JP4765253B2 - Negative electrode active material for lithium secondary battery, lithium secondary battery negative electrode and lithium secondary battery - Google Patents

Description

  The present invention relates to a negative electrode active material for a lithium secondary battery, a lithium secondary battery negative electrode, and a lithium secondary battery. More specifically, the present invention provides a negative active material for a lithium secondary battery suitable for an automotive lithium secondary battery, which can achieve high output and high input by thinning the active material layer, and has a long life and high safety. And a lithium secondary battery negative electrode and a lithium secondary battery using the negative electrode active material.

  Conventionally, various secondary batteries have been developed as driving power sources for notebook computers, mobile phones, automobiles, etc. However, due to recent demands for higher functionality and acceleration in particular for automotive applications, There is a need for secondary batteries with high output and high input characteristics that can discharge or charge current.

  That is, a cordless device such as an electric drill or a cutter, a battery for an electric vehicle or a hybrid vehicle needs to be driven by a large current. In particular, batteries for hybrid vehicles do not need to have a high capacity, and have high output performance for instantaneously operating a motor that assists engine power and high input characteristics for regenerating energy when the vehicle stops. It is desired.

  On the other hand, lithium secondary batteries are excellent in energy density (Wh / kg) and power density (W / kg) when discharged with a small current, but in high current discharge (discharge with large power) In view of the durability deterioration of the battery, excellent high output characteristics were not necessarily obtained as compared with nickel hydride secondary batteries. For this reason, lithium secondary batteries are desired to be improved in short-time charge / discharge cycle characteristics with a large current value. Such performance has not been required for conventional usage as a lithium secondary battery for mobile devices.

  In a lithium secondary battery, in order to extract a large current in order to increase the output performance of each battery (single cell), it is desirable to make the electrode plate of the single cell thinner. In order to make the single cell thinner, it is necessary to make the members such as the positive electrode and the negative electrode constituting the battery thinner. Conventionally, an active material layer of a lithium secondary battery is a dispersion in which an active material capable of occluding and releasing lithium is dispersed in water or an organic solvent together with an organic substance having a binding and thickening effect on a current collector. (Slurry) is applied and dried. However, if the active material layer is made thin, the coating amount becomes non-uniform, and lithium metal is deposited due to repeated charge and discharge, causing a short circuit. There was a problem in terms of life and safety. In particular, in automobile applications, ensuring safety is extremely important and a major issue.

  WO00 / 022687 is a graphite powder having a specific surface area, aspect ratio, and tapping bulk density as a carbon material for a lithium battery, and substantially includes particles having a particle size of 3 μm or less and / or 53 μm or more. No graphite powder is described. In WO00 / 022687, it is pointed out that mixing of large particles having a particle size of 53 μm or more causes damage to the separator. However, in WO00 / 022687, it is said that particles having a particle size of 53 μm or more may be classified so that the content thereof is 1% by weight or less. In the example, the particles are sieved with a 270 mesh (53 μm) sieve. However, particles with a particle size of less than 53 μm remain, and in the case of flat graphite particles, particles with a particle size of 53 μm or more are usually about 5% by volume even if they are sieved several times with a 270 mesh sieve. It will remain.

Such graphite particles with coarse particles remaining cannot solve the problem of non-uniformity in the case where the active material layer is formed thin, and lithium metal precipitation due to repeated charge and discharge resulting from this, particularly 50 μm. This problem is remarkable in the negative electrode in which the following thinned active material layer is formed.
WO00 / 022687

  The present invention solves the above-mentioned conventional problems, and even when the negative electrode active material for a lithium secondary battery capable of thinning the active material layer, that is, when the active material layer is thinned to 50 μm or less, it is uniform. An active material that can form an active material layer and has no problem of lithium metal precipitation even after repeated charge and discharge, a lithium secondary battery negative electrode that can be thinned using the active material, and the negative electrode An object of the present invention is to provide a lithium secondary battery that is excellent in high output and high input characteristics and has a long battery life and high safety.

  The negative electrode active material for a lithium secondary battery of the present invention is a dispersion obtained by dispersing 100 g of the active material powder in 200 g of water together with 2 g of carboxymethylcellulose in a carbonaceous powder negative electrode active material for a lithium secondary battery. , JIS K5400 The particle diameter (hereinafter referred to as “maximum dispersed particle diameter”) at which grains begin to appear, measured in accordance with the degree of dispersion by the JIS K5400 grain gauge method, is 50 μm or less.

  That is, as a result of intensive investigations to solve the problems of the present invention, the present inventors have selected the physical properties of the negative electrode active material, so that even if the active material layer is thinned, short-circuiting due to lithium metal precipitation due to repeated charge and discharge is achieved. The present inventors have found that a problem can be prevented, and that a lithium secondary battery having a high output and a high input property with a long life and high safety can be realized, and the present invention has been completed.

  The negative electrode active material for a lithium secondary battery of the present invention preferably has 10 or less particles having a particle diameter of 35 μm or more and 50 μm or less as measured in accordance with the dispersity according to the JIS K5400 particle gauge method described above.

Lithium secondary battery negative electrode of the present invention, on a current collector and an active material, a lithium secondary battery negative electrode obtained by forming an active material layer containing a organic substance having a binding and thickening effect, active The material is carbonaceous powder, the thickness of the active material layer is 50 μm or less, and the arithmetic average roughness (Ra) measured in accordance with JIS B0601 is 5 μm or less.

  The lithium secondary battery of the present invention includes a positive electrode capable of occluding and releasing lithium, a negative electrode capable of occluding and releasing lithium, and a lithium secondary battery having an electrolyte. A secondary battery negative electrode is used.

  According to the negative electrode active material for a lithium secondary battery of the present invention, a thin active material layer having a thickness of 50 μm or less can be formed uniformly and without any problem of lithium metal precipitation due to repeated charge and discharge. Can do. Even if the thickness is 50 μm or less, the negative electrode of the lithium secondary battery of the present invention having an active material layer with a highly uniform surface can reduce the thickness of the negative electrode, extend its life, and improve safety. In addition, according to the lithium secondary battery of the present invention using this negative electrode, a lithium secondary battery excellent in high output / high input characteristics, long life and high safety is provided. Such a lithium secondary battery of the present invention is extremely useful industrially as a lithium secondary battery for automobiles and the like that particularly require high output performance.

  The present invention is described in further detail below.

  First, the negative electrode active material for a lithium secondary battery of the present invention will be described.

  The negative electrode active material for a lithium secondary battery of the present invention is a carbonaceous powder negative electrode active material for a lithium secondary battery, and it is essential to satisfy the following specific physical properties.

  That is, a dispersion composed of 100 g of this active material powder, 2 g of carboxymethyl cellulose and 200 g of water (hereinafter sometimes referred to as “sample dispersion”) is measured in accordance with the degree of dispersion according to the JIS K5400 grain gauge method. It is necessary that the maximum dispersed particle diameter at which grains begin to appear is 50 μm or less.

  Here, the sample dispersion is a dispersion in which the above-mentioned predetermined amounts of the active material powder, carboxymethyl cellulose and water are mixed at 25 ° C. for 30 minutes at revolution 780 rpm and rotation 144 rpm using a planetary twin-screw kneader. And

  In the present invention, the particle diameter at which particles start to appear, which is measured by the JIS K5400 particle gauge method for the above sample dispersion, is defined as the maximum dispersion particle diameter (distribution diagram method). Since the substance and / or carboxymethyl cellulose usually causes a certain degree of aggregation, grains are often observed in the streak when measuring the degree of dispersion by the grain gauge method. Therefore, in such a case, the particle diameter at which the filament begins to appear is defined as the maximum dispersed particle diameter (the filament method).

  The reason why the physical properties of the negative electrode active material specified in the present invention are effective for thinning the negative electrode active material layer will be described below.

  The negative electrode active material layer is usually a slurry-like material in which a negative electrode active material and an organic substance having a binding and thickening effect (hereinafter sometimes referred to as “binder”) are dispersed in water or an organic solvent. A material (hereinafter sometimes referred to as “active material slurry”) is formed by a thin coating and drying process on a current collector such as a metal foil, followed by a pressing process for compacting to a predetermined thickness and density. In the process of thinly applying the active material slurry on the current collector, a predetermined amount of slurry is usually obtained by slicing the active material slurry to a predetermined thickness using a blade or the like, or from a nozzle having a narrow slit-like opening. The method of discharging the water and applying it uniformly on the current collector is employed.

  By the way, the active material slurry used for forming the negative electrode active material layer is brought into the active material slurry for various reasons during the production process of the carbonaceous powder as the negative electrode active material, or aggregates under the application conditions in the active material layer forming step. Coarse particles generated by coarsening are included, but if such coarse particles are present in the active material slurry, they are retained in the gaps of the blades and the nozzle openings, and then the slurry is sufficiently supplied. Therefore, the application amount of the active material slurry on the current collector corresponding to the staying portion becomes insufficient, and then the thickness of the active material layer formed by drying and pressing is significantly nonuniform. Even when the coarse particles do not stay in the scraping blade or the discharge nozzle, the coarse particles in the active material layer exist as projections on the negative electrode plate even after pressing, which is a cause of significantly hindering surface uniformity. Become.

  When the negative electrode active material layer is non-uniform, or when a negative electrode with irregularities or protrusions on the negative electrode plate is used for the battery, the current density becomes dense, mainly in such areas with surface non-uniformity, resulting in long Through the charging and discharging of the period, lithium metal is deposited at the site where the current is concentrated, which may cause a fire accident. Therefore, the uniformity of the active material layer is required with higher accuracy as the battery has a higher current density or as the battery for pulse charge / discharge that allows a large current to flow instantaneously.

  In WO 00/022687 described above, it is described that coarse particles in the active material are eliminated in order to prevent the separator from being scratched. However, the active material layer on the negative electrode plate simply does not damage the separator. The uniformity that does not break through the separator thickness is insufficient, and high-precision uniformity that can maintain the current density uniformity even after a long charge / discharge cycle is required.

  In order to obtain an electrode plate satisfying such required performance, the present inventors need to remove coarse particles in the active material in advance under specific conditions, not simply by sieving. I found it important. And in the process of examining the conditions for eliminating the coarse particles, the present inventors have found that the carbonaceous powder such as graphite powder is not necessarily a true sphere, but has a simple particle size value and its active material layer. We paid attention to the fact that the behavior of the active material slurry during coating formation cannot be captured. Then, by observing the behavior of coarse particles in a given aqueous dispersion with individual particles, coarse particles that have an essential effect on the active material layer, although rare, in the active material powder, It does not affect the presence or absence of scratches on the separator, but it is sufficient to confirm the presence of coarse particles that cause the above-mentioned current density densification and lithium metal precipitation and satisfy any powder characteristics. Whether the performance can be obtained, the evaluation method and the acquisition method were found, and the present invention was completed.

  That is, in the present invention, as a condition for eliminating coarse particles, the maximum dispersion particle diameter is measured by the particle gauge measurement according to JIS K5400 for the above-described sample dispersion, and this value is 50 μm or less based on the maximum dispersion particle diameter. The negative electrode active material does not contain such coarse particles.

  Thus, by measuring the sample dispersion by the JIS K5400 particle gauge method, it is brought in for various reasons in the production process of the carbonaceous powder-like negative electrode active material, or under the coating conditions in the active material layer forming step. Coarse particles produced by agglomeration or coarsening can be detected or predicted. In the present invention, by using this carbonaceous powder-like negative electrode active material having a particle diameter of 50 μm or less by the measurement, unevenness of the thickness of the formed active material layer surface is prevented and highly uniform. As a result, the density of current density is suppressed. In particular, in the present invention, by making the active material free of coarse particles under such conditions, even in an active material layer formed to be very thin, such as 50 μm or less, the coarse particles are filled in the active material layer. It is presumed that the lithium battery can be prevented from acting as a kind of nucleus at the time of repeated discharge, and excellent battery characteristics as described in the examples described later can be obtained.

  In the present invention, the upper limit of the maximum dispersed particle size is 50 μm or less, preferably 35 μm or less, more preferably 30 μm or less, most preferably 25 μm or less, and the lower limit is 5 μm or more, preferably 10 μm or more. In an active material having a maximum dispersed particle diameter of more than 50 μm, in the formed active material layer, the above-mentioned coarse particles act as a kind of nucleus from which lithium metal is precipitated by repeated charge and discharge, and lithium metal is precipitated. Therefore, the maximum dispersed particle size is set to 50 μm or less. The preferable upper limit of the maximum dispersed particle size is appropriately determined in the range of 50 μm or less depending on the thickness of the active material layer formed on the negative electrode current collector and its uniformity. On the other hand, the preferable lower limit of the maximum dispersed particle size is that if the particle size is too small, the filling property tends to be impaired, and is usually set to 5 μm or more.

  The negative electrode active material for a lithium secondary battery of the present invention is a particle having a particle diameter of 35 μm or more and 50 μm or less (hereinafter referred to as “35-50 μm”) measured according to the dispersity according to JIS K5400 particle gauge method. The number of grains is preferably 10 or less. The upper limit of the number of 35-50 μm grains is more preferably 8 or less, and particularly preferably 5 or less. As for the lower limit, the smaller the better, the better.

  In the negative active material for a lithium secondary battery of the present invention, the ratio of the line scars measured in accordance with the degree of dispersion according to JIS K5400 grain gauge method in the sample dispersion is 50% or more in the gauge width direction. It is preferable that the particle diameter reaching this value (hereinafter referred to as “average dispersed particle diameter”) is usually 40 μm or less, preferably 35 μm or less, more preferably 30 μm or less, and most preferably 25 μm or less. That is, in the particle gauge measuring method based on JIS K5400 in the sample dispersion described above, coarse particles are usually recorded as filaments. As an index indicating the ratio of the coarse particles contained in the active material, the particle diameter at which the ratio of the line marks to the gauge width reaches 50% or more was adopted.

  In the above JIS K5400 particle gauge measurement, the particle diameter to be measured is not necessarily the particle diameter of the active material powder, but the particle diameter of the dispersed particles in the sample dispersion, and the active material powder and / or carboxymethylcellulose is The particle diameter of aggregated particles formed by aggregation is also included.

The negative electrode active material for a lithium secondary battery of the present invention also has the following average particle diameter (D ₅₀ ) and maximum particle diameter (D _max ) as an active material powder measured by a laser diffraction particle size distribution meter. It is preferably a value.

[Average particle diameter of active material powder (D ₅₀ )]
The average particle size (D ₅₀ ) is the median size (50% particle size) of the volume-based particle size distribution in the laser diffraction particle size distribution analyzer. In the carbonaceous powder of the negative electrode active material of the present invention, this (D ₅₀ ) is usually 20 μm or less, preferably 15 μm or less, more preferably 13 μm or less, and particularly preferably 10 to 13 μm.

  That is, the particle diameter according to the above-mentioned JIS K5400 particle gauge method corresponds to the maximum particle diameter of coarse particles that can exist in the active material layer when the active material layer is actually formed, whereas the laser diffraction particle The average particle diameter of the active material measured by the diameter distribution diameter indicates the average size of the active material particles. Therefore, the value obtained by the laser diffraction particle size distribution meter is not an index indicating a correlation with the electrode thickness but an important index for achieving a correlation with the battery performance.

When the average particle diameter (D ₅₀ ) of the active material exceeds the above upper limit, the diffusibility of lithium ions into the active material is deteriorated, and the input / output characteristics of the battery are deteriorated. The lower limit of the average particle diameter (D ₅₀ ) is usually 5 μm or more, preferably 7 μm or more. When an active material having an average particle size (D ₅₀ ) of less than 5 μm is used, the filling property of the active material is deteriorated. Therefore, the average particle size (D ₅₀ ) is preferably 5 μm or more.

[Maximum particle size of active material (D _max )]
The upper limit of the maximum particle size (D _max ) measured by a laser diffraction particle size distribution meter is usually 70 μm or less, preferably 60 μm or less, more preferably 52 μm or less, particularly preferably 45 μm or less, and particularly preferably 45 to 52 μm. The lower limit is usually 20 μm or more. When an active material having a maximum particle size (D _max ) of less than 20 μm is used, not only the filling property of the active material is deteriorated, but also the void structure in the battery electrode is subdivided, the movement of lithium ions is hindered, and the battery output Decreases. Therefore, the maximum particle size (D _max ) is preferably 20 μm or more.

As described above, the maximum dispersed particle size according to the JIS K5400 particle gauge method is a value in accordance with the situation in which the slurry-like active material is actually applied on the current collector, whereas the laser diffraction particle size distribution size is The maximum particle diameter (D _max ) is a maximum particle diameter (100% particle diameter) calculated according to a particle diameter distribution obtained by converting individual particles into a sphere. That is, the maximum dispersed particle size of the JIS K5400 grain gauge method indicates the size and number of coarse particles that are an obstacle to obtaining a uniform electrode plate. Furthermore, with this maximum dispersed particle size, for example, particles having flat anisotropy have a high probability of being measured with the major axis direction parallel to the gauge surface at the time of measurement. A value lower than the maximum particle diameter ( _Dmax ) to be measured may be obtained.

Furthermore, in the negative electrode active material for a lithium secondary battery of the present invention, the upper limit of the BET specific surface area by the nitrogen gas adsorption method is usually 13 m ² / g or less, preferably 8 m ² / g or less, more preferably 5 m ² / g or less. Particularly preferably, it is 2.5 to 4.5 m ² / g, and the lower limit is usually 1 m ² / g or more, preferably 2 m ² / g or more, more preferably 2.5 m ² / g or more. If this value exceeds the above upper limit, the storage durability tends to deteriorate, and if it falls below the lower limit, the input / output characteristics tend to deteriorate.

  Next, the carbonaceous powder material constituting the negative electrode active material for a lithium secondary battery of the present invention will be described.

  The “carbonaceous material” of the active material is not particularly limited as long as it contains a carbonaceous material capable of occluding and releasing lithium, and specific examples thereof include graphite, amorphous, graphitic / amorphous. Any of these may be used in the present invention.

  Graphite is a graphitic carbon selected from artificial graphite, natural graphite, mesophase pitch graphite, graphitized carbon fiber, high-purity purified products thereof, reheat-treated products thereof, or mixtures thereof. Examples of the form include mixed particles in which different types of graphitic carbon particles are mixed, and granulated particles in which many graphite carbon fine particles are isotropically bonded. Moreover, the thing in the following powder states is used suitably.

That is, it is preferable to use a graphite powder having a crystal plane (002) interval d ₀₀₂ of 0.348 nm or less and a laminated layer thickness Lc of 10 nm or more. It is more preferable that the crystal plane (002) has an interplanar spacing d ₀₀₂ of 0.338 nm or less and a thickness Lc of the laminated layer of 20 nm or greater, and the crystal plane (002) has an interplanar spacing d ₀₀₂ of 0.337 nm or less. It is most preferable that the thickness Lc of the laminated layer is 40 nm or more.

The capacitance theoretical value per carbon 1g lithium ions relative to the C ₆ Li, which is an interlayer compound produced is stored between the graphite layers is 372 mAh. The graphite selected in this manner has a specific capacity of 320 mAH / g or more, more preferably 340 mAh / in, in a capacitance measurement by a half-cell using a lithium metal counter electrode with a charge / discharge rate of 0.2 mA / cm ^2. g or more, more preferably 350 mAH / g or more.

As the amorphous material, it is preferable to use a carbonaceous powder whose crystal plane (002) has an interplanar spacing d ₀₀₂ of 0.349 nm or more and a laminated layer thickness Lc of less than 10 nm. It is more preferable that the interplanar spacing d ₀₀₂ of the crystal plane (002) is 0.349 nm to 0.355 nm and the crystallite thickness Lc in the C-axis direction is 7 nm or less. Most preferred is 10 nm, more preferably 1.5 to 5 nm.
Examples of the amorphous form include mixed particles in which different types of amorphous carbon particles are mixed, and granulated particles in which a large number of amorphous carbon fine particles are bonded.

  The graphite / amorphous composite system is not particularly limited in the form containing the above-mentioned graphite material and amorphous material, but, for example, a graphite powder partially or entirely coated with an amorphous material And a mixture of graphite powder and an amorphous material, and artificial graphite in which graphite fine particles are amorphous or a large number of them are isotropically bonded via a graphitized product thereof. Among these, graphite powder coated with a part or all of an amorphous material can provide high capacity, high output characteristics and pulse cycle durability performance with a large current. It is suitably used in applications of automobiles and hybrid cars.

As for the physical properties of the carbonaceous powdered negative electrode active material of the present invention, including these graphite and amorphous, the Raman spectrum using an argon ion laser beam having a wavelength of 514.3 nm is 1580 to 1620 cm ⁻¹ . The peak intensity ratio R (= IB / IA) is 0.7 when the peak intensity appearing in the range is IA, the half-width of the peak is Δν, and the peak intensity appearing in the range of 1350 to 1370 cm ⁻¹ is IB. What is below is preferable, What is 0.5 or less is more preferable, What is 0.3 or less is still more preferable. Moreover, what the minimum of this peak intensity ratio R is 0.01 or more is preferable. Further, it is preferable that the upper limit of the half-value width Δν is 60 cm ⁻¹ or less, preferably 40 cm ⁻¹ or less, more preferably 30 cm ⁻¹ or less, and particularly preferably 24 cm ⁻¹ or less. The lower limit of the half-value width Δν is preferably as narrow as possible, but is usually 14 cm ⁻¹ or more.

  The production method of the carbonaceous material applied to the active material of the present invention is not particularly limited. For example, from the carbon precursor described below, carbonization or graphitization is performed by appropriately changing the firing conditions. Obtainable.

  In this case, as the carbon precursor for proceeding carbonization in the liquid phase, coal tar pitch from soft pitch to hard pitch, or heavy coal based oil such as dry distillation liquefied oil, normal pressure residual oil, reduced pressure residual oil DC Heavy oils such as ethylene tar produced as a by-product during pyrolysis of heavy oils such as crude oils, crude oils, naphtha, aromatic hydrocarbons such as acenaphthylene, decacyclene, anthracene, phenanthrene, N ring compounds such as phenazine and acridine, S ring compounds such as thiophene and bithiophene, polyphenylenes such as biphenyl and terphenyl, polyvinyl chloride, polyvinyl alcohol, polyvinyl butyral, insolubilized products of these, organic polymers such as nitrogen-containing polyacrylonitrile and polypyrrole, Sulfur-containing polythiophene, organic polymers such as polystyrene, cellulose Natural polymers such as lignin, mannan, polygalacturonic acid, chitosan, polysaccharides such as saccharose, thermoplastic resins such as polyphenylene sulfide, polyphenylene oxide, furfuryl alcohol resin, phenol-formaldehyde resin, imide resin, etc. One or more carbonizable organic compounds selected from thermosetting resins, mixtures of the above and low molecular organic solvents such as benzene, toluene, xylene, quinoline, and n-hexane are used.

  Below, the general method for obtaining the negative electrode active material for lithium secondary batteries of a carbonaceous powder is demonstrated.

  In order to produce a carbonaceous powder-like negative electrode active material, first, graphite powder and / or amorphous powder are pulverized and classified. For pulverization of graphite powder and amorphous powder, high-speed rotary pulverizer (hammer mill, pin mill, etc.), various ball mills (rolling type, vibration type, planetary type, etc.), stirring mill (bead mill, etc.), screen mill Any pulverizer can be used as long as it can be pulverized into a preferred particle size range, such as a turbo mill and a jet mill. The pulverization can be carried out either wet or dry.

  The classification operation for bringing the obtained powder into a predetermined particle size range may be performed as long as the particles can be separated, and can be performed either dry or wet. Wet or dry sieving methods, forced vortex type centrifugal classifiers (micron separators, turboplexes, turbo classifiers, super separators), air classifiers such as inertia classifiers (elbow jets, etc.), and wet sedimentation separation methods Centrifugal classification can also be employed.

  In the present invention, when mixed particles in which different types of graphitic carbon particles are mixed are used as the graphite, a plurality of types of graphitic carbon particles may be appropriately mixed in a desired type and ratio. In addition, as a method for producing granulated particles in which a large number of isotropic graphite particles are bonded as graphite, for example, one or more kinds of graphite carbon particles and a carbon precursor are further required. Depending on the solvent (usually organic solvent such as aromatic hydrocarbon solvent such as toluene, xylene, etc.) and mixed using a mixer or kneader, it is usually until a crystal structure equivalent to the graphitic carbon fine particles is obtained. Heat treatment is preferably performed at a temperature of 2800 ° C. or more, especially 2900 ° C. or more, usually 3500 ° C. or less, particularly 3100 ° C. or less, and the mixture is usually difficult to oxidize. In the volatile gas atmosphere generated from the raw material in the above process, firing is performed in an inert gas atmosphere such as nitrogen, and thereafter, pulverization and classification are appropriately performed to adjust to a desired particle size. At this time, the graphitic carbon fine particles and the carbon precursor are mixed with a solvent as necessary, and once formed into a block shape, a rod shape or the like, and then heated and fired. The mixer used here is a high-speed shear mixer, a bead mill, a Henschel Kimiser, a vertical mixer such as a mixer equipped with a mixing tank in which a shaft and a plurality of stirring blades fixed to the shaft are arranged in different phases. Or a horizontal type mixer is mentioned. The kneader includes a kneader-type device in which a sigma-type stirring blade rotates along the side surface of the mixing tank, and a kneader such as a uniaxial or biaxial kneader that is usually used for resin processing or the like. Can be mentioned.

  In the present invention, when mixed particles in which different types of amorphous carbon particles are mixed as amorphous are used, a plurality of types of amorphous carbon particles may be appropriately mixed in a desired type and ratio. . Moreover, as a manufacturing method when using a granulated particle in which a large number of amorphous carbon fine particles are bonded as an amorphous material, for example, one or more kinds of amorphous carbon fine particles and a carbon precursor are further required. Depending on the solvent (usually an organic solvent such as an aromatic hydrocarbon solvent such as toluene, xylene, etc.) mixed with a mixer or kneader, the temperature at which the carbon precursor does not grow into a graphite structure, usually 700 ° C. or higher, preferably 800 ° C. or higher, particularly 1000 ° C. or higher, usually 2800 ° C. or lower, especially 2000 ° C. or lower, especially 1500 ° C. or lower, and usually under the conditions that the mixture is not easily oxidized Preferably, for example, in a vacuum, in a volatile gas atmosphere generated from a raw material in the course of a mixture or heat treatment, firing in an inert gas atmosphere such as nitrogen, and then appropriately pulverized and classified to obtain desired particles And the like can be adjusted. The mixer used here is a high-speed shear mixer, a bead mill, a Henschel Kimiser, a vertical or horizontal type mixer such as a mixer equipped with a mixing tank in which a shaft and a plurality of stirring blades fixed to the shaft are arranged in different phases. Can be mentioned. The kneader includes a kneader-type device in which a sigma-type stirring blade rotates along the side surface of the mixing tank, and a kneader such as a uniaxial or biaxial kneader that is usually used for resin processing or the like. Can be mentioned.

  In the present invention, the graphite powder and the amorphous powder can be mixed and used in an arbitrary quantity ratio depending on the use of the battery. In this case, the mixing ratio of the graphite powder and the amorphous powder can be used in any quantitative ratio, but the weight ratio of the graphite powder to the total amount of the graphite powder and the amorphous powder is , Preferably 50% or more, more preferably 70% or more. When the ratio of the amorphous powder to the total amount of the graphite powder and the amorphous powder is large, the influence of the irreversible capacity characteristic of the amorphous becomes large. .

  Further, in the present invention, a powder obtained by combining amorphous carbon with a graphite powder as a base material can also be used as an active material. In this case, the graphite powder as the base material can be selected from those satisfying the above-mentioned requirements for graphitic carbon and the following requirements for particle size and specific surface area. On the other hand, the composite amorphous can be selected from those satisfying the above-mentioned requirements for amorphous carbon.

The preferred particle size and specific surface area of the graphite powder as the base material are as follows. In the laser diffraction particle size distribution analyzer, the average particle size (D ₅₀ ) is usually 20 μm or less, preferably 15 μm or less, more preferably 13 μm or less, and particularly preferably 8 to 13 μm. BET specific surface area, ^{15 m} 2 / g or less, preferably ^2m 2 / g or more ^13m 2 / g or less, more preferably ^3m 2 / g or more ^12m 2 / g or less, and most preferably, ^8m 2 / g or more ^12m 2 / g or less.

  Graphite and amorphous composites are obtained by heat-treating a mixture of carbon precursors and graphite powder using the carbon precursors to obtain amorphous, and then grinding the composite powders. A method of obtaining the above-mentioned amorphous powder in advance, mixing it with the graphite powder, and heat-treating the composite, preparing the above-mentioned amorphous powder in advance, A method of mixing powder, amorphous powder, and a carbon precursor, and performing a heat treatment to form a composite can be employed. In the latter two methods of preparing an amorphous powder in advance, it is preferable to use amorphous particles having an average particle diameter of 1/10 or less of the average particle diameter of the graphite particles.

  Usually, such graphite particles or a mixture of graphite particles and amorphous particles and a carbon precursor are heated to obtain an intermediate substance, and then carbonized, fired, and pulverized to finally form graphite particles. A graphite amorphous composite powder obtained by compounding an amorphous material can be obtained. The ratio of the amorphous material in such a graphite amorphous composite powder is 50% by weight or less, preferably 25% by weight or less. More preferably 15% by weight or less, particularly preferably 10% by weight or less, 0.1% by weight or more, preferably 0.5% by weight or more, more preferably 1% by weight or more, particularly preferably 2% by weight or more. It is better to adjust as follows.

  The manufacturing process for obtaining such a graphite amorphous composite powder is usually divided into the following four processes.

  First step: Graphite particles or a mixed powder of graphite particles and amorphous particles, a carbon precursor, and, if necessary, a solvent are mixed using various commercially available mixers and kneaders, and the mixture is mixed. Get.

  Second step: If necessary, the mixture is heated with stirring to obtain an intermediate substance from which the solvent has been removed.

  Third step: The mixture or intermediate substance is heated to 700 ° C. or higher and 2800 ° C. or lower in an inert gas atmosphere such as nitrogen gas, carbon dioxide gas or argon gas to obtain a graphite amorphous composite material.

  Fourth step: The composite material is subjected to powder processing such as pulverization, pulverization, and classification as required.

  Among these steps, the second step and the fourth step may be omitted depending on circumstances, and the fourth step may be performed before the third step.

  In addition, the heat history temperature condition is important as the heat treatment condition in the third step. The lower temperature limit is usually 700 ° C. or higher, preferably 900 ° C. or higher, although it varies slightly depending on the type of carbon precursor and its thermal history. On the other hand, the upper limit temperature can basically be raised to a temperature that does not have a structural order exceeding the crystal structure of the graphite particle nucleus. Therefore, the upper limit temperature of the heat treatment is usually 2800 ° C. or lower, preferably 2000 ° C. or lower, more preferably 1500 ° C. or lower. Under such heat treatment conditions, the heating rate, cooling rate, heat treatment time, etc. can be arbitrarily set according to the purpose. Further, after heat treatment in a relatively low temperature region, the temperature can be raised to a predetermined temperature. In addition, the reactor used for this process may be a batch type or a continuous type, and may be one or more.

The material obtained by combining amorphous with graphite obtained as described above has a peak intensity ratio R value by Raman spectrum analysis, a half-value width Δν of a peak near 1580 cm ⁻¹ , and a diffraction diagram of X-ray wide angle diffraction. In the values of d ₀₀₂ and Lc obtained in the above, the crystallinity of the graphite material is not exceeded, that is, the R value is greater than that of graphite, the half-value width Δν is greater than that of graphite, and the d ₀₀₂ value is It is preferable that Lc is not less than that of graphite and not more than that of graphite. The R value of the specific graphite amorphous composite powder material is 0.01 or more and 1.0 or less, preferably 0.05 or more and 0.8 or less, more preferably 0.2 or more and 0.7 or less, and still more preferably. Is not less than 0.3 and not more than 0.5, and is not less than the value of the graphite as a base material.

  Such a graphite amorphous composite powder material has a high output property that is manifested by a low-potential charge / discharge curve characteristic of graphitic carbon, and excellent lithium acceptability that is characteristic of amorphous carbon. Therefore, it is more suitable as an active material of the present invention because high performance and high pulse durability can be obtained. This is used for large drive power supplies, electric vehicles, particularly hybrid vehicles. Is more prominent.

  The lithium of the present invention is in the form of a carbonaceous powder produced as described above, and satisfies the above-mentioned specific maximum dispersed particle size, further 35 to 50 μm number of grains, average dispersed particle size and the like. A method for preparing a negative electrode active material for a secondary battery will be described.

  Conventionally, negative electrode active materials for lithium secondary batteries have been used by pulverizing and classifying graphite powder, amorphous powder, and graphite / amorphous composite powder, but in conventional normal classification, Even if the sieve opening is selected, flat particles and the like pass through the sieve, and once such coarse particles are mixed, they cannot be removed, and these coarse particles may damage the separator. Even if not, the battery performance was adversely affected, such as being the nucleus of lithium metal precipitation in the active material layer.

  In the present invention, in order to obtain an active material that satisfies the above-mentioned specific maximum dispersed particle diameter, 35 to 50 μm number of grains, average dispersed particle diameter, and the like, for example, the following technical measures are taken.

  (1) The coarse particles are surely removed by repeating the sieving operation. Usually, by repeating sieving twice or more, preferably 4 times or more with a sieve of ASTM 400 mesh or less, sieving of flat particles is performed to reliably remove coarse particles.

  (2) Use a wet sieve to increase classification efficiency.

  For example, as a medium, a liquid that is not reactive with active material powders such as water and alcohols such as ethanol, or a mixture thereof is used, and the solid content concentration on the sieve is usually 1% by weight or more, especially 5% % Or more, usually 20% by weight or less, and particularly preferably about 10% by weight or less. When this solid content concentration exceeds 20% by weight, the active material powder is likely to be clogged, and the productivity tends to be lowered. In addition, the separation of the coarse particles in the medium liquid surface direction on the sieve is further ensured, but if the solid content concentration exceeds 20% by weight, the coarse particles tend to hardly move in the medium liquid surface direction. On the other hand, when the solid content concentration is less than 1% by weight, the productivity is lowered, and on the contrary, the chances that the flat coarse particles rotate and pass through the openings of the sieve are easily increased.

  It is preferable to perform a treatment of passing such a wet sieve twice or more, more preferably four times or more. Note that a wind classifier and a wet classifier, which will be described later, may be used in combination.

  (3) The coarse particles are surely removed by repeating the wind-type classification usually twice or more, preferably 4 times or more. Usually, the upper limit number of times varies depending on the properties of the target active material and cannot be generally specified, but is about 10 times or less, especially about 8 times or less.

  If the air volume of the wind classifier used is too large, the active material powder is taken out with coarse particles contained. Moreover, when the supply amount of the active material powder to be processed is too large, the energy received from the air current per particle is small, the adjustment of the classification point is difficult, and the target active material powder is difficult to manufacture. Furthermore, in air classification of flat active material particles, the coarser the particles, the greater the difference in resistance depending on the direction in which the air current strikes.

  In order to make air classification more reliable, the coarse particles fall smoothly by reducing the amount of processing to prevent the coarse particles from floating and mixing with the small particles by the air flow. It is better to be done. Further, in order to efficiently classify powder that does not contain coarse powder, it is effective to reduce the amount of raw material supply. Incidentally, the degree of the reduction is preferably a powder supply amount of ¼ to ¼ with respect to conventional conditions including general coarse particles.

  It is also important to devise a long airflow space in the vertical direction from the airflow introduction position of the powder classification chamber to the outlet of the airflow containing the target powder.

As specific conditions for the wind classification, as for the wind classification of powder having an average particle diameter (D ₅₀ ) of 20 μm or less, as an industrial classifier, the lower limit is usually 5 m ³ / min or more, especially 10 m. ³ / min or more, upper limit is 80 m ³ / min or less, especially 50 m ³ / min or less, a gas flow that is not reactive with the active material powder, usually by supplying air, and the lower limit is usually 0 It is better to classify the powder at a processing speed of 5 kg / min or more, especially 1 kg / min or more, and the upper limit is usually 10 kg / min or less, especially 8 kg / min or less.

  Next, the lithium secondary battery negative electrode of the present invention will be described.

  The lithium secondary battery negative electrode of the present invention may be referred to as an active material layer (hereinafter referred to as a “negative electrode mixture layer”) containing a negative electrode active material and an organic substance having a binding and thickening effect on a current collector. .), The thickness of the active material layer is 50 μm or less, and the arithmetic average roughness (Ra) measured in accordance with JIS B0601 is 5 μm or less. Even if the active material layer is thinned as described above, if the active material layer has a highly uniform surface, a lithium secondary battery having excellent long-term cycle characteristics of pulse charge / discharge, as shown in the examples described later, Can be realized.

In addition, this surface roughness (Ra) is the above-mentioned average particle diameter (D ₅₀ ) measured using a laser diffraction particle size distribution meter in accordance with JIS B0601 using a laser microscope. This is done by calculating within a measurement interval with 10 times as a guide. Although it depends on the particle diameter of the active material powder, it is usually appropriate to carry out this measurement section at 100 μm.

  The upper limit of the surface roughness (Ra) of this active material layer is 5 μm or less, preferably 2 μm or less. The lower limit is better, but if it is about 0.1 μm, lithium metal deposition can be reliably prevented. .

  Usually, the active material layer is often provided on both sides of the current collector. However, according to the lithium secondary battery negative electrode of the present invention, the thickness of one active material layer (one side) is 100 μm or less, particularly 80 μm or less. Of these, the thickness can be reduced to 50 μm or less, particularly 40 μm or less, for example, 30 to 40 μm.

  Such an active material layer of the lithium secondary battery negative electrode of the present invention can be realized by using the above-described negative electrode active material for lithium secondary battery of the present invention as an active material.

As described above, the negative electrode active material layer (negative electrode mixture layer) is usually a slurry obtained by dispersing an organic substance having a binding and thickening effect with a negative electrode active material in an aqueous solvent or an organic solvent. For example, a thin coating and drying process on a current collector, followed by a pressing process for compacting to a predetermined thickness and density. The density of the negative electrode active material layer (negative electrode mixture layer) is usually 0.9 g / cm ³ or more, particularly 1.2 g / cm ³ or more, particularly 1.5 g / cm ³ or more, and usually 2.2 g / cm ^3. In the following, 1.9 g / cm ³ or less is preferable, and 1.7 g / cm ³ or less is particularly preferable.

The organic material having a binding and thickening effect used for forming the negative electrode active material layer is not particularly limited, but may be either a thermoplastic resin or a thermosetting resin. Preferred binders in the present invention include, for example, polyethylene, polypropylene, polytetrafluoroethylene (PTFE), polyvinylidene fluoride (PVDF), styrene butadiene rubber, tetrafluoroethylene-hexafluoroethylene copolymer, tetrafluoroethylene. -Hexafluoropropylene copolymer (FEP), tetrafluoroethylene-perfluoroalkyl vinyl ether copolymer (PFA), vinylidene fluoride-hexafluoropropylene copolymer, vinylidene fluoride-chlorotrifluoroethylene copolymer, ethylene -Tetrafluoroethylene copolymer (ETFE resin), polychlorotrifluoroethylene (PCTFE), vinylidene fluoride-pentafluoropropylene copolymer, propylene-tetrafluoro Ethylene copolymer, ethylene-chlorotrifluoroethylene copolymer (ECTFE), vinylidene fluoride-hexafluoropropylene-tetrafluoroethylene copolymer, vinylidene fluoride-perfluoromethyl vinyl ether-tetrafluoroethylene copolymer, ethylene -Acrylic acid copolymer or (Na ⁺ ) ion crosslinked product of the material, ethylene-methacrylic acid copolymer or (Na ⁺ ) ion crosslinked product of the material, ethylene-methyl acrylate copolymer or ( Na ⁺ ) ion cross-linked body, ethylene-methyl methacrylate copolymer, or (Na ⁺ ) ion cross-linked body of the above materials can be mentioned, and these materials can be used alone or as a mixture. Among these materials, more preferable materials are styrene butadiene rubber, polyvinylidene fluoride, ethylene-acrylic acid copolymer, or (Na ⁺ ) ion-crosslinked product of the material, ethylene-methacrylic acid copolymer, or ( Na ⁺ ) ion-crosslinked product, ethylene-methyl acrylate copolymer, (Na ⁺ ) ion-crosslinked product of the material, ethylene-methyl methacrylate copolymer, or (Na ⁺ ) ion-crosslinked product of the material.

  If necessary, a negative electrode conductive agent can be used for the negative electrode active material layer. The negative electrode conductive agent may be anything as long as it is an electron conductive material and does not impair the uniformity of the active material layer. For example, natural graphite (such as flake graphite), graphite such as artificial graphite and expanded graphite, carbon black such as acetylene black, ketjen black, channel black, furnace black, lamp black, thermal black, carbon fiber, Conductive fibers such as metal fibers, metal powders such as copper and nickel, and organic conductive materials such as polyphenylene derivatives can be contained alone or as a mixture thereof. Among these conductive agents, artificial graphite, acetylene black, and carbon fiber are particularly preferable. Usually, it is more effective in terms of suppressing the formation of coarse particles on the electrode plate that the conductive agent has an average particle size of 3 μm or less, particularly 1 μm or less. If the lower limit of the average particle diameter of the conductive agent is about several nm, there is no particular problem in the performance of the electrode plate.

  In addition to the conductive agent, the negative electrode active material layer may further contain a filler, a dispersant, an ionic conductor, a pressure enhancer, and other various additives. Any filler can be used as long as it is a fibrous material that does not cause a chemical change in the constructed battery. Usually, olefin polymers such as polypropylene and polyethylene, fibers such as glass and carbon are used.

  For the preparation of the active material slurry, an aqueous solvent or an organic solvent is used as a dispersion medium.

  As the aqueous solvent, water is usually used, and additives such as alcohols such as ethanol and cyclic amides such as N-methylpyrrolidone may be added to water up to about 30% by weight or less. it can.

  As the organic solvent, usually, cyclic amides such as N-methylpyrrolidone, linear amides such as N, N-dimethylformamide and N, N-dimethylacetamide, and aromatic carbonization such as anisole, toluene and xylene Examples thereof include alcohols such as hydrogens, butanol and cyclohexanol, among which cyclic amides such as N-methylpyrrolidone, linear amides such as N, N-dimethylformamide and N, N-dimethylacetamide are preferable. .

  An active material slurry is prepared by mixing an active material, an organic material having a binding and thickening effect as a binder, and a conductive agent for a negative electrode and other fillers blended as necessary in these solvents. Is applied to the negative electrode current collector so as to have a predetermined thickness, whereby a negative electrode active material layer is formed.

  The upper limit of the concentration of the active material in this active material slurry is usually 70% by weight or less, preferably 55% by weight or less, and the lower limit is usually 30% by weight or more, preferably 40% by weight or more. If the concentration of the active material exceeds this upper limit, the active material in the active material slurry tends to aggregate, and if it falls below the lower limit, the active material tends to settle during storage of the active material slurry.

  Moreover, the upper limit of the binder concentration in the active material slurry is usually 30% by weight or less, preferably 10% by weight or less, and the lower limit is usually 0.1% by weight or more, preferably 0.5% or more. When the concentration of the binder exceeds this upper limit, the internal resistance of the electrode increases, and when the concentration is lower than the lower limit, the binding property between the obtained electrode and the electrode powder becomes poor.

  Furthermore, the concentration of the negative electrode conductive agent in the active material slurry is preferably 0 to 5% by weight, and the concentration of other fillers and the like is preferably 0 to 30% by weight.

  Any negative electrode current collector may be used as long as it is an electronic conductor that does not cause a chemical change in the constituted battery. For example, in addition to stainless steel, nickel, copper, titanium, carbon, conductive resin, etc., materials obtained by treating the surface of copper or stainless steel with carbon, nickel, or titanium are used. In particular, copper or a copper alloy is preferable. The surface of these materials can be oxidized and used. Further, it is desirable to make the current collector surface uneven by surface treatment. As the shape, a film, a sheet, a net, a punched product, a lath body, a porous body, a foamed body, a molded body of fiber group, and the like are used in addition to the foil. The thickness of such a negative electrode current collector is not particularly limited, but a thickness of 1 to 500 μm is used.

  In the present invention, in order to satisfy the surface average roughness (Ra) of 5 μm or less of the negative electrode active material layer described above, an active material, a binder, and other components as necessary are blended in a solvent. Prior to application of the active material slurry onto the current collector, filtration with a sieve may be performed. In this case, it is usually at least once using a sieve of ASTM 270 mesh (aperture 53 μm) or less, preferably ASTM 325 mesh or less (aperture 43 μm), more preferably ASTM 400 mesh or less (aperture 35 μm), preferably 2 It is preferable to perform the filtration operation more than once. The lower limit of the temperature condition in this filtration operation is usually 5 ° C or higher, particularly 10 ° C or higher, and the upper limit is preferably 50 ° C or lower, particularly 30 ° C or lower. When this temperature condition exceeds the above upper limit, the dispersion medium tends to evaporate, and when the temperature condition is below the lower limit, the viscosity of the dispersion medium tends to increase.

  In this filtration operation, the lower side of the sieve mesh is pressurized from the atmospheric pressure as the filtration proceeds. Therefore, it is preferable to periodically release the atmosphere to return to the atmospheric pressure. Furthermore, you may make the under sieve side into a pressure reduction state. At this time, the reduced pressure is preferably about 10 to 30 kPa. Moreover, it is also preferable to attach a scraper on the upper side of the sieve and stir it so that the dispersion is always in contact with the sieve evenly.

  Next, the lithium of the present invention having a positive electrode capable of inserting and extracting lithium, a negative electrode capable of inserting and extracting lithium, and an electrolyte, and using such a negative electrode of the lithium secondary battery of the present invention as the negative electrode The secondary battery will be described.

  Similarly to the negative electrode plate, the positive electrode plate in the lithium secondary battery of the present invention also has a positive electrode active material and an active material layer containing an organic substance (binder) having a binding and thickening effect on the current collector. (Hereinafter sometimes referred to as “positive electrode mixture layer”), and like the negative electrode active material layer, the positive electrode active material layer is usually made of an organic substance having a binding and thickening effect with the positive electrode active material. A slurry-like material dispersed in water or an organic solvent is formed by a thin coating and drying process on a current collector such as a metal foil, followed by a pressing process for compacting to a predetermined thickness and density.

  The positive electrode active material is not particularly limited as long as it has a function capable of occluding and releasing lithium. For example, a lithium-containing transition metal oxide can be used.

Examples of the lithium-containing transition metal oxide include Li _x CoO ₂ , Li _x NiO ₂ , Li _x MnO ₂ , Li _x Co _y Ni _{1 -y} O ₂ , Li _x Co _y M _{1 -y} O _z , and Li _{x. Ni 1-y M y O z} , Li x Mn 2 O 4, Li x Mn 2-y M y O 4 (M = Na, Mg, Sc, Y, Mn, Fe, Co, Ni, Cu, Zn, Al , Cr, Pb, Sb, B. x = 0 to 1.2, y = 0 to 0.9, z = 2.0 to 2.3). Here, said x value is a value before the start of charging / discharging, and it increases / decreases by charging / discharging. Furthermore, it is possible to use a material in which a part of Co, Ni, and Mn is replaced with an element such as another transition metal. However, it is also possible to use other positive electrode materials such as transition metal chalcogenides, vanadium oxides and lithium compounds thereof, niobium oxides and lithium compounds thereof, conjugated polymers using organic conductive substances, and chevrel phase compounds. . It is also possible to use a mixture of a plurality of different positive electrode materials. The average particle diameter of the positive electrode active material particles is not particularly limited, but is preferably 1 to 30 μm.

  A positive electrode conductive agent can be used for the positive electrode active material layer. The positive electrode conductive agent may be any electron conductive material that does not cause a chemical change in the charge / discharge potential of the positive electrode material used. For example, natural graphite (such as flake graphite), graphite such as artificial graphite, carbon black such as acetylene black, ketjen black, channel black, furnace black, lamp black, thermal black, carbon fiber, metal fiber, etc. Conductive fibers, metal powders such as carbon fluoride and aluminum, conductive whiskers such as zinc oxide and potassium titanate, conductive metal oxides such as titanium oxide, and organic conductive materials such as polyphenylene derivatives It can be included alone or as a mixture thereof. Among these conductive agents, artificial graphite and acetylene black are particularly preferable. Although the addition amount of a electrically conductive agent is not specifically limited, 1-50 weight% is preferable with respect to positive electrode material, and 1-30 weight% is especially preferable. In the case of carbon or graphite, 2 to 15% by weight is particularly preferable.

There is no restriction | limiting in particular as an organic substance which has a binding and thickening effect used for formation of a positive electrode active material layer, Any of a thermoplastic resin and a thermosetting resin may be sufficient. For example, polyethylene, polypropylene, polytetrafluoroethylene (PTFE), polyvinylidene fluoride (PVDF), styrene butadiene rubber, tetrafluoroethylene-hexafluoroethylene copolymer, tetrafluoroethylene-hexafluoropropylene copolymer (FEP), Tetrafluoroethylene-perfluoroalkyl vinyl ether copolymer (PFA), vinylidene fluoride-hexafluoropropylene copolymer, vinylidene fluoride-chlorotrifluoroethylene copolymer, ethylene-tetrafluoroethylene copolymer (ETFE resin) , Polychlorotrifluoroethylene (PCTFE), vinylidene fluoride-pentafluoropropylene copolymer, propylene-tetrafluoroethylene copolymer, ethylene-chlorotrif Oroethylene copolymer (ECTFE), vinylidene fluoride-hexafluoropropylene-tetrafluoroethylene copolymer, vinylidene fluoride-perfluoromethyl vinyl ether-tetrafluoroethylene copolymer, ethylene-acrylic acid copolymer or (Na ⁺ ) ion crosslinked product, ethylene-methacrylic acid copolymer or (Na ⁺ ) ion crosslinked product of the material, ethylene-methyl acrylate copolymer, or (Na ⁺ ) ion crosslinked product of the material, ethylene-methacrylic acid Examples thereof include an acid methyl copolymer or a (Na ⁺ ) ion-crosslinked product of the above materials, and these materials can be used alone or as a mixture. Among these materials, more preferable materials are polyvinylidene fluoride (PVDF) and polytetrafluoroethylene (PTFE).

  In addition to the conductive agent, the positive electrode active material layer may further contain a filler, a dispersant, an ionic conductor, a pressure enhancer, and other various additives. Any filler can be used as long as it is a fibrous material that does not cause a chemical change in the constructed battery. Usually, olefin polymers such as polypropylene and polyethylene, fibers such as glass and carbon are used. Although the addition amount of a filler is not specifically limited, 0-30 weight% is preferable as content in an active material layer.

  For the preparation of the positive electrode active material slurry, the same aqueous solvent or organic solvent as described above is used as the dispersion medium of the negative electrode active material slurry.

  An active material, a binder, an organic substance having a thickening effect, and a positive electrode conductive agent blended as necessary, other fillers and the like are mixed in these solvents to prepare an active material slurry. The positive electrode active material layer is formed by applying the positive electrode current collector to a predetermined thickness.

  The upper limit of the concentration of the active material in this active material slurry is usually 70% by weight or less, preferably 55% by weight or less, and the lower limit is usually 30% by weight or more, preferably 40% by weight or more. If the concentration of the active material exceeds this upper limit, the active material in the active material slurry tends to aggregate, and if it falls below the lower limit, the active material tends to settle during storage of the active material slurry.

  Moreover, the upper limit of the binder concentration in the active material slurry is usually 30% by weight or less, preferably 10% by weight or less, and the lower limit is usually 0.1% by weight or more, preferably 0.5% or more. When the concentration of the binder exceeds this upper limit, the internal resistance of the electrode increases, and when the concentration is lower than the lower limit, the binding property between the obtained electrode and the electrode powder becomes poor.

  As the current collector for the positive electrode, any electronic conductor that does not cause a chemical change at the charge / discharge potential of the positive electrode material to be used may be used. For example, in addition to stainless steel, aluminum, titanium, carbon, conductive resin, etc., materials obtained by treating carbon or titanium on the surface of aluminum or stainless steel are used. In particular, aluminum or an aluminum alloy is preferable. The surface of these materials can be oxidized and used. Further, it is desirable to make the current collector surface uneven by surface treatment. As the shape, a film, a sheet, a net, a punched product, a lath body, a porous body, a foamed body, a fiber group, a non-woven body shaped body, and the like are used in addition to the foil. The thickness of such a positive electrode current collector is not particularly limited, but a thickness of 1 to 500 μm is used.

  In the lithium secondary battery of the present invention, the negative electrode plate and the positive electrode plate are preferably configured such that the negative electrode active material layer surface is present at least on the surface facing the positive electrode active material layer surface.

  Examples of the electrolyte used in the lithium secondary battery of the present invention include a nonaqueous electrolytic solution composed of a nonaqueous solvent and a lithium salt dissolved in the solvent.

  Examples of the non-aqueous solvent include ethylene carbonate (EC), propylene carbonate (PC), butylene carbonate (BC), cyclic carbonates such as vinylene carbonate (VC), dimethyl carbonate (DMC), Chain carbonates such as diethyl carbonate (DEC), ethyl methyl carbonate (EMC), dipropyl carbonate (DPC), aliphatic carboxylic acid esters such as methyl formate, methyl acetate, methyl propionate, ethyl propionate, γ- Γ-lactones such as butyrolactone, chain ethers such as 1,2-dimethoxyethane (DME), 1,2-diethoxyethane (DEE), ethoxymethoxyethane (EME), tetrahydrofuran, 2-methyltetrahydrofuran, etc. Cyclic ethers, dimethylsulfur Hoxide, 1,3-dioxolane, formamide, acetamide, dimethylformamide, dioxolane, acetonitrile, propylnitrile, nitromethane, ethyl monoglyme, phosphate triester, trimethoxymethane, dioxolane derivative, sulfolane, methylsulfolane, 1,3-dimethyl Aprotic organic solvents such as 2-imidazolidinone, 3-methyl-2-oxazolidinone, propylene carbonate derivatives, tetrahydrofuran derivatives, ethyl ether, 1,3-propane sultone, anisole, dimethyl sulfoxide, N-methylpyrrolidone These may be used alone or in combination of two or more. Of these, a mixed system of a cyclic carbonate and a chain carbonate, or a mixed system of a cyclic carbonate, a chain carbonate, and an aliphatic carboxylic acid ester is preferable.

Examples of the lithium salt dissolved in these solvents include LiClO ₄ , LiBF ₄ , LiPF ₆ , LiAlCl ₄ , LiSbF ₆ , LiSCN, LiCl, LiCF ₃ SO ₃ , LiCF ₃ CO ₂ , Li (CF ₃ SO ₂ ) ₂ , LiAsF ₆ , LiN (CF ₃ SO ₂ ) ₂ , LiB ₁₀ Cl ₁₀ , lower aliphatic lithium carboxylate, LiCl, LiBr, LiI, lithium chloroborane, lithium tetraphenylborate, imides, etc. One or a combination of two or more can be used, but it is particularly preferable to include LiPF ₆ .

A particularly preferred nonaqueous electrolytic solution in the present invention is an electrolytic solution containing at least ethylene carbonate and ethyl methyl carbonate and LiPF ₆ as a supporting salt.

  The amount of such an electrolyte added to the battery is not particularly limited, but a necessary amount can be used depending on the amount of the positive electrode material and the negative electrode material and the size of the battery. Although the dissolution amount with respect to the nonaqueous solvent of lithium salt which is a supporting electrolyte is not specifically limited, 0.2-2 mol / l is preferable. In particular, 0.5 to 1.5 mol / l is more preferable.

Further, as the electrolyte, the following solid electrolyte can be used in addition to the above-described electrolytic solution. The solid electrolyte is classified into an inorganic solid electrolyte and an organic solid electrolyte. Well-known inorganic solid electrolytes include Li nitrides, halides, oxyacid salts, and the like. Of these _{Li 4 SiO 4, Li 4 SiO} 4 -LiI-LiOH, xLi 3 PO 4 - (1-x) Li 4 SiO 4, Li 2 SiS 3, Li 3 PO 4 -Li 2 S-SiS 2, phosphosulfurized Compounds and the like are effective. For organic solid electrolytes, for example, polymer materials such as polyethylene oxide, polypropylene oxide, polyphosphazene, polyaziridine, polyethylene sulfide, polyvinyl alcohol, polyvinylidene fluoride, polyhexafluoropropylene, and their derivatives, mixtures, and composites are effective. is there.

  Furthermore, it is also effective to add other compounds to the electrolyte for the purpose of improving discharge and charge / discharge characteristics. Examples of such additives include triethyl phosphite, triethanolamine, cyclic ether, ethylenediamine, n-glyme, pyridine, hexaphosphoric acid triamide, nitrobenzene derivatives, crown ethers, quaternary ammonium salts, ethylene glycol dialkyl ethers. Etc.

  As the separator used in the present invention, an insulating microporous thin film having a large ion permeability and a predetermined mechanical strength is used. Moreover, it is preferable that this separator has a function of closing the holes at a certain temperature or higher and increasing the resistance. From the viewpoint of organic solvent resistance and hydrophobicity, a sheet, a nonwoven fabric, or a woven fabric made of olefin polymers such as polypropylene and polyethylene, glass fibers, or the like is used as the separator. The pore diameter of the separator is desirably in a range in which the positive and negative electrode materials, the binder, and the conductive agent detached from the electrode do not permeate, for example, 0.01 to 1 μm is desirable. The thickness of the separator is generally 10 to 300 μm. The porosity is determined according to the permeability of electrons and ions, the material, and the film thickness, but is generally preferably 30 to 80%.

  In addition, a polymer in which an organic electrolyte composed of a solvent and a lithium salt dissolved in the solvent is absorbed and held in a polymer material is included in the positive electrode mixture and the negative electrode mixture, and the organic electrolyte is further absorbed and held. It is also possible to constitute a battery in which a porous separator made of is integrated with a positive electrode and a negative electrode. The polymer material is not particularly limited as long as it can absorb and retain the organic electrolyte, but a copolymer of vinylidene fluoride and hexafluoropropylene is particularly preferable.

  The upper limit of the thickness of such a separator is usually 60 μm or less, preferably 50 μm or less, more preferably 30 μm or less, and the lower limit is usually 10 μm or more, preferably 15 μm or more. If the thickness of the separator exceeds the above upper limit, the internal resistance of the battery tends to increase, and if it falls below the lower limit, the positive and negative electrodes are likely to be short-circuited.

  The shape of the lithium secondary battery of the present invention is not particularly limited, and may be any of a coin type, a button type, a sheet type, a laminated type, a cylindrical type, a flat type, and a square type, and is limited to a small lithium secondary battery. It can be applied to any type such as a large one used for an electric vehicle.

  The lithium secondary battery of the present invention can be used for a portable information terminal, a portable electronic device, a small electric power storage device for home use, a motorcycle, an electric vehicle, a hybrid electric vehicle, etc., but is not particularly limited thereto. .

  According to the present invention, by using a negative electrode active material having a maximum dispersed particle size of 50 μm or less as measured by JIS K5400 particle gauge, it is possible to effectively suppress an increase in internal resistance in a pulse cycle and precipitation of lithium metal on the negative electrode surface. For example, 10C (current value that reduces the amount of electricity 10 times the battery capacity in 1 hour) 10 seconds pulse (10C current is continued for 10 seconds) When charge / discharge is performed for 100,000 cycles, the internal resistance increases (in other words, If this is done, the reduction in output) can be kept within 10%, and the pulse charge / discharge cycle characteristics at a high current value of the lithium secondary battery can be greatly improved.

  Therefore, according to the present invention, for example, when a pulse charge / discharge cycle test is performed under a high load current condition of 10 C as a lithium secondary battery, charge / discharge is stably repeated even after 200,000 cycles. A high output / high input lithium secondary battery exhibiting the above battery capacity recovery rate is provided. The lithium secondary battery of the present invention exhibiting such high output and high input characteristics is an electric drill or cutter that requires high output and high input characteristics, among the above-mentioned wide range of lithium secondary battery applications. It is suitable as a lithium secondary battery for a hybrid vehicle such as a large drive power source, an electric vehicle, and a hybrid electric vehicle.

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

Example 1
Commercially available natural graphite powder described in Example 4 in Table 1 and petroleum heavy oil obtained during naphtha pyrolysis are mixed, carbonized at 900 ° C. in an inert gas, and then sintered. By crushing and classifying the product, amorphous coated graphite in which the surface of the graphite particles was coated with amorphous carbon was obtained. In the classification process, in order to prevent mixing of coarse particles, ASTM 400 mesh sieving was repeated 5 times to obtain a negative electrode active material powder made of amorphous coated graphite. From the residual carbon ratio, it was confirmed that the obtained negative electrode active material powder was coated with 2 parts by weight of amorphous carbon with respect to 100 parts by weight of graphite.

  This active material powder was subjected to various analyzes by X-ray measurement, Raman measurement, laser diffraction particle size distribution measurement, specific surface area measurement, and JIS K5400 particle gauge measurement according to the following methods. The results are listed in Table 1.

(1) X-ray diffraction About 15% by weight of X-ray standard high-purity silicon powder is added to the sample, mixed, packed in a sample cell, and monochromatic with a graphite monochromator. A wide-angle X-ray diffraction curve was measured by the fractometer method. Based on the Gakushin method, the wide-angle X-ray diffraction curve obtained by the measurement was used to measure the (002) plane spacing (d ₀₀₂ ) and the crystallite size (Lc) in the C-axis direction.

(2) Raman measurement In a Raman spectrum analysis using an argon ion laser beam having a wavelength of 514.5 nm, a peak intensity IA of 1580 to 1620 cm ⁻¹ and a half width Δν thereof, a peak intensity IB of 1350 to 1370 cm ⁻¹ are measured, The intensity ratio R = IB / IA was measured. In the preparation of the sample, the powder was charged into the cell by natural dropping, and the measurement was performed by rotating the cell in a plane perpendicular to the laser beam while irradiating the sample surface in the cell with the laser beam.

(3) Volume-based average particle size / maximum particle size measurement About 1 cc of a 2% by volume aqueous solution of polyoxyethylene (20) sorbitan monolaurate is used as a surfactant, which is mixed in advance with an active material powder, and then ionized. The volume-based average particle size (D ₅₀ ) and the maximum particle size (D _max ) were measured with a laser diffraction particle size distribution analyzer using exchange water as a dispersion medium.

(4) Specific surface area measurement It heated to 350 degreeC as preliminary drying, and after flowing nitrogen gas for 15 minutes, it measured by the BET 1 point method in the relative pressure 0.3 by nitrogen gas adsorption | suction.

(5) Particle Gauge Measurement 100 g of active material powder, 2 g of carboxymethylcellulose, and 200 g of water were mixed for 30 minutes at a revolution of 780 rpm, a rotation of 144 revolutions, and a temperature of 25 ° C. using a 0.8 L planetary motion biaxial kneader. Next, for the obtained dispersion, using a particle gauge tester in accordance with JIS K5400, the number of particles 35 to 50 μm is determined from the maximum dispersed particle diameter at which particles begin to appear and the number of filaments formed by coarse particles. It was measured. Further, the average dispersed particle diameter at which the ratio of the line scars reached 50% or more in the gauge width direction was measured.

  Next, using the obtained amorphous coated graphite powder as a negative electrode active material, a battery was prepared according to the following procedure. According to the following method, the surface roughness of the negative electrode plate was measured and the battery performance was evaluated. It was shown to.

[Production of positive electrode]
90% by weight of lithium nickelate (LiNiO ₂ ) as a positive electrode active material, 5% by weight of acetylene black as a conductive agent, and 5% by weight of polyvinylidene fluoride (PVdF) as a binder, an N-methylpyrrolidone solvent After mixing in a slurry to form a slurry, it was applied to both sides of an aluminum foil having a thickness of 20 μm, dried, and further rolled to a thickness of 70 μm with a press. This was cut out into a width of 52 mm and a length of 830 mm to obtain a positive electrode.

[Production of negative electrode]
Carboxymethylcellulose and styrene-butadiene rubber (SBR) were added to 94 parts by weight of the negative electrode active material so as to be 3 parts by weight in solid content, respectively, and stirred and mixed using distilled water as a dispersion medium to obtain a negative electrode active material slurry. The obtained slurry was usually already mixed uniformly, but was filtered (backed) three times with a screen of ASTM 325 mesh (aperture 43 μm) as necessary. By agitation, the aggregate of the active material powder rarely remaining in the slurry can be crushed and removed. This negative electrode active material slurry was uniformly applied onto a 18 μm thick copper foil, dried, and then rolled to a thickness of 40 μm with a press machine, cut into a width of 56 mm and a length of 850 mm, to form a negative electrode. These operations were performed in an environment of 25 ° C.

[Preparation of electrolyte]
Under a dry argon atmosphere, a well-dried hexahexadioxide in a mixed solvent of purified ethylene carbonate (EC), dimethyl carbonate (DMC) and diethyl carbonate (DEC) in a volume ratio of 3: 3: 4 at a concentration of 1 mol / liter. Lithium fluorophosphate (LiPF ₆ ) was dissolved as an electrolyte to obtain an electrolytic solution.

[Battery assembly]
The positive electrode and the negative electrode were wound around a porous polyethylene sheet separator (thickness: 25 μm) to form an electrode group and enclosed in a battery can. Thereafter, 5 ml of the electrolyte solution was poured into a battery can loaded with an electrode group, sufficiently infiltrated into the electrode, and caulked to form an 18650 type cylindrical battery.

(6) Surface roughness measurement of negative electrode plate The surface roughness measurement was implemented about the produced negative electrode using the laser microscope. The measurement was carried out with reference to a section range 10 times the average particle diameter (D ₅₀ ) of the negative electrode active material measured with a laser diffraction particle size distribution meter, and this was repeated 5 times. In Example 1, it measured in the area of 100 micrometers. For each measurement data, arithmetic average roughness (Ra) was calculated in accordance with JIS B0601B, and the average value was defined as surface roughness (Ra).

(7) Evaluation of battery performance 1) Initial charge / discharge Charge / discharge (capacity confirmation) was performed in a room temperature environment of 25 ° C., and the charge state of each lithium secondary battery was adjusted to 50% based on this result.
2) Initial output evaluation Under a room temperature environment of 25 ° C., the battery in the state 1) was discharged at 1 / 4C, 1 / 2C, 1.0C, 1.5C, 2.5C, 3.0C (1 hour rate discharge). A constant current discharge was performed for 10 seconds at each current value of 1C, which is a current value for discharging the rated capacity in one hour in 1 hour (the same applies hereinafter), and a voltage drop after 10 seconds in the discharge under each condition was measured. When the discharge lower limit voltage is set to 3.0 V from these measured values, the current value I that can flow for 10 seconds is calculated, and the value calculated by the formula of 3.0 × I (W) is calculated for each battery. Initial output. Table 1 shows the output ratio when the output of the comparative battery 1 described later is 100%.
3) High-temperature cycle test The high-temperature cycle test was performed in a high-temperature environment of 60 ° C, which is regarded as the actual upper limit temperature of the lithium secondary battery. For the battery whose output evaluation was completed in 2), after charging the battery with the constant current constant voltage method of 2C up to the charge upper limit voltage of 4.1V, the charge / discharge cycle is discharged with the constant current of 2C up to the discharge end voltage of 3.0V. This cycle was repeated up to 500 cycles. The ratio of the discharge capacity at the 500th cycle to the discharge capacity at the first cycle at this time was defined as a capacity retention rate.
4) Pulse cycle test The pulse cycle test was performed at 25 ° C in a room temperature environment. The battery whose output evaluation has been completed in 2) is adjusted to 50% charge state, and a high load current of 10 C is applied for about 10 seconds in both the charge and discharge directions, centering on the voltage, and 15 seconds per cycle including the rest period. The test was repeated continuously. The battery was taken out at the time of 100,000 cycles, and the recovery rate after the pulse cycle was calculated by the following procedure. Discharge to 3.0 V at a current value of 1/2 C, charge to 4.1 V, and use the discharge capacity when discharged to 3.0 V again as the numerator. As a recovery rate.

Example 2
A negative electrode active material powder was prepared in the same manner as in Example 1 except that 8 parts by weight of amorphous carbon was produced with respect to 100 parts by weight of graphite, and various evaluations were performed in the same manner. The results are shown in Table 1.

Example 3
A negative electrode active material powder was prepared in the same manner as in Example 1 except that 18 parts by weight of amorphous carbon was produced with respect to 100 parts by weight of graphite, and various evaluations were performed in the same manner. The results are shown in Table 1.

Example 4
A negative electrode active material powder was prepared in the same manner as in Example 1 except that the commercially available natural graphite powder was classified, and various evaluations were similarly performed. The results are shown in Table 1.

Example 5
The same as in Example 1 except that the amorphous coated graphite powder with a large particle diameter prepared in Comparative Example 1 described later was passed through an ASTM 400 mesh sieve 5 times to remove coarse particles precisely. A negative electrode active material powder was prepared, various evaluations were performed in the same manner, and the results are shown in Table 1.

Example 6
The artificial graphite powder in which a number of graphite fine particles described in Comparative Example 2 to be described below are bonded isotropically through a binder pitch graphitized material is passed through an ASTM 400 mesh screen five times to accurately remove coarse particles. Except for what was performed, a negative electrode active material powder was prepared in the same manner as in Example 1, various evaluations were performed in the same manner, and the results are shown in Table 1.

Example 7
A negative electrode active material powder was prepared in the same manner as in Example 1 except that the commercially available amorphous carbon powder was classified, and various evaluations were similarly performed. The results are shown in Table 1.

Comparative Example 1
Various evaluations were performed in the same manner as in Example 1 except that amorphous coated graphite powder having a large particle size as a whole was used as the negative electrode active material, and the results are shown in Table 1.

  At this time, a back work was performed prior to the application of the negative electrode active material slurry, but a large number of coarse particles remained on the sieve. However, such operations alone are not sufficient to remove coarse particles, and the grain gauge test resulted in many streak marks remaining on the gauge.

  The obtained battery showed a low initial output value. Furthermore, in the pulse cycle test, before reaching 200,000 cycles, the battery voltage dropped to 3 V or less during the measurement, and the cycle measurement was interrupted. The cause of the voltage abnormality was presumed to be a local short circuit in the battery element.

Comparative Example 2
A large number of fine graphite particles were dispersed in the binder pitch, and graphitization and powder processing were performed to produce an artificial graphite powder in which the graphitized material was bonded isotropically through the graphitized material of the binder pitch. Various evaluations were performed in the same manner as in Example 1 except that this artificial graphite powder was used as the negative electrode active material powder, and the results are shown in Table 1.

  The obtained battery had a result that the pulse cycle test was interrupted in the same way as in Comparative Example 1.

Comparative Example 3
Various evaluations were made in the same manner as in Example 1 except that the amorphous coated graphite powder having a large particle size as described in Comparative Example 1 was passed through an ASTM 400 mesh sieve once to obtain a negative electrode active material powder. The results are shown in Table 1.

  The obtained battery had a result that the pulse cycle test was interrupted in the same way as in Comparative Example 1.

Claims (4)

In the carbonaceous powder-like negative electrode active material for lithium secondary battery,
With respect to a dispersion obtained by dispersing 100 g of the active material powder in 200 g of water together with 2 g of carboxymethylcellulose, the particle diameter at which particles begin to appear is 50 μm or less, measured according to the degree of dispersion according to JIS K5400 particle gauge method. A negative electrode active material for a lithium secondary battery.   2. The negative electrode active material for a lithium secondary battery according to claim 1, wherein the number of particles having a particle diameter of 35 μm or more and 50 μm or less is 10 or less as measured in accordance with the degree of dispersion according to the JIS K5400 particle gauge method. In a lithium secondary battery negative electrode formed by forming an active material layer containing an active material and an organic material having a binding and thickening effect on a current collector,
The active material is a carbonaceous powder, the thickness of the active material layer is 50 μm or less, and the arithmetic average roughness (Ra) measured in accordance with JIS B0601 is 5 μm or less. Secondary battery negative electrode. In a lithium secondary battery having a positive electrode capable of inserting and extracting lithium, a negative electrode capable of inserting and extracting lithium, and an electrolyte,
The lithium secondary battery negative electrode of Claim 3 was used as this negative electrode, The lithium secondary battery characterized by the above-mentioned.