JP2009238584A - Carbon particle for lithium-ion secondary battery anode, anode for lithium-ion secondary battery, and lithium-ion secondary battery - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide carbon particles for a lithium-ion secondary battery anode of high capacity and excellent cycle characteristics, an anode for a lithium-ion secondary battery using the same, and a lithium-ion secondary battery. <P>SOLUTION: The carbon particle used for the lithium-ion secondary battery anode is to have a roundness of a particle cross section of 0.6 to 0.9, an interlayer distance d (002) of graphite crystal found by X-ray diffraction measurement of 3.38 Å or less, and a crystallite size Lc (002) in a C-axis direction of 500 Å or more. As to a sample anode using the carbon particles, a peak intensity ratio Ih002/Ih110 of a carbon 002 face (a face horizontal to a graphite layer) to a carbon 110 face (a face vertical to a graphite layer) measured by the X-ray diffraction is to be 600 or less. <P>COPYRIGHT: (C)2010,JPO&INPIT

Description

  The present invention relates to carbon particles for a negative electrode of a lithium ion secondary battery, a negative electrode for a lithium ion secondary battery, and a lithium ion secondary battery. More specifically, the present invention relates to a negative electrode for a lithium ion secondary battery that is suitable for use in portable equipment, electric vehicles, power storage, etc. and has a high capacity and excellent cycle characteristics, and a lithium ion secondary battery using the negative electrode.

  Examples of negative electrode materials for conventional lithium ion secondary batteries include natural graphite particles, artificial graphite particles graphitized with coke, artificial graphite particles graphitized with organic polymer materials and pitch, graphite particles obtained by pulverizing these, etc. There is. These graphite particles are mixed with an organic binder and an organic solvent to form a graphite paste. The graphite paste is applied to the surface of the copper foil, and the solvent is dried and molded to form a negative electrode for a lithium ion secondary battery. I use it. By using graphite for the negative electrode, the problem of content short-circuiting due to lithium dendrite is solved, and cycle characteristics are improved (for example, see Patent Document 1).

  However, natural graphite, which has developed graphite crystals, has weaker bond strength between crystal layers in the C-axis direction than the bond in the crystal plane direction. It becomes what is called scale-like graphite particles. Since the scaly graphite has a large aspect ratio, when the electrode is prepared by kneading with an organic binder and applying to the current collector, the scaly graphite particles are oriented in the surface direction of the current collector, As a result, not only the charge / discharge capacity and rapid charge / discharge characteristics are likely to deteriorate, but also the internal destruction of the electrode occurs due to expansion and contraction in the C-axis direction caused by repeated insertion and extraction of lithium into and from the graphite crystal. There is a problem that the characteristics deteriorate.

  In order to improve this problem, spheroidized graphite obtained by modifying flaky graphite so as to approximate a sphere is disclosed (for example, see Patent Document 2). The cycle characteristics are improved by subjecting the flaky graphite to mechanical processing to spheroidize the particles.

  However, when the particles are spherical, the contact between the particles becomes a point contact, and the contact area between the particles decreases. In addition, the contact area between the particles decreases due to the expansion and contraction of the particles due to repeated insertion and extraction of lithium into the graphite crystal. As a result, as the number of cycles increases, the conductivity between the particles is not maintained, and as a result, the cycle characteristics are adversely affected. Therefore, there is still an insufficient point for further improvement of the cycle characteristics.

Japanese Examined Patent Publication No. 62-23433 Japanese Patent No. 3787030

  The present invention provides a carbon particle for a lithium ion secondary battery negative electrode having a high capacity and more excellent cycle characteristics, and a negative electrode for a lithium ion secondary battery and a lithium ion secondary battery using the same.

As a result of producing and examining various negative electrode materials for lithium ion secondary batteries, the present inventors made a negative electrode by using carbon particles having a specific shape parameter and a specific crystal structure. The present inventors have found that the carbon particles in a state exhibit a preferable orientation, have high capacity and excellent cycle characteristics, and have reached the present invention.
Specifically, the present invention is characterized by the matters described in the following (1) to (6).
(1) The circularity of the particle cross section is 0.6 to 0.9, the interlayer distance d (002) of the graphite crystal determined by X-ray diffraction measurement is 3.38 mm or less, and the crystallite size Lc (C-axis direction) 002) is a carbon particle for a negative electrode of a lithium ion secondary battery having a thickness of 500 mm or more,
A carbon 002 plane (plane parallel to the graphite layer) and a carbon 110 plane (plane perpendicular to the graphite layer) measured by X-ray diffraction of a sample prepared by the following methods (a) to (b). A carbon particle for a negative electrode of a lithium ion secondary battery, wherein the peak intensity ratio Ih002 / Ih110 is 600 or less.
(A) Water in which water is added so that the viscosity at 25 ° C. of the mixture is 1500 to 2500 mPa · s with respect to a mixture of 98 parts by mass of the carbon particles, 1 part by mass of the styrene butadiene resin, and 1 part by mass of carboxymethyl cellulose. Make a dispersion paint.
(B) The water-dispersed paint is coated on a copper foil and dried at 120 ° C. for 1 hour to obtain a sample.
(2) The lithium ion secondary battery according to the above (1), wherein the carbon particles have a pore volume of 10 ² to 10 ⁶細孔 of 0.4 to 2.0 ml / g per mass of the carbon particles. Carbon particles for negative electrode.
(3) A negative electrode for a lithium ion secondary battery containing the carbon particle material for a lithium secondary battery negative electrode according to (1) or (2) above.
(4) The lithium ion secondary battery which has a positive electrode containing the negative electrode and lithium compound as described in said (3).

According to the present invention, carbon particles for a lithium ion secondary battery negative electrode having a high capacity and excellent cycle characteristics can be obtained.
Moreover, according to the present invention, carbon particles for a lithium ion secondary battery negative electrode further excellent in cycle characteristics can be obtained by suppressing excessive deformation of carbon particles during electrode production.

Hereinafter, the present invention will be described in detail.
The carbon particles for a negative electrode of a lithium ion secondary battery of the present invention have a circularity of the particle cross section of 0.6 to 0.9, and the interlayer distance d (002) of the graphite crystal determined by X-ray diffraction measurement is 3.38Å. Hereinafter, a carbon 002 plane (plane parallel to the graphite layer) and carbon 110 measured by X-ray diffraction of a sample having a crystallite size Lc (002) in the C-axis direction of 500 mm or more and the same state as the negative electrode. The peak intensity ratio Ih002 / Ih110 of the plane (plane perpendicular to the graphite layer) is 600 or less.

  The circularity of the carbon particle cross section is an index indicating how close the particle cross section is to a circle, and the closer the circularity is to 1, the closer to a perfect circle.

Usually, an electrode material of a lithium ion secondary battery is mixed with a solvent and a binder to form a slurry, which is applied to a copper foil or the like as a current collector, and the solvent is dried and molded. In this case, for example, the scaly graphite having a small circularity has a plate-like shape, so the fluidity at the time of mixing with the solvent and the binder is poor, and the density variation of the lithium ion secondary battery negative electrode to be produced is large, And there exists a tendency for adhesiveness with a negative electrode electrical power collector to fall. As a result, the cycle characteristics of the obtained lithium ion secondary battery are degraded.
On the other hand, when the spheroidized particles having a circularity value close to 1 are too spherical, the contact between the particles tends to be point contact and the conductivity tends to decrease. Further, the contact area between the particles decreases due to the expansion and contraction of the particles due to repeated insertion and extraction of lithium into and from the graphite crystal, and as a result, the cycle characteristics tend to be adversely affected.
Therefore, in the present invention, by setting the circularity of the carbon particles to 0.6 to 0.9, the contour of the particle cross-sectional image in the state of being a negative electrode for a lithium ion secondary battery is a pseudo-polygonal shape. As a result, the contact area between the carbon particles increases, and the conductivity between the carbon particles can be easily maintained. As a result, by making such a shape, the contact area between the carbon particles does not decrease, and good cycle characteristics can be obtained.

The circularity of the carbon particles of the present invention is measured as follows. First, the cross section of the particle is photographed and obtained by the following formula.
Circularity = (perimeter of equivalent circle) / (perimeter of particle cross-sectional image)
Here, the “equivalent circle” is a circle having the same area as the particle cross-sectional image. The peripheral length of the particle cross-sectional image is the length of the contour line of the captured particle cross-sectional image. The circularity in the present invention is magnified to 1000 times with a scanning electron microscope, 10 carbon particles are arbitrarily selected, the circularity of each carbon particle is measured by the above method, and the average value is taken. Average circularity. As a method for taking a cross-sectional image of carbon particles in the case of a negative electrode, a sample electrode is prepared, the electrode is embedded in an epoxy resin, mirror-polished, and observed with a scanning electron microscope. In the present invention, the sample electrode has a solid content of 98 parts by mass of carbon particles as a negative electrode material, 1 part by mass of styrene butadiene resin as a binder, and 1 part by mass of carboxymethyl cellulose as a thickening material. A water-dispersed paint in which water is added so that the viscosity at 1500 is 2500 to 2500 mPa · s is prepared, and this is coated on a 10 μm copper foil to a thickness of about 70 μm (at the time of coating), and then 120 ° C. And dried for 1 hour.
In addition, the measuring method of a viscosity is as follows. Using a viscometer (manufactured by Brookfield, product name: DV-III spindle: SC4-18 # 14), the viscosity is measured at a rotation speed of 100 rpm and a temperature of 25 ° C.
The perimeter of the equivalent circle and the perimeter of the increase in particle cross-section can be determined by, for example, analysis software attached to the scanning electron microscope.

  The carbon particles for a lithium ion secondary battery negative electrode of the present invention preferably have a shape having an acute angle or an obtuse angle, including a linear portion in the contour line in the shape of the particle cross section. In the preferable shape, the shape of the particle cross section may include a contour line having a dent and a curved portion. Since the carbon particles have a circularity in the above range, the contact area between the carbon particles in the negative electrode state increases, and the contact area does not change greatly even if the lithium ion is repeatedly occluded / released. It is considered that the conductivity between particles can be easily maintained and good cycle characteristics can be obtained.

  In the present invention, in order to set the circularity of the carbon particles to 0.6 to 0.9, spheroidized natural graphite or spheroidized artificial graphite having a circularity of 0.9 to 1.0 is used as a raw material for the carbon particles. Thus, it can be prepared by modifying the graphite as a raw material for carbon particles. Spherical natural graphite or spheroidized artificial graphite having a circularity of 0.9 to 1.0 as a raw material for carbon particles will be described later, but flat natural graphite particles such as scaly natural graphite and scaly natural graphite are used. Is obtained by performing mechanical treatment for reforming treatment.

In the present invention, the interlaminar distance d (002) of the graphite crystal of the carbon particles is a value calculated from the measurement by wide angle X-ray diffraction of the carbon particles used for the negative electrode of the lithium ion secondary battery, and this value is 3.38 cm or less. And The range of 3.35 to 3.37cm is more preferable. When d (002) exceeds 3.38 mm, the discharge capacity tends to decrease. There is no particular limitation on the lower limit of d (002), but the theoretical value of d (002) of pure graphite crystal is usually 3.35 mm or more.
In detail, the d (002) of the carbon particles of the present invention is measured by irradiating the carbon particles with X-rays (CuKα rays) and measuring the diffraction lines with a goniometer. From the diffraction peak corresponding to the carbon d (002) plane appearing in the vicinity of 24 to 26 °, calculation is performed using the Bragg equation.
In the present invention, natural graphite having high crystallinity or artificial graphite having high crystallinity may be used in order to make d (002) of the carbon particles 3.38 mm or less. In order to increase the crystallinity, for example, heat treatment may be performed at a temperature of 2000 ° C. or higher.

In addition, the crystallite size Lc (002) in the C-axis direction of the carbon particles is a value calculated from measurement by wide-angle X-ray diffraction, and if this value is less than 500 mm, the discharge capacity tends to be small. The carbon particles used for the negative electrode material of the lithium ion secondary battery of the invention have Lc (002) of 500% or more. There is no particular limitation on the upper limit value of Lc (002), but it is usually set to 10000 kg or less.
The measurement of Lc (002) of the carbon particles of the present invention is performed by a usual method, and specifically, it is performed as follows. The crystallite size Lc is calculated based on the Gakushin method using a wide-angle X-ray diffractometer.
In order to make the Lc (002) of the carbon particles of the present invention 500 or more, natural graphite with high crystallinity or artificial graphite with high crystallinity may be used. In order to increase the crystallinity, for example, heat treatment may be performed at a temperature of 2000 ° C. or higher.

The carbon particles for a negative electrode of a lithium ion secondary battery of the present invention are a carbon sample 002 plane (plane parallel to the graphite layer) and a carbon 110 plane (graphite) measured by wide-angle X-ray diffraction in a sample sample prepared as follows. The peak intensity ratio Ih002 / Ih110 of the plane perpendicular to the layer is 600 or less.
(A) Water in which water is added so that the viscosity at 25 ° C. of the mixture is 1500 to 2500 mPa · s with respect to a mixture of 98 parts by mass of the carbon particles, 1 part by mass of the styrene butadiene resin, and 1 part by mass of carboxymethyl cellulose. Make a dispersion paint.
(B) The water-dispersed paint is coated on a copper foil to a thickness of 70 μm and dried at 120 ° C. for 1 hour to obtain a sample.
The peak intensity ratio Ih002 / Ih110 is a value serving as an index of randomness of orientation, and can be measured by X-ray diffraction (reflection method) (Multi Flex, manufactured by Rigaku Corporation). The peak intensity ratio Ih002 / Ih110 between the carbon 002 plane (plane parallel to the graphite layer) and the carbon 110 plane (plane perpendicular to the graphite layer) is preferably 500 or less, more preferably 350 or less.
Here, in order to measure the peak intensity ratio Ih002 / Ih110, a sample electrode is prepared by the above-described methods (a) to (b) as a sample for X-ray diffraction measurement. The diffraction intensity ratio Ih (002) / Ih (110) of this sample electrode is detected by measuring the surface of the sample electrode by X-ray diffraction using CuKα rays as an X-ray source, and near a diffraction angle 2θ = 26 to 27 degrees. The intensity of the carbon (002) plane diffraction peak detected and the carbon (110) plane diffraction peak detected near the diffraction angle 2θ = 70 to 80 degrees can be obtained by the following formula (1).
(002) Plane diffraction peak intensity / (110) Plane diffraction peak intensity Formula (1)
In order to set the diffraction intensity ratio (002) / (110) to 600 or less, it is possible to appropriately adjust the physical properties of the carbon particles to be used, for example, by setting the average particle diameter of the carbon particles to 1 to 100 μm. .
In addition, when the circularity of the carbon particles is set in the above range, the carbon particles tend to be in a random orientation state even if the carbon particles have a layered crystal structure.
The diffraction intensity ratio (002) / (110) can also be adjusted by appropriately adjusting the amount of pore volume per mass of carbon particles, or by suppressing the change in shape or destruction by using a hard material for the carbon particles. It can be adjusted.

Further, the carbon particles used for the negative electrode preferably have a pore volume of 10 ² to 10 ⁶細孔 of 0.4 to 2.0 ml / g per carbon particle mass, and 0.4 to 1.6 ml. / G is more preferable, and 0.6 to 0.8 ml / g is more preferable. When the carbon particles are used for the negative electrode of a lithium ion secondary battery, the electrolytic solution can easily penetrate into the particles, the rapid charge / discharge characteristics are excellent, and the cycle characteristics of the lithium ion secondary battery can be improved. If the amount is less than 0.4 ml / g, lithium ions are difficult to move inside the particle, and the rapid charge / discharge characteristics tend to deteriorate. If the amount exceeds 2.0 ml / g, the particle tends to collapse and the cycle characteristics tend to deteriorate. .

The pore volume can be determined by pore diameter distribution measurement by mercury porosimetry using the carbon particles of the present invention (for example, Autopore 9520 manufactured by Shimadzu Corporation). The pore size can also be determined by measuring the pore size distribution by mercury porosimetry.
In the present invention, the pore volume of the carbon particles can be adjusted by pressure treatment, modification by mechanical treatment, coating treatment, or the like to make the pore volume within the above range.

The carbon particles of the present invention preferably have a specific surface area of 10 m ² / g or less, more preferably 6 m ² / g or less. When the carbon particles are used for the negative electrode, the cycle characteristics of the obtained lithium ion secondary battery can be improved, and the irreversible capacity in the first cycle can be reduced. When the specific surface area exceeds 10 m ² / g, the irreversible capacity of the first cycle of the obtained lithium ion secondary battery tends to be large, the energy density is small, and many organic compounds are produced when producing a negative electrode. There is a tendency to require a dressing. From the cycle characteristics of the lithium ion secondary battery to be obtained better point, the specific surface area is more preferably 0.5~8m ² / g, it is highly preferably 1~6m ² / g.
The specific surface area can be measured by a known method such as the BET method (nitrogen gas adsorption method).
In the present invention, in order to set the specific surface area of the carbon particles to 10 m ² / g or less, mechanical surface modification treatment, pulverization, or the like may be performed. Further, when the particle size is decreased, the specific surface area tends to increase, and when the particle size is increased, the specific surface area tends to decrease.

The carbon particles of the present invention preferably have a true specific gravity of 2.22 or more and 2.26 or less. If the true specific gravity is less than 2.22, the charge / discharge capacity per volume of the lithium ion secondary battery tends to decrease, and the initial charge / discharge efficiency tends to decrease. On the other hand, when the true specific gravity exceeds 2.26, the life characteristics of the lithium ion secondary battery tend to deteriorate.
The true specific gravity can be determined by a pycnometer method using butanol.
In the present invention, in order to make the true specific gravity of the carbon particles 2.22 or more and 2.26 or less, heat treatment may be performed at a high temperature of 2000 ° C. or more.

The carbon particles of the present invention preferably have an average particle size in the range of 1 to 100 μm as measured by a laser diffraction particle size distribution analyzer. Setting the average particle size within this range is one of the factors that cause the peak intensity ratio Ih002 / Ih110 to be 600 or less. More preferably, it is 1-80 micrometers, More preferably, it is 5-30 micrometers. When the average particle size is 100 μm or more, the coating property is poor when applied to a paste, and the rapid charge / discharge characteristics tend to be inferior. On the other hand, if the average particle size is 1 μm or less, the particles cannot efficiently participate in the electrochemical reaction with lithium ions, and the capacity and cycle characteristics tend to decrease.
In the present invention, the average particle size is calculated as 50% D when measured with a laser diffraction particle size distribution meter.
In the present invention, in order to make the average particle diameter of the carbon particles within the above range, for example, particles having a desired size may be obtained using a pulverizer or a sieve.

The bulk density of the carbon particles of the present invention is preferably 0.3 g / cm ³ or more. When the bulk density is less than 0.3 g / cm ³ , many organic binders are required when producing the negative electrode, and as a result, the energy density of the produced lithium ion secondary battery tends to be small. Although there is no restriction | limiting in particular in the upper limit of bulk density, Usually, it is 1.5 g / cm < ³ > or less.
For the bulk density, graduated a 100 cm ³ graduated cylinder, slowly put 100 cm ³ of sample powder into it with a spoon, plug the graduated cylinder, and then drop the graduated cylinder 30 times from a height of 5 cm. It is a 30 times tap density which can be calculated from the mass and volume of the sample powder after.
In the present invention, in order to set the bulk specific gravity of the carbon particles within the above range, for example, particles having a desired size may be obtained using a pulverizer or a sieve.

In the present invention, carbon particles having an interlayer distance d (002) of 3.38 mm or less and a crystallite size Lc (002) in the C-axis direction of 500 mm or more determined by X-ray diffraction measurement are, for example, flaky natural What is necessary is just to heat-process at 2000 degreeC or more using the flat natural graphite particle | grains, such as graphite and scale natural graphite, Preferably it is 2600-3000 degreeC.
Further, in order to adjust the circularity of the carbon particles to 0.6 to 0.9 and to adjust the average particle diameter and pore volume of the carbon particles within the range of the present invention, the following modification treatment is performed. First, flat natural graphite particles having an average particle diameter of 1 to 100 μm and a circularity of 0.2 to 0.55 are used as a preferred raw material, and subjected to mechanical treatment, so that the average particle diameter of carbon particles is 5 to 50 μm and circular. Spherical natural graphite having a degree of 0.9 to 1.0 is obtained. The mechanical treatment refers to a treatment in which the particles collide with a part of the processing apparatus or particles.
Next, the spheroidized natural graphite is subjected to isotropic pressure treatment. The method of isotropic pressure treatment of the spheroidized natural graphite is not particularly limited as long as it is an isotropic pressurization method. For example, raw material graphite is placed in a container such as a rubber mold, and water is pressurized medium. And a hydrostatic pressure isotropic press, and an isotropic press with an air pressure using a gas such as air as a pressurizing medium. Moreover, you may repeat a uniaxial press from multiple directions.
The pressure of the isotropic pressure treatment of the pressurized medium of the spherical natural graphite, preferably in the range of 50~2000kgf / cm ^2, more preferably be in the range of ^{300~2000kgf / cm 2, 500~1000kgf / cm} 2 If it is the range, it is still more preferable. When the pressure is less than 50 kgf / cm ² , the effect of improving the cycle characteristics of the obtained lithium ion secondary battery tends to be small. Moreover, when the pressure exceeds 2000 kgf / cm ² , the specific surface area of the obtained lithium ion secondary battery negative electrode material increases, and as a result, the irreversible capacity at the first cycle of the obtained lithium ion secondary battery tends to increase. It is in.
When the isotropic pressure treatment is performed on the spherical natural graphite as described above, the obtained carbon particles are likely to aggregate with each other. Therefore, after the isotropic pressure treatment, it is preferable to perform treatment such as crushing and sieving. . In addition, when carbon particles do not aggregate, it is not necessary to crush.

  The negative electrode for a lithium ion secondary battery according to the present invention forms the negative electrode layer by mixing the carbon particles with an organic binder and a solvent or water, applying the mixture to a current collector, drying the solvent or water, and applying pressure. And a negative electrode for a lithium ion secondary battery.

  Examples of the organic binder include polymer compounds such as polyethylene, polypropylene, ethylene propylene rubber, butadiene rubber, styrene butadiene rubber, carboxymethyl cellulose, polyvinylidene fluoride, polyethylene oxide, polyepichlorohydrin, and polyacrylonitrile. The mixing ratio of the carbon particles and the organic binder is preferably 1 to 20 parts by mass of the organic binder with respect to 100 parts by mass of the carbon particles.

The solvent used for mixing the carbon particles and the organic binder is not particularly limited, and N-methylpyrrolidone, dimethylacetamide, dimethylformamide, γ-butyrolactone and the like are used.
As the current collector, for example, a foil or mesh of nickel, copper or the like can be used.

In the negative electrode for a lithium ion secondary battery of the present invention, the density of the mixture layer (negative electrode layer) containing the carbon particles and the organic binder on the current collector is 1.40 to 1.90 g / cm ^3. Is preferred. The density is more preferably 1.45~1.80g / cm ^3, more preferably 1.50~1.70g / cm ^3.
By increasing the density of the negative electrode layer containing the carbon particles and the organic binder on the current collector in the negative electrode of the present invention, the energy density per volume of the lithium ion secondary battery obtained using this negative electrode is reduced. Can be bigger. When the density of the negative electrode layer containing the carbon particles and the organic binder is less than 1.40 g / cm ³ , the energy density per volume of the obtained lithium secondary battery tends to be small. On the other hand, when the density of the negative electrode layer containing the carbon particles and the organic binder exceeds 1.90 g / cm ³ , the pouring property of the electrolytic solution when producing a lithium ion secondary battery tends to deteriorate. In addition, there is a tendency that rapid charge / discharge characteristics and cycle characteristics of a lithium ion secondary battery to be manufactured are deteriorated.

Here, the density of the negative electrode layer containing the carbon particles and the organic binder can be calculated from the measured values of the mass and volume of the negative electrode layer containing the carbon particles and the organic binder.
The density of the negative electrode layer containing the carbon particles and the organic binder after integration of the negative electrode layer into the current collector is appropriately adjusted by, for example, the pressure at the time of integral molding, the clearance of a device such as a roll press, etc. can do.

In order to obtain the lithium ion secondary battery of the present invention using the obtained negative electrode, for example, the positive electrode containing a lithium compound is placed opposite to the separator, and an electrolytic solution is injected. The positive electrode containing a lithium compound, for _example, can be used alone or as a mixture of _{LiNiO 2, LiCoO 2, LiMn 2} O 4 or the like. The positive electrode can be obtained by forming a positive electrode layer on the current collector surface in the same manner as the negative electrode.
Further, the electrolytic solution is, for example, a lithium salt such as LiClO ₄ , LiPF ₄ , LiAsF, LiBF ₄ , LiSO ₃ CF ₄ dissolved in, for example, ethylene carbonate, diethyl carbonate, dimethoxyethane, dimethyl carbonate, methyl ethyl carbonate tetrahydrofuran, etc. Can be used. Also, a solid or gel so-called polymer electrolyte can be used in place of the electrolytic solution.

  As the separator, for example, a nonwoven fabric mainly composed of polyolefin such as polyethylene or polypropylene, cloth, microporous film, or a combination thereof can be used. In addition, when it is set as the structure where the positive electrode and negative electrode of the lithium ion secondary battery to produce are not directly contacted, it is not necessary to use a separator.

The structure of the lithium ion secondary battery of the present invention is not particularly limited. Usually, a positive electrode and a negative electrode, and a separator provided as necessary, are wound into a flat spiral to form a wound electrode group. Or these are laminated | stacked as flat form, and it is common to set it as the laminated | stacked type | formula electrode group, and set it as the structure which enclosed these electrode plate groups in the exterior body.
Although the lithium ion secondary battery of this invention is not specifically limited, It is used as a paper-type battery, a button battery, a coin-type battery, a laminated battery, a cylindrical battery, etc.

Examples of the present invention will be described below.
(Example 1)
(1) Production of negative electrode for lithium ion secondary battery Spherical natural graphite (average particle size 20 μm, circularity 0.98, specific surface area 5.4 m ² / g, true specific gravity 2.243, Lc> 1000 Å, d (002) 3.354 mm, bulk density 0.84 g / cm ³ ) was filled into a rubber container and sealed, and then the rubber container was isotropic with a hydrostatic press at a pressure of 1000 kgf / cm ² of the pressurized medium. A pressure treatment was performed. Subsequently, it was pulverized with a cutter mill to obtain carbon particles used for a negative electrode for a lithium secondary battery.
D (002), Lc (002), peak intensity ratio Ih002 / Ih110, circularity, pore volume, specific surface area, true specific gravity, bulk density, average particle size of carbon particles used in the obtained negative electrode for lithium ion secondary battery The diameter is shown in Table 1.
The circularity and the peak intensity ratio Ih002 / Ih110 were measured by preparing a sample electrode as follows. The sample electrode is composed of 98 parts by mass of carbon particles, 1 part by mass of a styrene butadiene resin (SBR 40% aqueous dispersion) (manufacturer: Nippon Zeon Co., Ltd., product name: BM-408B) as a binder, and carboxymethyl cellulose (as a thickener). (Manufacturer: Daiichi Kogyo Seiyaku Co., Ltd., Product Name: Serogen WS-C) A mixture of 1 part by mass is used as a solid content, and a water-dispersed paint is prepared by adding water so that the viscosity at 25 ° C. is 1623 mPa · s. The sample electrode was coated on a 10 μm copper foil to a thickness of about 70 μm and then dried at 120 ° C. for 1 hour.
First, after the sample electrode was embedded in an epoxy resin, the circularity was mirror-polished and observed with a scanning electron microscope (VE-7800 manufactured by Keyence Corporation).
The peak intensity ratio Ih002 / Ih110 was obtained by measuring the surface of the sample electrode by X-ray diffraction using CuKα rays as an X-ray source.
The viscosity of the water-dispersed paint was determined with a viscometer (DV-III (spindle SC4-18 # 14 temperature: 25 ° C., rotation speed: 100 rpm) manufactured by Brookfield).
The perimeter of the equivalent circle and the perimeter of the increase in the particle cross section were determined by analysis software (VE-7800 observation application) attached to the scanning electron microscope.

(2) Evaluation cell preparation method The sample electrode is 98% by mass of the carbon particles, and styrene butadiene resin (SBR 40% aqueous dispersion) as a binder (manufacturer: Nippon Zeon Co., Ltd., product name: BM-408B) 1% by mass. As a thickener, carboxymethylcellulose (manufacturer: Daiichi Kogyo Seiyaku Co., Ltd., product name: Serogen WS-C) 1% by mass was used as a solid content, and water-dispersed paint (viscosity 1623 mPa · s) with water added was prepared. This was applied to a thickness of about 70 μm on a 50 μm copper foil. The coated electrode was dried at 80 ° C. for 5 hours and 120 ° C. for 3 hours. After drying, pressed to two 1.5 g / cm ³ and 1.7 g / cm ³ is obtained, as two sample electrode of 1.5 g / cm ³ and 1.7 g / cm ³ (negative electrode), A 9.5 mmφ circular shape was punched for evaluation of the discharge capacity.
The evaluation battery was produced by injecting an electrolyte solution with a CR2016 coin cell facing the negative electrode and metallic lithium through a 40 μm polypropylene separator. The electrolytic solution is ethyl carbonate (EC) and methyl ethyl carbonate (MEC) mixed in a volume ratio of 3 to 7 by adding 0.5% by mass of vinylene carbonate to a mixed solvent and dissolving LiPF ₆ to a concentration of 1 mol / L. Was used (1M LiPF ₆ EC: MEC = 3: 7 VC 0.5 wt%).
(3) Evaluation conditions The discharge capacity evaluation was the discharge capacity of the first charge / discharge test. As the sample electrode, a sample electrode having an electrode density of 1.7 g / cm ³ obtained by the above-described evaluation cell manufacturing method was used. The sample electrode was evaluated under the conditions of 25 ° C., charged to 0 V at a constant current of 0.2 mA (0.28 mA / cm ² ), charged to a current value of 0.02 mA at a constant voltage of 0 V, and then 0 Discharging to a voltage value of 1.5 V at a constant current of 2 mA was repeated 50 cycles, and the discharge capacity retention rate at the 50th cycle was measured. The results are shown in Table 2.

(Example 2)
In Example 1, the same experiment was conducted except that the rubber container was subjected to isotropic pressure treatment with a hydrostatic pressure press at a pressure of 300 kgf / cm ² of the pressure medium. D (002), Lc (002), peak intensity ratio Ih002 / Ih110, circularity, pore volume, specific surface area, true specific gravity, bulk density, average particle size of carbon particles used in the obtained negative electrode for lithium ion secondary battery The diameter is shown in Table 1. The results of the 50th cycle discharge capacity retention rate are shown in Table 2.

(Comparative Example 1)
In Example 1, the same experiment was conducted except that the rubber container was not subjected to an isotropic pressure treatment with a hydrostatic press. D (002), Lc (002), peak intensity ratio Ih002 / Ih110, circularity, pore volume, specific surface area, true specific gravity, bulk density, average particle size of carbon particles used in the obtained negative electrode for lithium ion secondary battery The diameter is shown in Table 1. The results of the 50th cycle discharge capacity retention rate are shown in Table 2.

(Comparative Example 2)
In Example 1, instead of spheroidized natural graphite, Chinese scale graphite (average particle size 22 μm, circularity 0.44, specific surface area 4.5 m ² / g, true specific gravity 2.250, Lc> 1000 Å, d ( 002) 3.354 mm, bulk density 0.31 g / cm ³ )). D (002), Lc (002), peak intensity ratio Ih002 / Ih110, circularity, pore volume, specific surface area, true specific gravity, bulk density, average particle size of carbon particles used in the obtained negative electrode for lithium ion secondary battery The diameter is shown in Table 1. The results of the 50th cycle discharge capacity retention rate are shown in Table 2.

Claims (4)

The circularity of the particle cross section is 0.6 to 0.9, the interlayer distance d (002) of the graphite crystal determined by X-ray diffraction measurement is 3.38 mm or less, and the crystallite size Lc (002) in the C-axis direction is A carbon particle for a negative electrode of a lithium ion secondary battery having a capacity of 500 mm or more,
A carbon 002 plane (plane parallel to the graphite layer) and a carbon 110 plane (plane perpendicular to the graphite layer) measured by X-ray diffraction of a sample prepared by the following methods (a) to (b). A carbon particle for a negative electrode of a lithium ion secondary battery, wherein the peak intensity ratio Ih002 / Ih110 is 600 or less.
(A) Water in which water is added so that the viscosity at 25 ° C. of the mixture is 1500 to 2500 mPa · s with respect to a mixture of 98 parts by mass of the carbon particles, 1 part by mass of the styrene butadiene resin, and 1 part by mass of carboxymethyl cellulose. Make a dispersion paint.
(B) The water-dispersed paint is coated on a copper foil to a thickness of 70 μm and dried at 120 ° C. for 1 hour to obtain a sample. ^{2. The} carbon particles for a negative electrode of a lithium ion secondary battery according to claim 1, wherein the carbon material has a pore volume of 10 ² to 10 ⁶ pores of 0.4 to 2.0 ml / g per mass of the carbon particles. .   The negative electrode for lithium secondary batteries containing the carbon particle for lithium ion secondary battery negative electrodes of Claim 1 or 2.   A lithium ion secondary battery comprising the negative electrode according to claim 3 and a positive electrode containing a lithium compound.