WO2005015660A1 - 非水系電解液二次電池用セパレータ及びそれを用いた非水系電解液二次電池 - Google Patents
非水系電解液二次電池用セパレータ及びそれを用いた非水系電解液二次電池 Download PDFInfo
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- WO2005015660A1 WO2005015660A1 PCT/JP2004/001466 JP2004001466W WO2005015660A1 WO 2005015660 A1 WO2005015660 A1 WO 2005015660A1 JP 2004001466 W JP2004001466 W JP 2004001466W WO 2005015660 A1 WO2005015660 A1 WO 2005015660A1
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- electrolyte secondary
- secondary battery
- aqueous electrolyte
- filler
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/38—Selection of substances as active materials, active masses, active liquids of elements or alloys
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
- H01M4/133—Electrodes based on carbonaceous material, e.g. graphite-intercalation compounds or CFx
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/052—Li-accumulators
- H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
- H01M4/483—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides for non-aqueous cells
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
- H01M4/52—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of nickel, cobalt or iron
- H01M4/523—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of nickel, cobalt or iron for non-aqueous cells
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
- H01M4/52—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of nickel, cobalt or iron
- H01M4/525—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of nickel, cobalt or iron of mixed oxides or hydroxides containing iron, cobalt or nickel for inserting or intercalating light metals, e.g. LiNiO2, LiCoO2 or LiCoOxFy
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/58—Selection of substances as active materials, active masses, active liquids of inorganic compounds other than oxides or hydroxides, e.g. sulfides, selenides, tellurides, halogenides or LiCoFy; of polyanionic structures, e.g. phosphates, silicates or borates
- H01M4/583—Carbonaceous material, e.g. graphite-intercalation compounds or CFx
- H01M4/587—Carbonaceous material, e.g. graphite-intercalation compounds or CFx for inserting or intercalating light metals
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
- H01M50/40—Separators; Membranes; Diaphragms; Spacing elements inside cells
- H01M50/409—Separators, membranes or diaphragms characterised by the material
- H01M50/411—Organic material
- H01M50/414—Synthetic resins, e.g. thermoplastics or thermosetting resins
- H01M50/417—Polyolefins
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
- H01M50/40—Separators; Membranes; Diaphragms; Spacing elements inside cells
- H01M50/489—Separators, membranes, diaphragms or spacing elements inside the cells, characterised by their physical properties, e.g. swelling degree, hydrophilicity or shut down properties
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
- H01M50/40—Separators; Membranes; Diaphragms; Spacing elements inside cells
- H01M50/489—Separators, membranes, diaphragms or spacing elements inside the cells, characterised by their physical properties, e.g. swelling degree, hydrophilicity or shut down properties
- H01M50/491—Porosity
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
- H01M50/40—Separators; Membranes; Diaphragms; Spacing elements inside cells
- H01M50/409—Separators, membranes or diaphragms characterised by the material
- H01M50/446—Composite material consisting of a mixture of organic and inorganic materials
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02T—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO TRANSPORTATION
- Y02T10/00—Road transport of goods or passengers
- Y02T10/60—Other road transportation technologies with climate change mitigation effect
- Y02T10/70—Energy storage systems for electromobility, e.g. batteries
Definitions
- the present invention relates to a separator for a non-aqueous electrolyte secondary battery and a non-aqueous electrolyte secondary battery using the same.
- Aqueous electrolyte This is related to a secondary battery.
- the present invention provides a separator for a non-aqueous electrolyte secondary battery, which realizes a secondary battery having excellent battery performance, in which the discharge efficiency is hardly reduced even during high-load discharge, and a non-aqueous electrolyte using the separator.
- the present invention relates to an aqueous electrolyte secondary battery.
- the present invention reduces specific impurities contained in a separator containing an inorganic filler, thereby suppressing the formation of minute short-circuits caused by these impurities, preventing corrosion of the current collector, and the like.
- Another object of the present invention is to provide a separator for a non-aqueous electrolyte secondary battery which realizes a secondary battery having excellent battery performance such as cycle characteristics, and a non-aqueous electrolyte secondary battery using the separator.
- Lithium rechargeable batteries which are non-aqueous electrolyte rechargeable batteries that have high energy densities and are lightweight, have been used in a wide range of fields as lighter and smaller electric appliances have become smaller.
- 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 cobalt oxide is formed on a current collector, and a lithium storage cell typified by graphite.
- a negative electrode active material layer is formed on the current collector containing a negative electrode active material such as a carbon material capable release, the electrolyte such as lithium salt, such as L i PF 6 usually aprotic non-aqueous solvent It is mainly composed of a dissolved non-aqueous electrolyte and a separator composed of a porous membrane.
- a negative electrode active material such as a carbon material capable release
- the electrolyte such as lithium salt, such as L i PF 6 usually aprotic non-aqueous solvent It is mainly composed of a dissolved non-aqueous electrolyte and a separator composed of a porous membrane.
- Separators used in lithium secondary batteries are required to satisfy requirements such as not disturbing ionic conduction between the two electrodes, capable of holding an electrolyte, and having resistance to the electrolyte.
- Mainly thermoplastics such as polyethylene and polypropylene
- a porous film made of a conductive resin is used.
- the extraction method (1) described above as a method for obtaining a porous membrane made of a thermoplastic resin needs to treat a large amount of waste liquid, and is problematic in terms of both environment and economy. In addition, it is difficult to obtain a uniform film due to contraction of the film generated during the extraction process, and there is a problem in productivity such as yield.
- the stretching method (2) requires a long-time heat treatment to control the pore size distribution by controlling the structure of the crystalline phase and the amorphous phase before stretching, which is problematic in terms of productivity.
- Japanese Patent Application Laid-Open No. 6-200436 discloses a polyolefin solution containing an ultra-high molecular weight component and having a large molecular weight distribution, which is extruded to form a sheet.
- the gel-like sheet obtained by forming into a shape and quenching is subjected to stretching and solvent removal operations at a specific temperature to obtain a polyolefin having a sharp pore size distribution with a maximum pore size of 1.5 or less. It is disclosed to obtain a porous membrane.
- this method requires a large number of steps because it is necessary to perform two stretching operations at different temperatures in order to form a uniform hole and expand it to a practically suitable size. Is more complicated than the extraction method, and there is a problem in productivity. In addition, since the stretching process is performed twice, there may be a problem such as uneven stretching in each process. Furthermore, since this method is essentially an extraction method, it is necessary to treat a large amount of waste liquid as described above, and there is a problem in terms of environment and economy. In addition, it is difficult to obtain a uniform film due to shrinkage of the film generated in the extraction process. There is also a problem in productivity such as ball.
- the interfacial peeling method (3) has no waste liquid and is excellent in terms of both environment and economy.
- a porous membrane can be obtained without the need for a pretreatment such as heat treatment, and the productivity is also excellent. It is a technique.
- Japanese Patent Application Laid-Open No. 2002-201298 discloses a porous film composed of a thermoplastic resin and a filler, and having a thickness of Y (; um).
- the present invention applies a separator composed of a porous membrane made of a filler-containing thermoplastic resin obtained by an interfacial peeling method excellent in environment, economy and productivity to a nonaqueous electrolyte secondary battery. Even in such a case, an object is to realize a non-aqueous electrolyte secondary battery having excellent battery performance such as load characteristics. In addition, the present invention further provides a cycle characteristic It is an object of the present invention to realize a non-aqueous electrolyte secondary battery excellent in the above.
- the separator for a non-aqueous electrolyte secondary battery of the present invention is a separator for a non-aqueous electrolyte secondary battery comprising a porous film containing a filler in a thermoplastic resin, wherein ASTMF 3 16 -86
- the ratio d ave / d max between the average pore diameter d ave ( ⁇ ) and the maximum pore diameter d max ( ⁇ m) determined by the above method is 0.6 or more.
- the non-aqueous electrolyte secondary battery of the present invention is a non-aqueous electrolyte having a positive electrode capable of occluding and releasing lithium ions, a negative electrode capable of occluding and releasing lithium ions, an electrolyte containing an electrolyte in a non-aqueous solvent, and a separator.
- An electrolyte secondary battery is characterized in that such a separator of the present invention is used as a separator.
- the present inventors have conducted intensive studies on the properties of the filler and the control of the physical properties of the porous film made of a thermoplastic resin containing the filler, and as a result, the filler has not been used industrially as a filler so far.
- the porous membrane made of thermoplastic resin obtained by the interfacial peeling method has a remarkably uniform pore size and extremely excellent battery performance as a separator for non-aqueous electrolyte secondary batteries. In particular, they have found that the load characteristics can be improved, and have completed the present invention.
- the particle size distribution of the filler has an extremely large effect on the film structure because the interface between the base resin and the filler is peeled off by a stretching operation to form a porous structure.
- particles with a wide particle size distribution will be mixed with particles with a large particle size, so the total number of particles will be smaller than that with a narrow particle size distribution. This means that the number of starting points of the holes in the stretching operation is reduced, which is thought to result in an increase in the ion passage resistance due to a decrease in the communication of the holes.
- the control of the particle size distribution of the filler can be controlled by selecting the shape of the filler, which makes it difficult for those skilled in the art to control the porous state which is very delicate for battery performance. It is very advantageous industrially.
- a separator having a uniform pore diameter is realized by controlling the particle size distribution of the filler, thereby increasing the ion passage resistance due to a shortage of the opening starting points.
- the load capacity at discharge rate 6 C is 60% or more of the discharge capacity at discharge rate C / 3.
- An aqueous electrolyte secondary battery is realized.
- the present inventors have found that, in a polymer porous membrane obtained by the interfacial peeling method, an inorganic filler remains in the film as it is, so that the influence of impurities that are mainly entrained in the inorganic filler and mixed into the film.
- the present inventors have found that by suppressing the specific impurities contained in the separator to a predetermined amount or less, it is possible to further suppress a decrease in cycle characteristics at a high temperature, and have reached the present invention.
- the porous polymer membrane produced by the conventional interfacial peeling method contains a halogen element and an iron element as impurities.
- the present inventors focused on such impurity elements in the separator, which were inevitably brought along with the inorganic filler, and examined the effects caused by inclusion of these elements in the separator.
- the reduction in the vital properties at high temperatures can be further suppressed by keeping the halogen element and the iron element, among the impurities, particularly below a predetermined amount.
- a separator for a non-aqueous electrolyte secondary battery having a uniform pore diameter which is made of a thermoplastic resin porous membrane containing a filler. Battery performance, especially excellent load characteristics, stable non-aqueous performance A system electrolyte secondary battery is provided.
- the separator for a non-aqueous electrolyte secondary battery according to the present invention has a reduced non-aqueous electrolyte with a reduced content of halogen elements and iron elements, thereby further improving battery performance, especially cycle characteristics at high temperatures. Rechargeable batteries can be provided.
- the non-aqueous electrolyte secondary battery separator of the present invention comprises a porous film containing a filler in a thermoplastic resin, and has an average pore diameter d ave (m) determined by ASTM F316-86.
- the ratio d ave Zd raax to the maximum pore diameter d max ( ⁇ ⁇ ) is 0.6 or more.
- the average pore size and the maximum pore size according to the present invention are those specified in ASTM F316-86.
- the average pore diameter of the separator of the present invention that is, the lower limit of the average pore diameter d ave of the porous membrane constituting the separator is usually 0.03 / m or more, preferably 0.05 / m or more, and more preferably 0 / m or more. It is at least 1 ⁇ , particularly preferably at least 0.5 im, and the upper limit is usually at most, preferably at most 3 ⁇ , more preferably at most 2 ⁇ . If the average pore diameter d ave is less than 0.03 Aim, it becomes difficult to connect the pores formed by interfacial separation, and clogging due to by-products of the reaction inside the battery is likely to occur.
- the electric resistance increases and the load characteristics of the obtained secondary battery tend to decrease. If the average pore size d ave exceeds 5 m, the by-products of the reaction inside the battery tend to move, promoting the deterioration of the electrode active material, and the cycle characteristics of the resulting secondary battery tend to decrease. .
- the ratio of the average pore diameter to the maximum pore diameter of the separator of the present invention that is, the value of the average pore diameter d ave maximum pore diameter d raax of the porous membrane constituting the separator of the present invention is 0.6 or more.
- This ratio d ave / d max is preferably 0.65 or more, more preferably 0.7 or more. If d ave / d max is less than 0.6, variations in the pore size of the separator may occur. The problem is that the battery performance such as load characteristics decreases.
- d ave / d max be higher, since the variation in the pore diameter of the separator is smaller and especially the variation to the larger side is smaller, but if the upper limit of d ave Z d max is about 0.95, It is enough.
- thermoplastic resin that is the base resin of the porous membrane constituting the separator of the present invention is not particularly limited as long as the filler can be dispersed evenly.
- examples thereof include polyolefin resin and fluorine.
- Resins, styrene resins such as polystyrene, ABS resins, vinyl chloride resins, vinyl acetate resins, acrylic resins, polyamide resins, acetal resins, polycarbonate resins, and the like.
- a polyolefin resin is particularly preferred because of its excellent balance of heat resistance, solvent resistance, and flexibility.
- polyolefin resin examples include monoolefin polymers such as ethylene, propylene, 1-butene, 1-hexene, 1-otaten and 1-decene, and ethylene, propylene, 1-butene, 1-hexene, and 1-hexene.
- the main component is a copolymer of octene or 1-decene with another monomer such as 4-methyl-11-pentene or biel acetate.
- Specific examples thereof include low-density polyethylene, linear Examples include low-density polyethylene, high-density polyethylene, polypropylene, crystalline raw ethylene-propylene block copolymer, polybutene, and ethylene monoacetate vinylinole copolymer.
- thermoplastic resins such as polyolefin resins may be used alone or in a combination of two or more.
- the weight average molecular weight of such a thermoplastic resin has a lower limit of usually 50,000 or more, especially 100,000 or more, and an upper limit of usually 500,000 or less, preferably 400,000 or less, more preferably 300,000 or less, and especially 200,000 or less. What is necessary is just about 100,000 or less. If the upper limit is exceeded, in addition to the decrease in fluidity due to the addition of the filler, the melt viscosity of the resin increases, so that melt molding becomes difficult. Also, even when a molded product is obtained, the filler is evenly dispersed in the resin. However, it is not preferable because pore formation due to interfacial peeling becomes non-uniform. Below this lower limit, the mechanical strength is undesirably reduced.
- the filler contained in the porous membrane according to the present invention is important as a factor affecting the pore size distribution of the separator of the present invention, and it is important to control its particle size distribution as described later. Any filler may be used as long as it meets the conditions, and one type of filler may be used alone, or two or more types may be used in combination.
- the type of the filler is not particularly limited, but it is preferable to use an inorganic filler in that it is difficult to react with the electrolytic solution and is hardly subjected to oxidation and reduction. Among them, those having the property of not decomposing the carbonate-based organic electrolyte used in the lithium secondary battery are preferable.
- examples of such a filler include sparingly water-soluble sulfates and alumina. Barium sulfate and alumina are preferably used, and barium sulfate is particularly preferably used.
- the term "poorly water-soluble" as used herein means that the solubility in water at 25 ° C is 5 mgZ1 or less.
- carbonates such as calcium carbonate, titanium oxide, and silica, which are often used as a filler, are not preferable because they cause decomposition of a nonaqueous electrolyte component of a lithium secondary battery as described later.
- the decomposition of the organic electrolyte component, 1 ML i PF 6 in EC / EMC 3: 7 in the electrolyte consisting of a mixed nonaqueous solvent solution (volume ratio), the electrolytic solution 1 m 1 per filler added to 85 ° in a ratio of 0. 5 g C, 72 hours the concentration of lithium ions in the electrolyte after the holding is defined as a decrease child below 0. 7 5 m mo 1 / g .
- the amount of lithium ions is measured by an ion chromatography method.
- the electrolyte must be placed in a closed container so that it does not come into contact with the outside air during the 72-hour hold. This is because the decomposition of the electrolyte component proceeds by reacting with the moisture in the air.
- Electrolyte in the table below (1M L i PF 6 / ( EC + EMC) (3: 7, volume ratio) shows the results held by the addition of the seed filler under the conditions described above. Compared to the ionic composition of the electrolyte solution without the addition of filler, there was hardly any change in the composition of barium sulfate-alumina, indicating that it is suitable as the filler in the present invention. On the other hand, carbonates such as calcium carbonate, lithium carbonate, or silica or titanium oxide show a remarkable decrease in lithium ion and an increase in fluorine ions due to the generation of hydrofluoric acid. Is not preferable as a filler
- the lower limit of the number-based average particle size is usually at least 0.01 / m, preferably at least 0.1 lm, especially at least 0.2 / m, and the upper limit is usually at most Below, preferably 1.5 ⁇ or less, more preferably 1 / m or less. If the number-average particle diameter of the filler exceeds 2 ⁇ m, the diameter of the pores formed by stretching becomes too large, which tends to cause stretching fracture and a decrease in film strength. If the number-based average particle size is smaller than 0.01 im, the filler is likely to aggregate, so that it is difficult to uniformly disperse the filler in the base resin.
- the lower limit of the amount of the filler in the porous membrane according to the present invention is usually 40 parts by weight or more, preferably 50 parts by weight or more, and more preferably 60 parts by weight, based on 100 parts by weight of the thermoplastic resin. Parts by weight, more preferably 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 1 part by weight based on 100 parts by weight of the thermoplastic resin. It is 50 parts by weight or less.
- the amount of the filler is less than 40 parts by weight with respect to 100 parts by weight of the thermoplastic resin in the porous membrane, it is difficult to form a communication hole, and it is difficult to exhibit a function as a separator. It becomes. On the other hand, if the amount exceeds 300 parts by weight, the viscosity at the time of film formation becomes high and the processability is deteriorated. In addition, the film breaks at the time of stretching for making the film porous, which is not preferable.
- the compounding amount range of the filler is determined by the amount of the filler in the porous film. Agent content range.
- the number of fillers to be mixed affects the number of pores formed in the porous membrane
- the lower limit is usually 1 ⁇ 10 10 as the number of fillers per 1 cm 3 of resin volume.
- the upper limit is usually 1 X 1 0 1 4 or less, preferably 7 X 1 0 1 3 or less. If the number of components exceeds the above upper limit, the number of pores formed becomes too large, the by-products of the reaction inside the battery move easily, and the deterioration of the electrode active material is promoted. Tend to deteriorate the cycle characteristics.
- the value is below the lower limit, it is difficult to obtain a connection between the formed holes, and as a result, the electric resistance increases, and the load characteristics of the obtained secondary battery tend to decrease.
- thermoplastic resin examples include those that have been surface-treated with a surface treating agent to enhance dispersibility in a thermoplastic resin.
- a surface treating agent to enhance dispersibility in a thermoplastic resin.
- the thermoplastic resin is a polyolefin resin, for example, treatment with a fatty acid such as stearic acid or a metal salt thereof, or a polysiloxane / silane coupling agent can be mentioned.
- a low molecular weight compound having compatibility with the thermoplastic resin may be added.
- This low molecular weight compound penetrates between the molecules of the thermoplastic resin, reducing the interaction between the molecules and inhibiting crystallization, and as a result, The stretchability of the resin composition at the time of sheet molding is improved.
- the low molecular weight compound has an effect of appropriately increasing the interfacial adhesive strength between the thermoplastic resin and the filler to prevent the pores from being coarsened by stretching, and has the interfacial adhesive strength between the thermoplastic resin and the filler. This has the effect of preventing the filler from falling off the film.
- the low molecular weight compound those having a molecular weight of from 200 to 300 are preferably used, and those having a molecular weight of from 200 to 100 are more preferably used. If the molecular weight of the low molecular weight compound exceeds 300, the low molecular weight compound will not easily enter between the molecules of the thermoplastic resin, and the effect of improving the stretchability will be insufficient. If the molecular weight is less than 200, the compatibility is increased, but low molecular weight compounds tend to precipitate on the surface of the porous membrane, so-called blooming is likely to occur, resulting in deterioration of the membrane properties and blocking. Absent.
- thermoplastic resin when the thermoplastic resin is a polyolefin resin, an aliphatic hydrocarbon or dalyceride is preferably used.
- polyolefin resin when the polyolefin resin is polyethylene, liquid paraffin or low melting point wax is preferably used.
- the lower limit of the compounding amount of the low molecular weight compound is 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, based on 100 parts by weight of the thermoplastic resin. If the compounding amount of the low molecular weight compound is less than 1 part by weight based on 100 parts by weight of the thermoplastic resin, the above-mentioned effect due to the compounding of the low molecular weight compound cannot be sufficiently obtained, and also exceeds 20 parts by weight. Interaction between the polymer and the thermoplastic resin is excessively reduced, and sufficient strength cannot be obtained. In addition, smoke is generated at the time of forming the sheet, or slip occurs at the screw portion, and it is difficult to form a stable sheet.
- additives such as a heat stabilizer can be added to the resin composition as a film-forming material of the porous film according to the present invention.
- Any known additives can be used without particular limitation.
- the amount of these additives is usually 0.05 to 1% by weight based on the total amount of the resin composition.
- the porosity of the 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 porous membrane, and usually 80% or less as the upper limit. It is preferably at most 70%, more preferably at most 65%, particularly preferably at most 60%.
- the porosity is less than 30%, the ion permeability is insufficient, and the porosity cannot function as a separator, which is not preferable.
- the porosity exceeds 80%, the actual strength of the film becomes low, so that it is not preferable because breakage at the time of producing the battery, penetration through the active material, and short-circuit occur.
- the porosity of the porous film is a value calculated by the following formula.
- Porosity P V (%) 100 X (1 -w / [p ⁇ S. T])
- the upper limit of the thickness of the porous membrane according to the present invention is usually 100/2 m or less, especially 50 / im or less, preferably 40 / m or less.
- the lower limit is usually 5 // m or more, preferably 10 m or more.
- the thickness is less than 5 / xm, since the actual strength is low, the battery may be broken at the time of fabrication, or may be pierced and short-circuited by the active material, which is not preferable. On the other hand, if the thickness exceeds 100 ⁇ , the electric resistance of the separator increases, and the capacity of the battery decreases, which is not preferable. By setting the thickness in the range of 5 to 100 m, a separator having good ion permeability can be obtained.
- the lower limit of the Gurley air permeability is 20 seconds / 100 cc or more, particularly 100 seconds Z100 cc or more, and the upper limit is 500 seconds / It is preferably at most 100 cc, particularly preferably at most 300 seconds / 100 cc. If the Gurley air permeability is below this lower limit, the porosity is often too high or too thin, and as described above, the actual strength of the film becomes low, causing breakage during battery fabrication and the occurrence of active material. Undesirable penetration and short circuit occur. If it exceeds the upper limit, the ion permeability is not sufficient, and it cannot function as a separator, which is not preferable.
- the Gurley air permeability is measured according to JISP 8117, and indicates the number of seconds that 100 cc of air permeates the membrane at a pressure of 1.22 kPa.
- the method for producing the thermoplastic resin-containing porous membrane containing a filler is not particularly limited, and includes the following extraction method (1), stretching method (2), and interfacial peeling method (3), and is particularly preferable. This is the interface peeling method.
- Extraction method A resin composition obtained by mixing a polymer material, a filler, and a plasticizer that can be removed by solvent extraction in a later step is melted, and this is formed into a film by a molding method such as extrusion molding. After forming into a shape, it is treated with a solvent to remove the plasticizer, thereby making it porous.
- Interfacial peeling method A resin composition obtained by mixing a polymer material with a filler is melted, formed into a film by a molding method such as extrusion molding, and then stretched to obtain a high-strength material. The interface between the molecular material and the filler is exfoliated to form micropores.
- a molding method such as extrusion molding
- the filler contained in the plasticizer is removed together with the plasticizer during extraction. Therefore, it is not efficient compared to the interfacial separation method.
- the stretching method if a filler is included in the polymer material, pores are formed by stretching in the interface between the polymer material and the filler in addition to the amorphous part, so that it is essentially different from the interface peeling method. . Therefore, in the present invention, it is preferable to employ the interfacial peeling method.
- the production of the porous membrane is more specifically performed by the following method.
- a resin composition is prepared by blending a predetermined amount of a filler, a thermoplastic resin, and additives such as a low molecular weight compound and an antioxidant, which are added as required, and melt-kneading.
- the above resin composition is preliminarily mixed by a Henschel mixer or the like, and then may be prepared by using a commonly used single-screw extruder, twin-screw extruder, mixing wool or twin-screw kneader or the like.
- the resin composition may be directly prepared by the above-mentioned extruder or the like without pre-mixing.
- the resin composition is formed into a sheet.
- the sheet can be formed by a commonly used T-die method using a T-die or an inflation method using a circular die.
- the formed sheet is stretched. In the stretching, the direction in which the sheet is taken
- MD uniaxial stretching in the longitudinal direction
- TD transverse direction
- TD transverse direction
- TD transverse direction
- TD transverse direction
- TD transverse direction
- a simultaneous biaxial stretching method in which the film is stretched simultaneously in the machine direction and the transverse direction.
- 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 to close the pores and lose communication.
- the stretching is performed in a temperature range from the melting point of the resin to 170 ° C to the melting point of the resin to 15 ° C.
- the stretching ratio is arbitrarily set according to the required pore diameter / strength, but preferably stretching is performed at least 1.2 times or more in one axis direction.
- the separator of the present invention having a ratio d ave Zd max between the average pore diameter d ave ( ⁇ ) and the maximum pore diameter d max (/ im) determined by ASTM F316-86 of 0.6 or more is manufactured. A method for performing the above will be described.
- the method for producing the porous film constituting the separator of the present invention may be any method as long as a porous film having a dave / dma ⁇ of 0.6 or more can be obtained, and the molding material and production method are particularly limited. There is no.
- the separator of the present invention includes a are produced by the manufacturing method similar to the method of a conventional separator mentioned above, in the present invention, a separator which is produced d ave / d ma x 0. 6 or more In order to achieve this, [1] strictly control the particle size distribution of the filler, [2] control the mixing and stretching conditions of the resin and the filler, or adopt both of these measures.
- Control of filler particle size distribution Control of skewness of number-based particle size distribution of filler
- the filler compounded in the porous membrane has a skewness of 0 in its number-based particle size distribution. It is preferably at least 5.
- the particle size distribution is evaluated by the laser diffraction / scattering method.
- the particle size distribution of the filler may be measured with the filler before kneading with the resin, or may be measured by pulverizing ash collected by baking the porous membrane.
- the skewness of the particle size distribution of the filler is derived from the particle size distribution using, for example, the formula described in “Statistical Engineering Handbook” edited by the Statistical Engineering Research Group of Tokyo Institute of Technology, pp. 194-195.
- the skewness of the particle size distribution is 0 or more, it indicates that the particle size distribution is biased toward the low particle size side, but when the skewness is near 0, the deviation of the particle size distribution toward the low particle size side is sufficient. not a, it is difficult to d av e Zd max to obtain a porous membrane of 0.6 or more, skewness is is 0.5 or higher, of large particles against the opening of the resulting porous membrane It is preferable to reduce the contribution and obtain a porous membrane of d ave / dma 5 ⁇ S0.6 or more.
- the d a ve / d ma x is 0.6 or more porous membranes Difficult to get.
- the filler used in the present invention preferably has a skewness derived from its number-based particle size distribution of 0.5 or more, more preferably 2 or more, and more preferably. More preferably, the skewness is 2.5 or more.
- the particle size may be adjusted using a classifier such as a sieve. This grain size adjustment can be repeated multiple times as needed.
- the mixing and stirring conditions are set so that the filler is sufficiently uniformly dispersed in the thermoplastic resin.
- the temperature and time of the melt-kneading conditions to be used are strictly controlled.
- the separator for a non-aqueous electrolyte secondary battery of the present invention further comprises a halogen element or a chlorine element contained in the separator of 10 ppm or less and an iron element of 10 O ppm or less. Cycle characteristics, especially at high temperatures, can be improved.
- the concentration of the halogen element and the iron element in the separator can be determined by the following method. In Examples and Comparative Examples described below, the separator is used by the following methods (i) and (ii). The halogen element and iron element in the constituent polymer porous membrane were quantified.
- the separator of the present invention To 5 g of the sample (polymer porous membrane constituting the separator), add 1 Oml of hydrochloric acid for 36% EL manufactured by Mitsubishi Chemical Corporation and 2 Om1 of pure water, and perform boiling extraction for 30 minutes. Thereafter, the extract is filtered, and the filtrate is used as a measurement solution, and Fe is quantified using an ICP emission spectrometer.
- the upper limit of the content of the halogen element, particularly the chlorine element, in the separator measured in this way is lOppm or less, especially 8ppm or less, and especially 5ppm or less. Is preferred. When the content of the halogen element, particularly the chlorine element, exceeds this upper limit, the corrosion of the battery can and the current collector tends to be easily promoted by the halogen element such as C1 eluted in the electrolytic solution.
- the upper limit of the iron element content in the separator measured in this way is lOO ppm or less, particularly 8 Oppm or less, and more preferably 70 ppm or less. Is preferred. If the iron element content exceeds this upper limit, Fe eluted in the electrolyte will precipitate on the negative electrode surface and micro-shorts will easily form, leading to a reduction in charge / discharge efficiency and deterioration in cycle characteristics. Tends to be easier. As the lower limit of the content of the halogen element and the iron element in the separator, excessively lowering the content of the halogen element and the iron element reduces the content of the halogen element and the iron element in the separator as described later.
- the number of steps such as purification of inorganic fillers is extremely large, and it is difficult to produce a polymer porous membrane.
- the lower limit of the content of the halogen element, particularly the chlorine element in the separator may be about 5 ppm, and the lower limit of the content of the iron element may be about 50 ppm.
- the polymer porous membrane constituting the separator of the present invention is, specifically, The separator is manufactured in the same manner as the general polymer porous membrane described above, but if the content of the halogen element or chlorine element in the separator manufactured in this way is set to 10 ppm or less, the content of the iron element is reduced to 1 ppm.
- impurities contained in the raw material for producing the polymer porous membrane and brought into the polymer porous membrane, and impurities contained in the polymer porous membrane during the production process of the polymer porous membrane are used. The following method is used to reduce the impurities mixed into the water.
- a polymer porous membrane is manufactured using an inorganic filler having a reduced content of a halogen element and an iron element.
- inorganic fillers are usually produced from natural ores, it is inevitable that impurities such as iron and halogen elements are inevitably several hundred ppm for iron and several tens of ppm for halogen elements. It inevitably mixes in about ppm. For this reason, it is possible to reduce the above-mentioned impurities in the produced inorganic filler through steps such as purification and washing with water. Alternatively, it is possible to reduce the amount of impurities in the inorganic filler by incorporating chemical synthesis into the production process of the inorganic filler. When a chemical synthesis is incorporated, a step in which a halide is generated during the synthesis is not preferable because a large amount of the halogen element remains in the final product.
- the inorganic filler produced using natural ore as a raw material is washed with water
- a method in which the inorganic filler is put into high water of about 20 to 100 ° C. and stirred may be employed.
- a cleaning agent may be added to the cleaning water to add a halogen element such as sulfuric acid / nitric acid and iron-free chemicals to enhance the cleaning effect.
- the concentration of the acid in the washing water is preferably 1 to 20% by weight. In the case of washing with water to which a chemical is added, it is preferable to finally finish and wash with pure water.
- a method of purifying an inorganic filler produced using natural ore as a raw material for example, a method of separating ground ore in air or water by a difference in specific gravity can be employed.
- barium sulfide obtained by reducing and sintering barite as a raw material ore is sulfated. It can be produced by reacting with sodium acid or sulfuric acid.
- sodium hydroxide is added to the raw material ore, poxite, to form sodium aluminate, which is hydrolyzed to precipitate aluminum hydroxide, which is then fired at a high temperature to manufacture. You can also.
- the inorganic filler is used to separate the halogen element or chlorine element content and the iron element in the separator composed of the polymer porous membrane produced by blending the same.
- the impurity content can be reduced so that the content is equal to or less than the upper limit specified above.
- the impurity content of the inorganic filler therefore depends on the amount of the inorganic filler in the polymer porous membrane. When the amount of the inorganic filler is small, the impurity content of the inorganic filler is relatively large. If the content of the inorganic filler is large, the content of impurities in the inorganic filler is preferably minimized.
- the amount of the inorganic filler is as described above, that is, usually at least 40 parts by weight, preferably at least 50 parts by weight, more preferably at least 60 parts by weight, more preferably at least 100 parts by weight, based on 100 parts by weight of the thermoplastic resin.
- 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 based on 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 It is preferable to reduce the impurity content so as to be at most 300 ppm, preferably at most 200 ppm, more preferably at most 100 ppm.
- the lower limit of the impurity content of the inorganic filler is about 7 ppm of the halogen element or chlorine element and about 70 ppm of the iron element for the same reason as the lower limit of the impurity content in the separator described above.
- the content of the halogen element and the iron element in the inorganic filler can be quantified by the following method in the same manner as the impurity content in the separator (polymer porous membrane) described above.
- the halogen element and the iron element in the inorganic filler were quantified by the following methods (iii) and (iv).
- the sample inorganic filler
- 1 Oml of hydrochloric acid for 36% EL manufactured by Mitsubishi Chemical Corporation and 2 Om1 of pure water After adding 1 Oml of hydrochloric acid for 36% EL manufactured by Mitsubishi Chemical Corporation and 2 Om1 of pure water, and perform boiling extraction for 30 minutes. Then, the extract is filtered, and the filtrate is used as a measurement solution, and Fe is quantified using an ICP emission spectrometer.
- the content of impurities in the inorganic filler contained in the separator can be measured by the same method as described above.
- the matrix resin of the polymer porous membrane constituting the separator may be baked at a high temperature, the inorganic filler may be separated from the collected ash, and the same quantification as described above may be performed.
- the base resin for the polymer porous membrane a resin having a reduced content of a halogen element and an iron element is used.
- 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.
- thermoplastic resin polymerization is carried out using a small amount of catalyst by, for example, increasing the catalytic activity, increasing the reaction time, or increasing the reaction temperature, and reducing the amount of catalyst remaining in the thermoplastic resin.
- impurities derived from the catalyst can be reduced.
- any of the above-described methods [1] and [2] may be employed.
- a membrane can be produced, since the halogen element and the iron element in the separator are mainly derived from the inorganic filler, at least the above [1] It is preferable to adopt the impurity reduction method described above.
- the non-aqueous electrolyte secondary battery of the present invention uses the separator for a nonaqueous electrolyte secondary battery of the present invention as described above will be described.
- the non-aqueous electrolyte secondary battery of the present invention has a positive electrode capable of storing and releasing lithium ions, a negative electrode capable of storing and releasing lithium ions, an electrolytic solution containing an electrolyte in a non-aqueous solvent, and a separator.
- any known solvent for a non-aqueous electrolyte secondary battery can be used.
- anolexylene carbonates such as ethylene carbonate, propylene carbonate, and butylene carbonate; dimethinolecarbonate, ethynolecarbonate,
- -Dialkyl carbonates such as n-propyl carbonate and ethyl methyl carbonate (the alkyl group of the dialkyl carbonate is preferably an alkyl group having 1 to 4 carbon atoms); cyclic ethers such as tetrahydrofuran and 2-methyltetrahydrofuran; Linear ethers such as toxetane and dimethoxymethane; cyclic carboxylic esters such as ⁇ -butyrolactone and ⁇ -valerolactone; and linear carboxylic esters such as methyl acetate, methyl propionate, and ethyl propionate. These may be used alone or in combination of two or more.
- any lithium salt which is a solute of the non-aqueous electrolyte, can be used.
- L i C 10 4 L i inorganic lithium salts such as 6 and i BF 4;? L i CF 3 S0 3, L i N (CF 3 SO 2) 2, L i N (C 2 F 5 S0 2 ) 2 , L i N (CF 3 S0 2 ) (C 4 F 9 S 0 2 ), L i C (CF 3 S 0 2 ) 3 , L i PF 4 (CF 3 ) 2 , L i PF 4 (C 2 F 5) 2, L i PF 4 (CF 3 S 0 2) 2, L i PF 4 (C 2 F 5 SO s) 2, L i BF 2 (CF 3) 2, L i BF 2 (C 2 F 5 ) 2, L i BF 2 (CF 3 SO z) such 2 ⁇ Pi L i BF 2 (C 2 F 5 S_ ⁇ 2) 2 fluorine-containing organic lithium
- L i PF 6, L i BF 4, L i CF 3 S0 3, L i N (CF 3 SO 2) 2 or L i N (C 2 F 5 S0 2) 2, in particular L i PF 6 Or L i BF 4 is preferred.
- One type of lithium salt may be used alone, or two or more types may be used in combination.
- the lower limit of the concentration of these lithium salts in the non-aqueous electrolyte is usually 0.5 mo 1/1 or more, especially 0.75 mo 1 or more, and the upper limit is usually 2 mo 1 or less. Above all, it is less than 1.5 m 0 1/1.
- the concentration of the lithium salt exceeds this upper limit, the viscosity of the non-aqueous electrolyte increases, and the electric conductivity decreases. Further, when the value is below the lower limit, the electric conductivity becomes low. Therefore, it is preferable to prepare a non-aqueous electrolyte within the above concentration range.
- the non-aqueous electrolyte according to the present invention may contain other useful components, if necessary, such as conventionally known overcharge preventive agents, dehydrating agents, deoxidizing agents, capacity retention characteristics after high-temperature storage, and cycle characteristics. And various additives such as an auxiliary agent for improving the quality.
- Auxiliary agents for improving the capacity retention characteristics and cycle characteristics after high-temperature storage include carbonate compounds such as vinylene carbonate, ethylene carbonate at phenolic outlet, propylene carbonate at trifinoleo, phenylethylene carbonate and erythritan carbonate; Succinic acid, glutaric anhydride, maleic anhydride, citraconic anhydride, glutaconic anhydride, itaconic anhydride, diglycolic anhydride, cyclohexandicarboxylic anhydride, cyclopentanetetracarboxylic dianhydride, phenylenosuccinic acid Carboxylic anhydrides such as anhydrides; ethylene sanolephite, 1,3-propane snoretone, 1,4-butane sultone, methyl methanesulfonate, psanorephane, snoreholane, snoreholene, dimethinoles noreh
- the positive electrode one obtained by forming an active material layer containing a positive electrode active material and a binder on a current collector is usually used.
- the positive electrode active material examples include materials capable of absorbing and releasing lithium, such as a lithium transition metal composite oxide material such as lithium cobalt oxide, lithium nickel oxide, and lithium manganese oxide. These can be used alone or in combination. You may use together.
- the binder is not particularly limited as long as it is a material that is stable with respect to the solvent and the electrolyte used in the production of the electrode and other materials used in the use of the battery.
- Specific examples are polyvinylidene fluoride, polytetrafluoroethylene, fluorinated polyvinylidene fluoride, EPDM (ethylene-propylene-one-diene terpolymer), SBR (styrene-butadiene rubber), and NBR (acrylonitrile-one rubber).
- Butadiene rubber fluorine rubber, polyvinyl acetate, polymethyl methacrylate, polyethylene, nitrocellulose, and the like. These may be used alone or in combination of two or more.
- the lower limit of the binder ratio in the positive electrode active material layer is usually at least 0.1% by weight, preferably at least 1% by weight, more preferably at least 5% by weight, and the upper limit is usually at most 80% by weight. It is preferably at most 60% by weight, more preferably at most 40% by weight, even more preferably at most 10% by weight. If the ratio of the binder is small, the active material cannot be sufficiently retained, so that the mechanical strength of the positive electrode may be insufficient and the battery performance such as cycle characteristics may be deteriorated. Will be lowered.
- the positive electrode active material layer usually contains a conductive agent to increase conductivity.
- the conductive agent examples include fine particles of graphite such as natural graphite and artificial black, and carbonaceous materials such as carbon black such as acetylene black and amorphous carbon fine particles such as needle coats. These may be used alone or in combination of two or more.
- the lower limit of the proportion of the conductive agent in the positive electrode active material layer 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. %, 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, while if too large, the battery capacity may be reduced.
- the positive electrode active material layer may further contain a usual additive for the 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 the electrolyte used in the production of the electrode and other materials used in the use of the battery.
- a specific example is Karboki Sinoremethylcenorelose, methinoresenorelose, hydroxymethinoresenorelose, ethylcellulose, polyvinyl alcohol, oxidized starch, phosphorylated starch, casein and the like. These may be used alone or in combination of two or more.
- aluminum, stainless steel, Eckerme steel, or the like is used for the current collector of the positive electrode.
- the positive electrode is formed by applying a slurry of the above-described positive electrode active material, a binder, a conductive agent, and other optional additives to a current collector and drying the slurry. can do.
- a solvent used for slurrying an organic solvent that dissolves the binder is usually used.
- N-methylpyrrolidone, dimethylformamide, dimethylacetamide, methylethylketone, cyclohexanone, methyl acetate, methyl acrylate, getyltriamine, N-N-dimethylaminopropylamine, ethylene Oxide, tetrahydrofuran and the like are used, but are not limited thereto. These may be used alone or in combination of two or more.
- a slurry of the active material can be prepared by adding a dispersant, a thickener, and the like to water, and using a latex such as SBR.
- the thickness of the positive electrode active material layer thus formed is usually about 10 to 200 zni.
- the active material layer obtained by coating and drying is preferably compacted by a roller press or the like in order to increase the packing density of the active material.
- the negative electrode one obtained by forming an active material layer containing a negative electrode active material and a binder on a current collector is usually used.
- negative electrode active material pyrolysates of organic substances under various pyrolysis conditions and carbonaceous materials that can absorb and release lithium such as artificial graphite and natural graphite; can absorb and release lithium such as tin oxide and silicon oxide Metal oxide materials; lithium metals; various lithium alloys, and the like.
- These negative electrode active materials may be used alone or in a combination of two or more.
- the binder is not particularly limited as long as it is a material that is stable with respect to the solvent and the electrolyte used in the production of the electrode and other materials used in the use of the battery.
- Specific examples include polyvinylidene fluoride, polytetrafluoroethylene, and styrene-butadiene. Rubber, isoprene rubber, butadiene rubber and the like. These may be used alone or in combination of two or more.
- the lower limit of the ratio of the binder in the negative electrode active material layer is usually 0.1% by weight or more, and preferably 1% by weight. / 0 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 further preferably 10% by weight or less. It is. If the ratio of the binder is small, the active material cannot be sufficiently retained, so that the mechanical strength of the negative electrode is insufficient and the battery performance such as cycle characteristics may be deteriorated.On the other hand, if the ratio is too large, the battery capacity and conductivity are reduced. Will be.
- the negative electrode active material layer usually contains a conductive agent to increase conductivity.
- the conductive agent examples 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 a needle coater. These may be used alone or in combination of two or more.
- the lower limit of the proportion of the conductive agent in the negative electrode active material layer is usually 0.01% by weight or more, preferably 0.1% by weight or more, and more preferably 1% by weight. /.
- 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, while if too large, the battery capacity may be reduced.
- the negative electrode active material layer may further contain a usual additive for the active material layer such as a thickener.
- the viscosity agent is not particularly limited as long as it is a material that is stable with respect to the solvent and the electrolyte used in the manufacture of the electrode and other materials used in the use of the battery.
- Specific examples thereof include carboxy cinolemethinoresenorelose, methylcellulose, hydroxymethinoresenorelose, ethyl lucenorelose, polyvinylinoleanolone, polyacid starch, phosphorylated starch, casein, and the like. . These may be used alone or in combination of two or more. Copper, nickel, stainless steel, nickel plating steel, etc. are used as the current collector of the negative electrode.
- the negative electrode is prepared by applying a slurry of the above-described negative electrode active material, a binder, a conductive agent, and other additives that are added as necessary with a solvent to a current collector, followed by drying. Can be formed.
- an organic solvent that dissolves a binder is usually used.
- N-methylpyrrolidone, dimethylformamide, dimethylacetamide, methylethylketone, cyclohexanone, methyl acetate, methyl acrylate, getyltriamine, N-N-dimethylaminopropylamine, ethyleneo Oxide, tetrahydrofuran and the like are used, but are not limited thereto. These may be used alone or in combination of two or more.
- a slurry of the active material can be formed by adding a dispersant, a thickener, and the like to water and using a latex such as SBR.
- the thickness of the negative electrode active material layer thus formed is usually about 10 to 200 / m.
- the active material layer obtained by coating and drying is preferably compacted 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 above-described positive electrode, negative electrode, non-aqueous electrolytic solution, and separator of the present invention into an appropriate shape. Further, if necessary, other components such as an outer case can be used.
- the shape of the battery is not particularly limited, and can be appropriately selected from various generally employed shapes according to the application.
- Examples of commonly used shapes include a cylinder type with a sheet electrode and a separator in a spiral shape, a cylinder type with an inside-out structure combining a pellet electrode and a separator, a coin type with a stacked pellet electrode and a separator, and a sheet.
- Examples include a laminate type in which an electrode and a separator are laminated.
- the method for assembling the battery is not particularly limited, and can be appropriately selected from various methods generally used in accordance with the shape of the intended battery.
- the lithium secondary battery of the present invention has been described above.
- 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 of the present invention.
- implementation is possible.
- the use of the lithium secondary battery of the present invention is not particularly limited, and the lithium secondary battery can be used for various known uses. Specific examples include notebook computers, pen input computers, mobile computers, e-book players, mobile phones, mobile fax machines, and mobile copy machines. 1.Mobile printers, headphone stereos, video movies, LCD TVs, handy cleaners, portable CDs, minidiscs, transceivers, electronic notebooks, calculators, memory cards, portable tape recorders, radios, backup power supplies, motors, lighting equipment, toys , Game machines, watches, strobes, cameras, and other small devices, and large devices, such as electric vehicles and hybrid vehicles. Example)
- Air permeability The measurement was performed using a B-type Gurley densaw meter (manufactured by Toyo Seiki Seisaku-sho, Ltd.) according to JIS P8117.
- Pore size The measurement was carried out using a porometer manufactured by Coulter Co. in accordance with ASTM F316-86.
- polypropylene 1 (homotype, “FY 6C” manufactured by Nippon Polychem Co., Ltd. (MFR: 2.4 g / 1 Om in)) 25.9 parts by weight and polypropylene 2 (copolymer, “I NS P i RE” manufactured by Dow Chemical Company) (MFR: 0.5 g / 1 Om in)) 6.5 parts by weight, hardened castor oil [HY-CASTOR OIL molecular weight 938, manufactured by Toyokuni Oil Co., Ltd.] 2.6 parts by weight, commercially available parium sulfate [as a filler] Number-based average particle size 0.17 m, skewness 2.9.1 1) A resin sheet obtained by blending 65 parts by weight was melt-molded at a temperature of 250 ° C to obtain a raw sheet.
- the thickness of the raw sheet was 50 on average, and the number of fillers was as shown in Table 2.
- the obtained raw sheet was stretched 4.5 times in the sheet longitudinal direction (MD) at 80 ° C, and the film thickness, porosity, gas permeability, and pore diameter shown in Table 2 were obtained.
- Table 2 shows the results of quantifying the halogen (C 1) and Fe contained in the obtained porous membrane and barium sulfate used as the inorganic filler, respectively, according to the above-described quantification method.
- L i C o 0 2 As the positive electrode active material, L i C o 0 2 8 5 parts by weight carbon black click 6 parts by weight of polyvinylidene fluoride (Kureha Chemical Co., trade name "KF- 1 00 OJ) 9 Parts by weight, mixed and dispersed with N-methyl-2-pyrrolidone to form a slurry, which was uniformly applied to one side of a 20 / im-thick aluminum foil as a positive electrode current collector and dried. Thereafter, a positive electrode was pressed by a press machine so that the density of the positive electrode active material layer became 1.9 gZcm 3 .
- KF- 1 00 OJ polyvinylidene fluoride
- a 2032 type coin cell was produced using the above electrolytic solution, the positive electrode and the negative electrode together. That is, a stainless steel can body also serving as a positive electrode conductor was punched into a disk shape having a diameter of 12.5 mm and the positive electrode impregnated with an electrolyte was accommodated therein. A negative electrode impregnated with an electrolytic solution was mounted on the resultant by punching out a disk having a diameter of 12.5 mm through a separator having a diameter of 18.8 mm impregnated with the electrolytic solution.
- the can body and the sealing plate also serving as a negative electrode conductor were caulked via an insulating gasket to seal the battery, thereby producing a coin-type battery.
- the impregnation of the battery member with the electrolytic solution was performed by immersing each member in the electrolytic solution for 2 minutes.
- CZ3 the current value that discharges the rated capacity per hour with a discharge capacity of 1 hour is 1 C, the same shall apply hereinafter
- each of 4 C and 6 C discharges
- the discharge capacity was measured at the speed, and the ratio of the discharge capacity based on the discharge capacity of CZ3 was determined.
- the results are shown in Table 2.
- the charge end voltage is 4.2 V
- the discharge is 3 cycles of charge / discharge with a final voltage of 3 V to stabilize, charge the 4th cycle with a current equivalent to 0.5 C to a final charge voltage of 4.2 V, and a charge current value of 0.05 C Charge until the current value is reached.
- 4.2 V Constant current constant voltage charge (CCCV charge) (0.05 C cut), then 3 V discharge at a constant current value equivalent to 0.2 C.
- Table 2 shows the results of quantifying the halogen (C1) and Fe contained in the obtained porous membrane and barium sulfate used as the inorganic filler according to the above-described quantification method.
- Table 2 shows the results of quantifying the halogen (C1) and Fe contained in the obtained porous membrane and barium sulfate used as the inorganic filler according to the above-described quantification method.
- a coin-type battery was assembled in the same manner as in Example 1 except that this porous membrane was used as a separator, and the same evaluation was performed. The results are shown in Table 2.
- a coin-type battery was assembled in the same manner as in Example 1 except that this porous membrane was used as a separator, and the same evaluation was performed. The results are shown in Table 2.
- Table 2 shows the results of quantifying the halogen (C 1) and Fe contained in the obtained porous membrane and barium sulfate used as the inorganic filler, respectively, according to the above-described quantification method.
- a coin-type battery was assembled in the same manner as in Example 1 except that this porous membrane was used as a separator, and the same evaluation was performed. The results are shown in Table 2.
- the discharge capacity of the coin-type battery using the porous membrane obtained in Examples 1 to 4 as a separator was C / 3 at both the discharge rate of 4 C and 6 C. At 60 ° / 0 or more.
- the discharge capacity of the coin-type battery using the porous membrane of Comparative Example 1 as a separator was less than 50% of that of C3 at any of the discharge rates of 4 C and 6 C. A decrease in performance was observed.
- barium sulfate in their physical properties, there is provided a variety of things, simply using sulfuric acid Bariumu as a filler, but not to achieve a d ave Zd m ax that specified in the present invention, By managing these physical properties, battery performance can be improved.
- High-density polyethylene ““HI-ZEX 7000 FP”, manufactured by Mitsui Chemicals, weight average molecular weight: 200,000, density: 0.956 g / cm 3 , menoleto flow rate: 0.04 g Z 10 min] 100 weight Parts, soft polypropylene [PER R 110 EJ, manufactured by Idemitsu Petrochemical Co., Ltd., weight average molecular weight: 330,000] 15.6 parts by weight, hardened castor oil [HY-CASTOR 01, manufactured by Toyokuni Oil Co., molecular weight 9 38] 9 4 parts by weight, Paridium sulfate as an inorganic filler (Saiko Chemical Co., Ltd. "B-55" volume-based average particle size 0.666 1!
- L i C o 0 2 85 parts by weight Kaponpura click 6 parts by weight of polyvinylidene fluoride (Kureha Chemical Co., trade name "KF 1000") 9 parts by weight
- KF 1000 polyvinylidene fluoride
- the mixture was mixed and dispersed with N-methyl-1-pyrrolidone to form a slurry. This is uniformly coated on one side of a 20-uin thick aluminum foil, which is a positive electrode current collector, dried, and then pressed by a press so that the density of the positive electrode active material layer becomes 3.O gZcm 3.
- the positive electrode was used.
- 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 is uniformly coated on one side of a 18 ⁇ thick copper foil, which is the negative electrode current collector, dried, and then pressed by a press so that the density of the negative electrode active material layer is 1.5 gZ cm 3. To form a negative electrode.
- a 2032-type coin cell was manufactured using the polymer porous membrane as a separator, together with the electrolyte, the positive electrode and the negative electrode. That is, a stainless steel can that also serves as the positive electrode conductor was punched into a disk shape with a diameter of 12.5 mm and impregnated with the electrolyte to collect the positive electrode. Then, a negative electrode impregnated with an electrolytic solution was mounted by punching out a 12.5 mm diameter disc through a 18.8 mm diameter separator impregnated with the electrolytic solution. The can body and the sealing plate also serving as the negative electrode conductor were caulked via an insulating gasket and sealed 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 1>
- the charge end voltage is 4.2 V
- the discharge is 3 cycles of charge / discharge with a final voltage of 3 V to stabilize, charge the 4th cycle with a current equivalent to 0.5 C to a final charge voltage of 4.2 V, and a charge current value of 0.05 C Charge until the current reaches 4.2 V—constant-current constant-voltage charge (CCCV charge) (0.05 C cut), followed by 3 V discharge at a constant current value equivalent to 0.2 C.
- CCCV charge constant-current constant-voltage charge
- Example except that barium sulfate (“BA” manufactured by Sakai Chemical Co., Ltd., volume-average particle diameter 8 m, number-average particle diameter 0, skewness 14.1) was used as the inorganic filler.
- BA barium sulfate
- a polymer porous membrane having a film thickness of 30 ⁇ m, a porosity of 68%, and a Gurley air permeability of 50 seconds / 100 cc was obtained.
- the halogen (C 1) and Fe contained in the barium sulfate were determined according to the above-mentioned methods, and the number of fillers, film thickness, porosity, Gurley air permeability and pore diameter were determined. Was as shown in Table 2.
- a coin-type battery was assembled and evaluated in the same manner as in Example 5 except that this polymer porous membrane was used as a separator. The results were shown in Table 3.
- Barium sulfate [Sakai Chemical Co., Ltd. “B Cj volume-average particle diameter 10 / im, number-average particle diameter 0.46 m, skewness 15.1”] was extracted with 5% by weight sulfuric acid for 1 hour and filtered. After washing with pure water, ultrasonic extraction for 30 minutes in pure water, filtration, and washing with pure water, the barium sulfate after washing was dried at 120 ° C. for 1 hour, and further dried. , And vacuum drying was performed at 120 ° C. for 12 hours, except that the barium sulfate treated as described above was used as an inorganic filler.
- a porous polymer membrane having a porosity of 67% and a Gurley air permeability of 40 seconds / 100 cc was obtained, and the halogen contained in the obtained porous polymer membrane and the sulfate barium used as the inorganic filler.
- Table 2 shows the results of quantifying (C 1) and Fe in accordance with the quantification methods described above, as well as the number of fillers, film thickness, porosity, Gurley air permeability, and pore size. It was as shown.
- a coin-type battery was assembled in the same manner as in Example 5 except that this polymer porous membrane was used as a separator, and the same evaluation was performed. The results are shown in Table 2.
- Example 1 except that barium sulfate (“B-1” manufactured by Sakai Chemical Co., volume-based average particle size 0.8 ⁇ , number-based average particle size 0.4, skewness 3.2) was used as the inorganic filler.
- B-1 barium sulfate
- the halogen (C 1) and Fe contained in the obtained polymer porous membrane and barium sulfate used as the inorganic filler were quantified according to the above-described quantification method, respectively.
- the porosity, Gurley air permeability and pore size were as shown in Table 2.
- a coin-type battery was assembled in the same manner as in Example 5 except that this polymer porous membrane was used as a separator, and the same evaluation was performed. The results are shown in Table 2.
- Example 2 The same procedure as in Example 1 was carried out except that barium sulfate (“BC” manufactured by Sakai Chemical Co., Ltd., volume-average particle diameter: 10 ⁇ m, number-average particle diameter: 0, skewness: 15.1) was used as the inorganic filler. As a result, a polymer porous membrane having a thickness of 33 ⁇ , a porosity of 66%, and a Gurley air permeability of 40 s / 100 cc was obtained.
- Halogen (C 1) and Fe contained in the obtained polymer porous membrane and barium sulfate used as the inorganic filler were quantified according to the above-described quantification method, respectively.
- the porosity, Gurley air permeability and pore size were as shown in Table 2.
- a coin-type battery was assembled in the same manner as in Example 5 except that this polymer porous membrane was used as a separator, and the same evaluation was performed.
- the results are shown in Table 2.
- the discharge capacity of the coin-type battery using the porous membranes obtained in Examples 5 to 9 as a separator was CZ 3 at both the discharge rates of 4 C and 6 C. At 68% or more, it was good as in Examples 1 to 4.
- Haguchi Genion dissolves the passivation of the metal surface and converts metal oxides to Metal Halide. Since metal halides are easily dissolved, corrosion proceeds. Therefore, as typified by the results 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 cycle characteristics deteriorate.
- the present invention is useful for improving the performance of a nonaqueous electrolyte secondary battery, particularly for improving load characteristics and its stability.
Abstract
Description
Claims
Priority Applications (4)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
EP04710505A EP1667252B1 (en) | 2003-08-06 | 2004-02-12 | Separator for nonaqueous electrolyte secondary battery and nonaqueous electrolyte secondary battery including the same |
CN2004800283645A CN1860627B (zh) | 2003-08-06 | 2004-02-12 | 非水电解液二次电池的隔板和利用它的非水电解液二次电池 |
US11/347,213 US8003262B2 (en) | 2003-08-06 | 2006-02-06 | Nonaqueous electrolyte solution secondary battery separator having defined ratio of average pore diameter to maximum pore diameter and nonaqueous electrolyte solution secondary battery using the same |
US13/047,106 US8597836B2 (en) | 2003-08-06 | 2011-03-14 | Nonaqueous electrolyte solution secondary battery separator having filler and controlled impurities |
Applications Claiming Priority (4)
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JP2003287903 | 2003-08-06 | ||
JP2003-287904 | 2003-08-06 | ||
JP2003-287903 | 2003-08-06 | ||
JP2003287904 | 2003-08-06 |
Related Child Applications (3)
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US11347213 A-371-Of-International | 2004-02-12 | ||
US11/347,213 Continuation US8003262B2 (en) | 2003-08-06 | 2006-02-06 | Nonaqueous electrolyte solution secondary battery separator having defined ratio of average pore diameter to maximum pore diameter and nonaqueous electrolyte solution secondary battery using the same |
US13/047,106 Continuation US8597836B2 (en) | 2003-08-06 | 2011-03-14 | Nonaqueous electrolyte solution secondary battery separator having filler and controlled impurities |
Publications (1)
Publication Number | Publication Date |
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WO2005015660A1 true WO2005015660A1 (ja) | 2005-02-17 |
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PCT/JP2004/001466 WO2005015660A1 (ja) | 2003-08-06 | 2004-02-12 | 非水系電解液二次電池用セパレータ及びそれを用いた非水系電解液二次電池 |
Country Status (4)
Country | Link |
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US (2) | US8003262B2 (ja) |
EP (1) | EP1667252B1 (ja) |
CN (1) | CN1860627B (ja) |
WO (1) | WO2005015660A1 (ja) |
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US9608291B2 (en) | 2006-04-27 | 2017-03-28 | Mitsubishi Chemical Corporation | Non-aqueous liquid electrolyte and non-aqueous liquid electrolyte secondary battery |
US10333172B2 (en) | 2006-04-27 | 2019-06-25 | Mitsubishi Chemical Corporation | Non-aqueous liquid electrolyte and non-aqueous liquid electrolyte secondary battery |
US11283107B2 (en) | 2006-04-27 | 2022-03-22 | Mitsubishi Chemical Corporation | Non-aqueous liquid electrolyte and non-aqueous liquid electrolyte secondary battery |
JP2017103030A (ja) * | 2015-11-30 | 2017-06-08 | 日本ゼオン株式会社 | 非水系二次電池用機能層およびその製造方法、並びに、非水系二次電池およびその製造方法 |
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US8597836B2 (en) | 2013-12-03 |
EP1667252A4 (en) | 2008-07-02 |
US20060127753A1 (en) | 2006-06-15 |
EP1667252A1 (en) | 2006-06-07 |
US20110165473A1 (en) | 2011-07-07 |
CN1860627B (zh) | 2011-01-26 |
US8003262B2 (en) | 2011-08-23 |
EP1667252B1 (en) | 2011-06-22 |
CN1860627A (zh) | 2006-11-08 |
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