having a porosity of 60% and a Gurley air permeability of 110 seconds / 100 cc was obtained (Gurley air permeability was measured using a B-type Gurley Densometer (Toyo Seiki Seisakusho) according to JIS P8117). Measured). Table 2 shows the results of quantification of halogen (Cl) and Fe contained in the obtained polymer porous membrane and barium sulfate used as an inorganic filler according to the above-described quantification method.

<Preparation of electrolyte>
Under a dry argon atmosphere, a sufficiently dried LiPF ₆ was dissolved in a mixture of ethylene carbonate and ethyl methyl carbonate (volume ratio 3: 7) so as to have a ratio of 1.0 mol / liter to obtain an electrolytic solution.

<Preparation of positive electrode>
LiCoO ₂ was used as the positive electrode active material, and 6 parts by weight of carbon black and 9 parts by weight of polyvinylidene fluoride (trade name “KF-1000” manufactured by Kureha Chemical Co., Ltd.) were added to 85 parts by weight of LiCoO ₂ and mixed. Disperse with 2-pyrrolidone to form a slurry. This was uniformly applied to one side of a 20 μm-thick aluminum foil as a positive electrode current collector, dried, and then pressed by a press machine so that the density of the positive electrode active material layer was 3.0 g / cm ^3. It was.

<Production of negative electrode>
Using natural graphite powder as a negative electrode active material, 94 parts by weight of natural graphite powder was mixed with 6 parts by weight of polyvinylidene fluoride, and dispersed with N-methyl-2-pyrrolidone to form a slurry. This was uniformly applied to one side of a 18 μm-thick copper foil as a negative electrode current collector, dried, and then pressed by a pressing machine so that the density of the negative electrode active material layer was 1.5 g / cm ^3. did.

<Battery assembly>
A 2032 type coin cell was produced using the porous polymer membrane as a separator together with the electrolytic solution, positive electrode and negative electrode. That is, a stainless steel can that also serves as a positive electrode conductor is accommodated with a positive electrode impregnated with an electrolyte by punching into a disk shape having a diameter of 12.5 mm, and a separator having a diameter of 18.8 mm impregnated with the electrolyte A negative electrode impregnated with an electrolyte by punching into a disk shape having a diameter of 12.5 mm was placed. The can body and a sealing plate serving also as a negative electrode conductor were caulked and sealed via an insulating gasket to produce a coin-type battery. Here, the impregnation of the battery member with the electrolytic solution was performed by immersing each member in the electrolytic solution for 2 minutes.

<Battery evaluation>
At a constant current corresponding to 0.2 C at 25 ° C. (the rated capacity due to the discharge capacity at 1 hour rate is 1 C, and the same applies hereinafter), the charge end voltage is 4.2 V and the discharge end voltage is 3 V. Charge and discharge are stabilized by 3 cycles, and the 4th cycle is charged to a charge end voltage of 4.2 V with a current corresponding to 0.5 C, and charged until the charge current value reaches a current value corresponding to 0.05 C. After 4.2V-constant current constant voltage charge (CCCV charge) (0.05C cut), 3V discharge was performed at a constant current value corresponding to 0.2C. Furthermore, 100 cycles of charge / discharge were performed at a constant current corresponding to a charge / discharge current value of 2C at 60 ° C. with a charge end voltage of 4.2 V and a discharge end voltage of 3 V, and changes in the discharge capacity at each cycle were examined. The results are shown in Table 2.

[Example 2]
A film thickness of 30 μm, a porosity of 68%, and a Gurley air permeability of 50 seconds / 100 cc were the same as in Example 1 except that barium sulfate (“BA” average particle diameter of 8 μm manufactured by Sakai Chemical Co., Ltd.) was used as the inorganic filler. A porous polymer membrane was obtained. Table 2 shows the results of quantification of halogen (Cl) and Fe contained in the obtained polymer porous membrane and barium sulfate used as an inorganic filler according to the above-described quantification method.

  A coin-type battery was assembled and evaluated in the same manner as in Example 1 except that this polymer porous membrane was used as a separator, and the results are shown in Table 2.

Example 3
Barium sulfate (“BC” manufactured by Sakai Chemical Co., Ltd., average particle size 10 μm) was extracted with 5% by weight sulfuric acid for 1 hour, filtered, washed with pure water, and further subjected to ultrasonic extraction for 30 minutes in pure water followed by filtration. Washed with pure water. The barium sulfate after washing was dried at 120 ° C. for 1 hour, and further vacuum dried at 120 ° C. for 12 hours. A polymer porous membrane having a film thickness of 34 μm, a porosity of 67%, and a Gurley permeability of 40 seconds / 100 cc was obtained in the same manner as in Example 1 except that barium sulfate subjected to the above treatment was used as an inorganic filler. It was. Table 2 shows the results of quantification of halogen (Cl) and Fe contained in the obtained polymer porous membrane and barium sulfate used as an inorganic filler according to the above-described quantification method.

  A coin-type battery was assembled and evaluated in the same manner as in Example 1 except that this polymer porous membrane was used as a separator, and the results are shown in Table 2.

[Comparative Example 1]
A film thickness of 22 μm, a porosity of 62%, and a Gurley air permeability were the same as in Example 1 except that barium sulfate (“B-1” average particle diameter 0.8 μm manufactured by Sakai Chemical Co., Ltd.) was used as the inorganic filler. A polymer porous membrane of 100 seconds / 100 cc was obtained. Table 2 shows the results of quantification of halogen (Cl) and Fe contained in the obtained polymer porous membrane and barium sulfate used as an inorganic filler according to the above-described quantification method.

  A coin-type battery was assembled and evaluated in the same manner as in Example 1 except that this polymer porous membrane was used as a separator, and the results are shown in Table 2.

[Comparative Example 2]
The film thickness was 33 μm, the porosity was 66%, and the Gurley air permeability was 40 seconds / 100 cc in the same manner as in Example 1 except that barium sulfate (“BC” average particle diameter 10 μm manufactured by Sakai Chemical Co., Ltd.) was used as the inorganic filler. A porous polymer membrane was obtained. Table 2 shows the results of quantification of halogen (Cl) and Fe contained in the obtained polymer porous membrane and barium sulfate used as an inorganic filler according to the above-described quantification method.

  A coin-type battery was assembled and evaluated in the same manner as in Example 1 except that this polymer porous membrane was used as a separator, and the results are shown in Table 2.

From Table 2, it can be seen that the cycle characteristics at high temperatures can be improved by limiting the specific impurity content of the halogen element, particularly chlorine element and iron element, for the separator.
In general, halogen ions dissolve metal surface passivation and convert metal oxides into metal halides. Since metal halide is easily dissolved, corrosion proceeds. Therefore, as represented by the result of chloride ions, it is considered that when the halogen concentration is high, the corrosion of the can and the current collector proceeds and the battery characteristics such as the cycle characteristics deteriorate.
Therefore, from the results of Examples 1 to 3, it is considered that the same effects can be achieved by limiting the halogen elements in general.

  The present invention is useful for improving the performance of a non-aqueous electrolyte secondary battery, in particular, cycle characteristics.

Claims (5)

A separator for a non-aqueous electrolyte secondary battery composed of a polymer porous membrane containing an inorganic filler, wherein the polymer porous membrane contains 40 to 40 inorganic fillers per 100 parts by weight of a thermoplastic resin membrane. A separator for a non-aqueous electrolyte secondary battery , which is a thermoplastic resin film containing 300 parts by weight, wherein the halogen element contained in the separator is 10 ppm or less and the iron element is 100 ppm or less. A separator for a non-aqueous electrolyte secondary battery composed of a polymer porous membrane containing an inorganic filler, wherein the polymer porous membrane contains 40 to 40 inorganic fillers per 100 parts by weight of a thermoplastic resin membrane. A separator for a non-aqueous electrolyte secondary battery , which is a thermoplastic resin film containing 300 parts by weight, wherein the chlorine element contained in the separator is 10 ppm or less and the iron element is 100 ppm or less.   The separator for a non-aqueous electrolyte secondary battery according to claim 1 or 2, wherein the inorganic filler includes a material selected from the group consisting of barium sulfate and alumina. An inorganic filler is added to an electrolytic solution composed of a mixed non-aqueous solvent solution of EC / EMC = 3: 7 (volume ratio) of 1M LiPF ₆ at a ratio of 0.5 g per ml of the electrolytic solution, and 85 ° C. 4. The non-aqueous electrolyte secondary battery according to claim 1, wherein the concentration of lithium ions in the electrolyte after holding for 72 hours exceeds 0.75 mmol / g. Separator. A non-aqueous electrolyte secondary battery having a positive electrode capable of inserting and extracting lithium ions, a negative electrode capable of inserting and extracting lithium ions, an electrolytic solution containing an electrolyte in a non-aqueous solvent, and a separator, as a separator. A non-aqueous electrolyte secondary battery using the separator according to any one of 1 to 4 .