Anode material for lithium ion secondary battery, method for producing anode material for lithium ion secondary battery, anode for lithium ion secondary battery, and lithium ion secondary battery

Abstract

This negative electrode material for lithium ion secondary batteries contains at least one selected from the group consisting of spherical natural graphite particles and composite particles that are aggregates of the spherical natural graphite particles. The spherical natural graphite particles and the composite particles have an average particle diameter (D50) of 12 µm or less, and satisfy at least one of (1) the linseed oil absorption is 45 mL / 100 g to 65 mL / 100 g and (2) the cumulative pore volume of the pore diameter range from 0.003 µm to 90 µm is 0.59 mL / g to 0.8 mL / g.

Description

[Technical Field]

[0001] The present disclosure relates to a negative electrode material for a lithium ion secondary battery, a method for producing a negative electrode material for a lithium ion secondary battery, a negative electrode for a lithium ion secondary battery, and a lithium ion secondary battery. [Background technology]

[0002] Taking advantage of their small size, light weight, and high energy density, lithium-ion secondary batteries have been widely used in electronic devices such as notebook PCs, mobile phones, smartphones, and tablet PCs. In recent years, environmental issues such as global warming caused by CO2 emissions have led to the widespread use of clean electric vehicles (EVs) that run solely on batteries and hybrid electric vehicles (HEVs) that combine gasoline engines with batteries. Recently, they have also been used for power storage, and their applications are expanding into a wide range of fields.

[0003] In recent years, lithium-ion secondary batteries with excellent input characteristics are increasingly required to improve energy utilization efficiency. Furthermore, lithium-ion secondary batteries are also required to have excellent life characteristics. However, there is generally a trade-off between input characteristics and life characteristics, and it is necessary to improve both characteristics simultaneously. In particular, in the automotive field, which is one of the important applications, there is a strong demand for improvements in both input characteristics and life characteristics.

[0004] For example, Patent Document 1 discloses spherical natural graphite particles in which flake, scale, or plate-like natural graphite particles are spheroidized by mechanical energy treatment to damage the graphite particle surface and improve the lithium ion input characteristics at the damaged areas. Patent Document 1 also proposes providing the spherical natural graphite particles with the properties of both graphite and amorphous carbon by adding amorphous carbon to the surfaces of the particles. [Prior art documents] [Patent documents]

[0005] [Patent Document 1] Japanese Patent Application Laid-Open No. 2000-340232 Summary of the Invention [Problem to be solved by the invention]

[0006] However, lithium-ion secondary batteries used in EVs, HEVs, etc. require high input characteristics to charge the power used for regenerative braking. Furthermore, automobiles are susceptible to the effects of outside temperatures, and lithium-ion secondary batteries are exposed to high temperatures, especially in the summer, so they require long life characteristics. High input characteristics and long life characteristics are also required in fields other than automobiles.

[0007] An object of one aspect of the present disclosure is to provide a negative electrode material for a lithium ion secondary battery, a method for manufacturing a negative electrode material for a lithium ion secondary battery, and a negative electrode for a lithium ion secondary battery, which are capable of manufacturing a lithium ion secondary battery having excellent input characteristics and life characteristics. Furthermore, an object of one aspect of the present disclosure is to provide a lithium ion secondary battery that is excellent in input characteristics and life characteristics. [Means for solving the problem]

[0008] Specific means for solving the above problems include the following aspects.

[0009] <1> The graphite particle contains at least one selected from the group consisting of spherical natural graphite particles and composite particles which are aggregates of the spherical natural graphite particles, The spherical natural graphite particles and the composite particles have an average particle diameter (D50) of 12 μm or less and a linseed oil absorption of 45 mL / 100 g to 65 mL / 100 g, in a negative electrode material for lithium ion secondary batteries. <2> The spherical natural graphite particles and the composite particles have an integrated pore volume of 0.59 mL / g to 0.80 mL / g in a pore diameter range of 0.003 μm to 90 μm. <1> The negative electrode material for a lithium ion secondary battery according to claim 1. <3> The graphite particle contains at least one selected from the group consisting of spherical natural graphite particles and composite particles which are aggregates of the spherical natural graphite particles, The spherical natural graphite particles and the composite particles have an average particle diameter (D50) of 12 μm or less, and an integrated pore volume of pore diameters in the range of 0.003 μm to 90 μm of 0.59 mL / g to 0.80 mL / g. <4> The spherical natural graphite particles and the composite particles have an average particle diameter (D50) of 12 μm or less, and an integrated pore volume of pores with a diameter of 2 nm or less of 1.15×10 -3 cm 3 / g~1.40×10 -3 cm 3 / g, <1> ~ <3> 10. The negative electrode material for a lithium ion secondary battery according to claim 9, wherein the negative electrode material is a lithium ion secondary battery material. <5> At least a portion of the surface of the spherical natural graphite particles and the composite particles is coated with a carbon material. <1> ~ <4> 10. The negative electrode material for a lithium ion secondary battery according to claim 9, wherein the negative electrode material is a lithium ion secondary battery material. <6> preparing a rubber mold containing graphite particles; a step of isotropically and dryly pressurizing the rubber mold from the outside; The method for producing a negative electrode material for a lithium ion secondary battery, comprising: <7> heat-treating the mixture containing the graphite particles and the carbon material precursor after the pressing step; <6> A method for producing the negative electrode material for a lithium ion secondary battery according to claim 1. <8> <1> ~ <5> The method for producing a negative electrode material for a lithium ion secondary battery according to any one of the above. <6> or <7> A method for producing the negative electrode material for a lithium ion secondary battery according to claim 1. <9> <1> ~ <5> 10. A negative electrode for a lithium ion secondary battery, comprising: a negative electrode material layer containing the negative electrode material for a lithium ion secondary battery according to any one of claims 1 to 9; and a current collector. <10> <9> A lithium ion secondary battery comprising the negative electrode for a lithium ion secondary battery according to claim 1, a positive electrode, and an electrolyte solution. [Effects of the Invention]

[0010] One aspect of the present disclosure can provide a negative electrode material for lithium ion secondary batteries, a method for producing a negative electrode material for lithium ion secondary batteries, and a negative electrode for lithium ion secondary batteries, which can produce lithium ion secondary batteries with excellent input characteristics and life characteristics. Furthermore, one embodiment of the present disclosure can provide a lithium ion secondary battery that is excellent in input characteristics and life characteristics. [Brief explanation of the drawings]

[0011]

Figure 1

[0012] Hereinafter, embodiments for carrying out the present invention will be described in detail. However, the present invention is not limited to the following embodiments. In the following embodiments, components (including element steps, etc.) are not essential unless otherwise specified. The same applies to numerical values ​​and their ranges, and do not limit the present invention. In the present disclosure, the term "process" includes not only a process that is independent of other processes, but also a process that cannot be clearly distinguished from other processes as long as the purpose of the process is achieved. In the present disclosure, numerical ranges indicated using "to" include the numerical values ​​before and after "to" as the minimum and maximum values, respectively. In the numerical ranges described in stages in this disclosure, the upper or lower limit value described in one numerical range may be replaced by the upper or lower limit value of another numerical range described in stages. Also, in the numerical ranges described in this disclosure, the upper or lower limit value of the numerical range may be replaced by the value shown in each test.

[0013] In the present disclosure, each component in the negative electrode material and the composition may contain multiple types of corresponding substances. When multiple types of substances corresponding to each component are present in the negative electrode material and the composition, the content and amount of each component refer to the total content and amount of the multiple types of substances present in the negative electrode material and the composition, unless otherwise specified. In the present disclosure, the negative electrode material and the composition may contain multiple types of particles corresponding to each component. When multiple types of particles corresponding to each component are present in the negative electrode material and the composition, the particle size of each component means the value for a mixture of the multiple types of particles present in the negative electrode material and the composition, unless otherwise specified. In the present disclosure, the term "layer" includes cases where the layer is formed over the entire area when the area in which the layer exists is observed, as well as cases where the layer is formed over only a portion of the area. In this disclosure, the term "lamination" refers to stacking layers, and two or more layers may be bonded together, or two or more layers may be detachable.

[0014] In the present disclosure, the spherical natural graphite particles refer to flake, scale, or plate-like natural graphite particles that have been spheroidized by mechanical energy treatment. The spherical natural graphite particles do not have to be perfectly spherical.

[0015] In the present disclosure, the average particle size (D50) is the particle size at 50% cumulative volume when a cumulative volume distribution curve is plotted from the smallest diameter side in a particle size distribution measured using a laser diffraction particle size analyzer. An example of a laser diffraction particle size analyzer is the SALD-3000J manufactured by Shimadzu Corporation.

[0016] In the present disclosure, the linseed oil absorption is measured in accordance with the method described in JIS K6217-4:2008 "Carbon black for rubber use - Fundamental properties - Part 4: Determination of oil absorption," except that linseed oil (manufactured by Kanto Chemical Co., Inc.) is used as the reagent liquid instead of dibutyl phthalate (DBP).

[0017] The specific method for measuring linseed oil absorption is as follows: linseed oil is titrated into a measurement sample using a constant-speed burette, and the change in viscosity characteristics is measured using a torque detector. The amount of reagent liquid added per unit mass of the measurement sample that corresponds to 70% of the maximum torque generated is defined as the linseed oil absorption (mL / 100g). An example of a measuring device is an absorption measuring device manufactured by Asahi Research Institute Co., Ltd.

[0018] In the present disclosure, the cumulative pore volume in the pore diameter range of 0.003 μm to 90 μm (hereinafter also referred to as "macropore volume") is a value measured by mercury intrusion porosimetry using a mercury porosimeter. An example of a mercury porosimeter is the Autopore IV 9500 manufactured by Shimadzu Corporation.

[0019] The specific method for measuring macropore volume is as follows. The measurement sample is sealed in a powder cell and pretreated by degassing for 5 minutes under vacuum (50 μmHg or less) at room temperature (25°C). After reducing the pressure to 2.00 psia (approximately 14 kPa) and introducing mercury, the pressure is increased stepwise to 60,000 psia (approximately 410 MPa) and then decreased to 0.10 psia (approximately 0.69 kPa). The number of steps during the pressure increase is 81 or more, and after each step, a 5-second equilibration period is allowed, after which the amount of mercury intrusion is measured. The pore distribution is determined from the obtained mercury intrusion curve using the Washburn equation, and the cumulative pore volume in the pore diameter range of 0.003 μm to 90 μm is calculated. The conditions for mercury porosimetry are as follows:

[0020] Mercury intrusion pressure: 2.00 psia (approx. 14 kPa) Pressure holding time at each measurement pressure: 5 seconds Contact angle between sample and mercury: 130° Surface tension of mercury: 485 dynes / cm (4.85 x 10 -3 N / cm) Density of mercury: 13.5335g / mL

[0021] In the present disclosure, the cumulative pore volume in the pore diameter range of 2 nm or less (hereinafter also referred to as "micropore volume") is a value measured by nitrogen gas adsorption. The micropore volume can be measured, for example, using a high-performance specific surface area / pore distribution analyzer (ASAP2020 Micromeritics).

[0022] The specific method for measuring micropore volume is as follows. The measurement sample is sealed in a powder cell and pretreated by placing it at 200°C under vacuum (7 μmHg or less) for 10 hours. Then, the adsorption isotherm (adsorbed gas: nitrogen) is measured at liquid nitrogen temperature with a relative pressure P / P0 of 0.00001 to 1.0 (P = equilibrium pressure, P0 = saturated vapor pressure). The resulting adsorption isotherm is used to determine the micropore distribution by SF analysis, and the cumulative pore volume in the pore diameter range of 2 nm or less is calculated.

[0023] <Anode material for lithium-ion secondary batteries> The negative electrode material for a lithium ion secondary battery in the first embodiment includes at least one selected from the group consisting of spherical natural graphite particles and composite particles that are aggregates of the spherical natural graphite particles, and the spherical natural graphite particles and the composite particles have an average particle size (D50) of 12 μm or less and a linseed oil absorption of 45 mL / 100 g to 65 mL / 100 g. The negative electrode material for lithium ion secondary batteries in the second embodiment includes at least one selected from the group consisting of spherical natural graphite particles and composite particles that are aggregates of the spherical natural graphite particles, and the spherical natural graphite particles and the composite particles have an average particle size (D50) of 12 μm or less and an integrated pore volume of 0.59 mL / g to 0.80 mL / g in the pore size range of 0.003 μm to 90 μm.

[0024] The spherical natural graphite particles and composite particles in the first embodiment may have an integrated pore volume of 0.59 mL / g to 0.80 mL / g in the pore diameter range of 0.003 μm to 90 μm. The spherical natural graphite particles and composite particles in the second embodiment may have a linseed oil absorption of 45 mL / 100 g to 65 mL / 100 g. The spherical natural graphite particles and composite particles in the first and second embodiments have an integrated pore volume of 1.15 × 10 in the range of pore diameters of 2 nm or less. -3 cm 3 / g~1.40×10 -3 cm 3 / g.

[0025] The total content of the spherical natural graphite particles and composite particles in the negative electrode material for lithium ion secondary batteries (hereinafter also simply referred to as "negative electrode material") is not particularly limited, and is, for example, preferably 50% by mass or more, more preferably 80% by mass or more, even more preferably 90% by mass or more, and particularly preferably 100% by mass. The negative electrode material may contain other carbon materials in addition to the spherical natural graphite particles and composite particles. The other carbon materials are not particularly limited, and examples thereof include non-spheroidized flake, scale, or plate-like natural graphite, artificial graphite, amorphous carbon, carbon black, fibrous carbon, and nanocarbon. The other carbon materials may be used alone or in combination of two or more. The negative electrode material may contain particles containing an element other than a carbon material that can occlude and release lithium ions. The element that can occlude and release lithium ions is not particularly limited, and examples thereof include Si, Sn, Ge, and In.

[0026] The average particle size (D50) of the spherical natural graphite particles and composite particles in the first and second embodiments is 12 μm or less. In order to prevent the diffusion distance of lithium from the surface to the interior of the negative electrode material from becoming longer and to further improve the input characteristics of the lithium ion secondary battery, the average particle size (D50) of the spherical natural graphite particles and composite particles is preferably 10 μm or less, more preferably 9.5 μm or less, even more preferably 9.0 μm or less, and particularly preferably 8.8 μm or less. The average particle size (D50) of the spherical natural graphite particles and composite particles is preferably 5 μm or more, and may be 7 μm or more, or 8.5 μm or more. When the average particle size (D50) of the spherical natural graphite particles and composite particles is 5 μm or more, the pressing pressure required to form the negative electrode material layer can be reduced, and as a result, lithium ion secondary batteries with better input characteristics tend to be manufactured.

[0027] The negative electrode material contains at least one selected from the group consisting of spherical natural graphite particles and composite particles. Therefore, the negative electrode material may contain only one of the spherical natural graphite particles and the composite particles, or may contain both the spherical natural graphite particles and the composite particles. In the present disclosure, the physical property values ​​of the spherical natural graphite particles and composite particles mean the physical property values ​​of the spherical natural graphite particles or the physical property values ​​of the composite particles when the negative electrode material contains only one of the spherical natural graphite particles and the composite particles, and mean the physical property values ​​of the spherical natural graphite particles and the composite particles as a whole when the negative electrode material contains both the spherical natural graphite particles and the composite particles. For example, "the average particle size (D50) of the spherical natural graphite particles and composite particles" means the average particle size (D50) of the spherical natural graphite particles when the negative electrode material contains only the spherical natural graphite particles of the spherical natural graphite particles and composite particles; it means the average particle size (D50) of the composite particles when the negative electrode material contains only the composite particles of the spherical natural graphite particles and composite particles; and it means the average particle size (D50) of the spherical natural graphite particles and composite particles as a whole when the negative electrode material contains both the spherical natural graphite particles and composite particles.

[0028] The composite particles are aggregates of spherical natural graphite particles. The composite particles may contain 2 to 6 spherical natural graphite particles, or may contain 3 to 5 spherical natural graphite particles. The method for producing an anode material containing the composite particles is not particularly limited and may be either a mechanical method or a chemical method, and is preferably a method for producing an anode material for lithium ion secondary batteries according to the present disclosure, which will be described later. In the composite particles produced by the method for producing an anode material for lithium ion secondary batteries according to the present disclosure, the spherical natural graphite particles are directly compounded together without the use of a binder or the like.

[0029] [First embodiment] The negative electrode material of the first embodiment includes at least one selected from the group consisting of spherical natural graphite particles and composite particles that are aggregates of spherical natural graphite particles, and the spherical natural graphite particles and composite particles have an average particle diameter (D50) of 12 μm or less and a linseed oil absorption of 45 mL / 100 g to 65 mL / 100 g.

[0030] When the negative electrode material for lithium ion secondary batteries satisfies the above requirements, it becomes possible to manufacture lithium ion secondary batteries that are excellent in input characteristics and life characteristics.

[0031] The input characteristics are improved when the spherical natural graphite particles and composite particles have an average particle size (D50) of 12 μm or less and a linseed oil absorption of 45 mL / 100 g or more. While the reasons for this are unclear, satisfying these requirements tends to increase the electrode density when the negative electrode material for lithium ion secondary batteries is applied to a current collector, thereby reducing the pressing pressure required to achieve the desired electrode density in the negative electrode for lithium ion secondary batteries. As a result, the planar orientation of the negative electrode material for lithium ion secondary batteries tends to be reduced, which facilitates the absorption of lithium ions during charge and discharge, improving the input characteristics. Furthermore, when the average particle size (D50) of the spherical natural graphite particles and composite particles is 12 μm or less, the deterioration of the life characteristics is suppressed by having a linseed oil absorption of 65 mL / 100 g or less.

[0032] Furthermore, since the linseed oil absorption is 45 mL / 100 g or more, the adhesion between the spherical natural graphite particles and composite particles, which are the negative electrode active material, and the current collector tends to be improved. Therefore, by using the negative electrode material for lithium ion secondary batteries of this embodiment, the adhesion between the spherical natural graphite particles and composite particles and the current collector is maintained even when the spherical natural graphite particles and composite particles repeatedly expand and contract during charge and discharge, and lithium ion secondary batteries with excellent cycle characteristics tend to be manufactured.

[0033] Furthermore, in the negative electrode material for lithium ion secondary batteries, the spherical natural graphite particles and composite particles have high adhesion to the current collector, which makes it possible to reduce the amount of binder required when producing the negative electrode, and this tends to enable the production of lithium ion secondary batteries with excellent energy density at low cost.

[0034] The spherical natural graphite particles and composite particles in the first embodiment have a linseed oil absorption of 45 mL / 100 g or more, preferably 46 mL / 100 g or more, and may be 48 mL / 100 g or more. Furthermore, the linseed oil absorption of the spherical natural graphite particles and composite particles in the first embodiment is 65 mL / 100 g or less, and from the viewpoint of further improving the input characteristics and cycle characteristics of the lithium ion secondary battery, it is preferably 55 mL / 100 g or less, more preferably 54 mL / 100 g or less, even more preferably 53 mL / 100 g or less, and particularly preferably 50 mL / 100 g or less.

[0035] The linseed oil absorption of spherical natural graphite particles and composite particles tends to increase when (1) the average particle size is reduced, (2) the tap density of the particles is lowered, or (3) the specific surface area of ​​the particles is increased. Regarding (1), this is thought to be because the number of particles present increases for the same mass, increasing the interparticle volume into which linseed oil is absorbed. Regarding (2), this is thought to be because the number of voids within the particles increases. Regarding (3), this is thought to be because the surface roughness of the particles increases. By balancing these factors, the linseed oil absorption of spherical natural graphite particles and composite particles can be adjusted to within the above range.

[0036] The macropore volume of the spherical natural graphite particles and composite particles in the first embodiment is not particularly limited, and may be 0.59 mL / g or more, 0.595 mL / g or more, or 0.60 mL / g or more. Furthermore, in order to further improve the life characteristics of the lithium ion secondary battery, the macropore volume of the spherical natural graphite particles and composite particles in the first embodiment may be 0.80 mL / g or less, 0.78 mL / g or less, 0.75 mL / g or less, 0.70 mL / g or less, or 0.65 mL / g or less.

[0037] The macropore volume of spherical natural graphite particles and composite particles tends to increase when (1) the average particle size is reduced, (2) the tap density of the particles is lowered, or (3) the specific surface area of ​​the particles is increased. Regarding (1), the reason is thought to be that the number of particles present for the same mass increases, increasing the interparticle volume into which mercury, which is used to measure the macropore volume, is absorbed. Regarding (2), the reason is thought to be that the number of voids within the particles increases. Regarding (3), the reason is thought to be that the surface roughness of the particles increases. By balancing these factors, the macropore volume of spherical natural graphite particles and composite particles can be adjusted to within the above range.

[0038] The micropore volume of the spherical natural graphite particles and composite particles in the first embodiment is not particularly limited. In order to further improve the input characteristics of the lithium ion secondary battery, it is preferred to use a volume of 1.15×10 -3 cm 3 above may be 1.19 x 10 -3 cm 3 It may be 1.20 x 10 or more. -3 cm 3 It may be 1.25 x 10 or more. -3 cm 3 It may be more than that. In order to further improve the life characteristics of the lithium ion secondary battery, the micropore volume of the spherical natural graphite particles and composite particles in the first embodiment is 1.40 × 10 -3 cm 3 It may be less than 1.35 x 10 -3 cm 3 It may be less than 1.30 x 10 -3 cm 3 It may be the following:

[0039] The micropore volume of spherical natural graphite particles and composite particles tends to increase when (1) the specific surface area of ​​the particles is increased, or (2) when at least a portion of the surface of the spherical natural graphite particles and composite particles is coated with a carbon material, the firing temperature during coating is lowered. The reason for (1) is thought to be increased irregularities on the particle surface. The reason for (2) is thought to be a decrease in density or sintering due to insufficient decomposition of the coating material. By achieving a balance between these factors, the micropore volume of the spherical natural graphite particles and composite particles can be adjusted to within the above range.

[0040] The spherical natural graphite particles and composite particles have a specific surface area (hereinafter also referred to as "N2 specific surface area") determined by nitrogen adsorption measurement at 77K of 2 m 2 / g~8m 2 / g, and 2.5m 2 / g~7m 2 / g, more preferably 3m 2 / g~6m 2 / g is even more preferable. If the N2 specific surface area is within the above range, a good balance between the input characteristics and the initial charge / discharge efficiency of the lithium ion secondary battery tends to be obtained. The N2 specific surface area is determined by the BET method from an adsorption isotherm obtained by nitrogen adsorption measurement at 77K.

[0041] The spherical natural graphite particles and composite particles have an average interplanar spacing d determined by X-ray diffraction. 002 The average interplanar spacing d is preferably 0.334 nm to 0.338 nm. 002 When the thickness is 0.338 nm or less, the initial charge / discharge efficiency and energy density of the lithium ion secondary battery tend to be excellent.

[0042] Average interplanar spacing d of spherical natural graphite particles and composite particles 002 The value of d tends to decrease, for example, by increasing the temperature of the heat treatment when preparing the negative electrode material. Therefore, by adjusting the temperature of the heat treatment when preparing the negative electrode material, the average interplanar spacing d of the carbon material can be reduced. 002 can be controlled.

[0043] In the present disclosure, the average interplanar spacing d 002 The diffraction peak corresponding to the carbon 002 plane, which appears at a diffraction angle 2θ of approximately 24° to 27°, is calculated using the Bragg equation from the diffraction profile obtained by irradiating a sample with X-rays (CuKα rays) and measuring the diffraction rays with a goniometer. Specifically, the measurement sample is filled into the recessed portion of a quartz sample holder and set on the measurement stage, and measurement is performed using a wide-angle X-ray diffractometer (manufactured by Rigaku Corporation) under the following measurement conditions. Radiation source: CuKα radiation (wavelength = 0.15418nm) Output: 40kV, 20mA Sampling width: 0.010° Scanning range: 10°~35° Scan speed: 0.5° / min

[0044] The R value of the spherical natural graphite particles and composite particles measured by Raman spectroscopy is preferably 0.1 to 1.0, more preferably 0.2 to 0.8, and even more preferably 0.3 to 0.7. When the R value is 0.1 or more, there are sufficient graphite lattice defects used for absorbing and releasing lithium ions, and the deterioration of input characteristics tends to be suppressed. When the R value is 1.0 or less, the decomposition reaction of the electrolyte is sufficiently suppressed, and the initial charge and discharge The decrease in efficiency tends to be suppressed.

[0045] The R value was measured at 1580 cm in the Raman spectrum. -1 The intensity Ig of the maximum peak near 1360 cm -1 It is defined as the intensity ratio (Id / Ig) of the intensity Id of the maximum peak in the vicinity.

[0046] In the present disclosure, Raman spectroscopy is performed using a laser Raman spectrophotometer by irradiating an argon laser beam onto a sample plate on which a measurement sample is placed so as to be flat. For example, an NRS-1000 manufactured by JASCO Corporation can be used as the laser Raman spectrophotometer. The measurement conditions are as follows: Argon laser light wavelength: 532 nm Wavenumber resolution: 2.56cm -1 Measurement range: 1180cm -1 ~1730cm -1 Peak Research: Background Removal

[0047] At least a portion of the surface of the spherical natural graphite particles and composite particles may be coated with a carbon material. The presence of the carbon material on the surface of the spherical natural graphite particles or composite particles can be confirmed by observation with a transmission electron microscope.

[0048] "At least a portion of the surface of the spherical natural graphite particles and composite particles is coated with a carbon material" means that, when the negative electrode material contains only one of spherical natural graphite particles and composite particles, at least a portion of the surface of the spherical natural graphite particles is coated with a carbon material, or at least a portion of the surface of the composite particles is coated with a carbon material. It also means that at least some of the spherical natural graphite particles and composite particles contained in the negative electrode material are coated with a carbon material. It is preferable that more than half of the spherical natural graphite particles and composite particles contained in the negative electrode material have a portion coated with a carbon material, more preferably 90% or more of the particles have a portion coated with a carbon material, and even more preferably 95% or more of the particles have a portion coated with a carbon material.

[0049] In order to improve the input characteristics of the lithium-ion secondary battery, the carbon material used as the coating material is preferably one having lower crystallinity than the spherical natural graphite particles and composite particles, and is more preferably amorphous carbon. Specifically, the carbon material is preferably at least one selected from the group consisting of carbonaceous substances and carbonaceous particles obtained from organic compounds that can be converted into carbonaceous materials by heat treatment (hereinafter also referred to as "carbonaceous material precursors"). The carbonaceous material may be one type alone or two or more types.

[0050] The precursor of the carbon material is not particularly limited, and examples thereof include pitch, organic polymer compounds, etc. Examples of pitch include ethylene heavy-end pitch, crude oil pitch, coal tar pitch, asphalt cracking pitch, pitch produced by thermal decomposition of polyvinyl chloride, etc., and pitch produced by polymerizing naphthalene, etc. in the presence of a super strong acid. Examples of organic polymer compounds include thermoplastic resins such as polyvinyl chloride, polyvinyl alcohol, polyvinyl acetate, and polyvinyl butyral, and natural substances such as starch and cellulose.

[0051] The carbonaceous particles used as the carbon material are not particularly limited, and examples thereof include particles of acetylene black, oil furnace black, ketjen black, channel black, thermal black, soil graphite, and the like.

[0052] The method for coating with a carbon material includes a step of heat-treating a mixture containing spherical natural graphite particles or composite particles as cores and a precursor of the carbon material. From the viewpoint of improving the input characteristics of the lithium ion secondary battery, the temperature at which the mixture is heat-treated is preferably 800° C. to 1500° C., more preferably 900° C. to 1300° C., and even more preferably 1050° C. to 1250° C. The temperature at which the mixture is heat-treated may be constant from the start to the end of the heat treatment, or may vary.

[0053] [Second embodiment] The negative electrode material in the second embodiment includes at least one selected from the group consisting of spherical natural graphite particles and composite particles which are aggregates of spherical natural graphite particles, and the spherical natural graphite particles and composite particles have an average particle diameter (D50) of 12 μm or less and a macropore volume of 0.59 mL / g to 0.80 mL / g.

[0054] When the negative electrode material for lithium ion secondary batteries satisfies the above requirements, it becomes possible to manufacture lithium ion secondary batteries that are excellent in input characteristics and life characteristics.

[0055] When the average particle diameter (D50) of the spherical natural graphite particles and composite particles is 12 μm or less, the number of sites available for lithium ion absorption is increased and input characteristics are improved by having a macropore volume of 0.59 mL / g or more. When the average particle diameter (D50) of the spherical natural graphite particles and composite particles is 12 μm or less, the macropore volume of the spherical natural graphite particles and composite particles is 0.80 mL / 100 g or less, life characteristics are maintained.

[0056] The spherical natural graphite particles and composite particles in the second embodiment have a macropore volume of 0.59 mL / g or more, and 0.595 mL / g or more. g to It is preferable that the viscosity is 0.60 mL / g or more, and more preferable that the viscosity is 0.60 mL / g or more. Furthermore, the macropore volume of the spherical natural graphite particles and composite particles in the second embodiment is 0.80 mL / g or less, preferably 0.78 mL / g or less, more preferably 0.75 mL / g or less, and may be 0.70 mL / g or less, or may be 0.65 mL / g or less.

[0057] The linseed oil absorption of the spherical natural graphite particles and composite particles in the second embodiment is not particularly limited, and may be 45 mL / 100 g or more, 46 mL / 100 g or more, or 48 mL / 100 g or more. Furthermore, in order to further improve the input characteristics and cycle characteristics of the lithium ion secondary battery, the linseed oil absorption of the spherical natural graphite particles and composite particles in the second embodiment may be 65 mL / 100 g or less, 63 mL / 100 g or less, 60 mL / 100 g or less, 55 mL / 100 g or less, 54 mL / 100 g or less, 53 mL / 100 g or less, or 50 mL / 100 g or less.

[0058] The micropore volume of the spherical natural graphite particles and composite particles in the second embodiment is not particularly limited. In order to further improve the input characteristics of the lithium ion secondary battery, it is preferred to use a volume of 1.15×10 -3 cm 3 / g abovemay be 1.19 x 10 -3 cm 3 / g It may be 1.20 x 10 or more. -3 cm 3 / g or more, and may be 1.25 × 10 -3 cm 3 / g or more. In order to further improve the life characteristics of the lithium ion secondary battery, the micropore volume of the spherical natural graphite particles and composite particles in the second embodiment is 1.40 × 10 -3 cm 3 / g or less, and may be 1.35 × 10 -3 cm 3 / g or less, 1.30 × 10 -3 cm 3 / g or less.

[0059] The average interplanar spacing d of the spherical natural graphite particles and composite particles in the second embodiment 002 Other physical properties, coating, and other items are the same as in the first embodiment.

[0060] <Method of manufacturing negative electrode material for lithium-ion secondary batteries> The method for producing a negative electrode material for a lithium-ion secondary battery according to the present disclosure includes the steps of preparing a rubber mold containing graphite particles and isotropically pressurizing the rubber mold from the outside in a dry manner. By performing the pressurization in a dry manner without using a medium such as water as an ambient environment, a negative electrode material for a lithium-ion secondary battery containing composite particles can be easily produced, thereby saving labor.

[0061] The rubber mold is not particularly limited as long as it can withstand external pressure. The pressure is transmitted isotropically to the graphite particles filled inside the rubber mold through the rubber mold. Isotropic pressure tends to produce a negative electrode material for lithium-ion secondary batteries containing composite particles with little anisotropy.

[0062] Furthermore, isotropic pressing of graphite particles tends to cause the graphite particles, which have a relatively small particle size, to aggregate, which suppresses the dilatancy of the slurry-like negative electrode material composition used to form the negative electrode material layer and improves workability during application.

[0063] Figure 1 shows an electron microscope photograph of a cross section of a negative electrode material obtained by the manufacturing method of the present disclosure. The negative electrode material in Figure 1 is in the form of composite particles formed by agglomeration of spherical natural graphite particles. The negative electrode material obtained by the manufacturing method of the present disclosure may contain both non-agglomerated spherical natural graphite particles and agglomerated composite particles.

[0064] Dry pressing methods include a circumferential / axial pressing method and a peripheral pressing method depending on the direction in which pressure is applied, and either method may be used. The pressure is preferably adjusted appropriately depending on the type of graphite particles, the size of the rubber mold, etc., and may be, for example, 10 MPa to 500 MPa.

[0065] The graphite particles used in the method for producing a negative electrode material for a lithium ion secondary battery according to the present disclosure may be any of artificial graphite particles, natural graphite particles, graphitized mesophase carbon particles, graphitized carbon fibers, etc. The natural graphite particles may be flake-like, scale-like, or plate-like natural graphite particles, or may be spherical natural graphite particles obtained by spheroidizing these natural graphite particles.

[0066] The method for producing a negative electrode material for a lithium ion secondary battery according to the present disclosure may be used as the method for producing a negative electrode material for a lithium ion secondary battery according to the first or second embodiment. In this case, spherical natural graphite particles obtained by spheronizing natural graphite particles are used as the graphite particles.

[0067] <Anode for lithium-ion secondary batteries> The negative electrode for a lithium ion secondary battery of the present disclosure includes a negative electrode layer containing the above-described negative electrode material for a lithium ion secondary battery of the present disclosure, and a current collector. The negative electrode for a lithium ion secondary battery may include other components as necessary in addition to the negative electrode layer containing the negative electrode material of the present disclosure and the current collector.

[0068] The negative electrode for a lithium ion secondary battery can be produced, for example, by kneading the negative electrode material and binder with a solvent to prepare a slurry-like negative electrode material composition, which is then applied to a current collector to form a negative electrode material layer, or by forming the negative electrode material composition into a shape such as a sheet or pellet and integrating it with a current collector. Kneading can be performed using a dispersing device such as a stirrer, ball mill, super sand mill, or pressure kneader.

[0069] The binder used in preparing the negative electrode material composition is not particularly limited. Examples of binders include styrene-butadiene copolymers, polymers of ethylenically unsaturated carboxylic acid esters such as methyl acrylate, methyl methacrylate, ethyl acrylate, ethyl methacrylate, butyl acrylate, butyl methacrylate, acrylonitrile, methacrylonitrile, hydroxyethyl acrylate, and hydroxyethyl methacrylate, polymers of ethylenically unsaturated carboxylic acids such as acrylic acid, methacrylic acid, itaconic acid, fumaric acid, and maleic acid, and polymeric compounds with high ionic conductivity such as polyvinylidene fluoride, polyethylene oxide, polyepichlorohydrin, polyphosphazene, and polyacrylonitrile. When the negative electrode material composition contains a binder, the amount thereof is not particularly limited. The content of the binder may be, for example, 0.5 to 20 parts by mass per 100 parts by mass of the total of the negative electrode material and binder.

[0070] The solvent is not particularly limited as long as it can dissolve or disperse the binder. Specific examples include organic solvents such as N-methyl-2-pyrrolidone, N,N-dimethylacetamide, N,N-dimethylformamide, and γ-butyrolactone. The amount of solvent used is not particularly limited as long as it can turn the negative electrode material composition into a desired state such as a paste. The amount of solvent used is preferably, for example, 60 parts by mass or more but less than 150 parts by mass per 100 parts by mass of the negative electrode material.

[0071] The negative electrode material composition may contain a thickener. Examples of thickeners include carboxymethyl cellulose or a salt thereof, methyl cellulose, hydroxymethyl cellulose, hydroxyethyl cellulose, ethyl cellulose, polyvinyl alcohol, polyacrylic acid or a salt thereof, alginic acid or a salt thereof, oxidized starch, phosphated starch, and casein. When the negative electrode material composition contains a thickener, the amount thereof is not particularly limited. The content of the thickener may be, for example, 0.1 to 5 parts by mass per 100 parts by mass of the negative electrode material.

[0072] The negative electrode material composition may contain a conductive auxiliary material. Examples of the conductive auxiliary material include carbon materials such as artificial graphite and carbon black (acetylene black, thermal black, furnace black, etc.), conductive oxides, and conductive nitrides. When the negative electrode material composition contains a conductive auxiliary material, the amount thereof is not particularly limited. The content of the conductive auxiliary material may be, for example, 0.5 to 15 parts by mass per 100 parts by mass of the negative electrode material.

[0073] The material of the current collector is not particularly limited and can be selected from aluminum, copper, nickel, titanium, stainless steel, etc. The state of the current collector is not particularly limited and can be selected from foil, perforated foil, mesh, etc. Porous materials such as porous metal (foamed metal) and carbon paper can also be used as the current collector.

[0074] When the negative electrode material composition is applied to a current collector to form a negative electrode material layer, the method is not particularly limited, and known methods such as metal mask printing, electrostatic coating, dip coating, spray coating, roll coating, doctor blade coating, comma coating, gravure coating, and screen printing can be used. After the negative electrode material composition is applied to the current collector, the solvent contained in the negative electrode material composition is removed by drying. Drying can be performed using, for example, a hot air dryer, an infrared dryer, or a combination of these devices. A rolling treatment may be performed as necessary. The rolling treatment can be performed using a plate press, a calendar roll, or the like.

[0075] When the negative electrode material composition formed into a shape such as a sheet or pellet is integrated with a current collector to form a negative electrode material layer, the integration method is not particularly limited. For example, it can be performed using a roll, a flat press, or a combination of these means. The pressure during integration is preferably, for example, 1 MPa to 200 MPa.

[0076] <Lithium-ion secondary battery> The lithium ion secondary battery of the present disclosure includes the above-described negative electrode for lithium ion secondary batteries of the present disclosure (hereinafter also simply referred to as "negative electrode"), a positive electrode, and an electrolyte solution.

[0077] The positive electrode can be obtained by forming a positive electrode material layer on a current collector in the same manner as the negative electrode described above. The current collector can be made of a metal or alloy such as aluminum, titanium, or stainless steel, and can be in the form of a foil, perforated foil, mesh, or the like.

[0078] The positive electrode material used to form the positive electrode layer is not particularly limited. For example, metal compounds (metal oxides, metal sulfides, etc.) that can dope or intercalate lithium ions and conductive polymer materials can be mentioned. More specifically, lithium cobalt oxide (LiCoO2), lithium nickel oxide (LiNiO2), lithium manganese oxide (LiMnO2), and their double oxides (LiCo x Ni y Mn z O2, x+y+z=1), and a double oxide containing an additional element M' (LiCo a Ni b Mn c M' d O2, a+b+c+d=1, M': Al, Mg, Ti, Zr or Ge), spinel-type lithium manganese oxide (LiMn2O4), lithium vanadium compounds, V2O5, V6O 13Examples of the positive electrode material include lithium-containing compounds such as VO2, MnO2, TiO2, MoV2O8, TiS2, V2S5, VS2, MoS2, MoS3, Cr3O8, Cr2O5, and olivine-type LiMPO4 (M: Co, Ni, Mn, Fe), conductive polymers such as polyacetylene, polyaniline, polypyrrole, polythiophene, and polyacene, and porous carbon. The positive electrode material may be one type alone or two or more types.

[0079] The electrolytic solution is not particularly limited, and for example, a solution in which a lithium salt as an electrolyte is dissolved in a non-aqueous solvent (a so-called organic electrolytic solution) can be used. Examples of lithium salts include LiClO4, LiPF6, LiAsF6, LiBF4, LiSO3CF3, etc. The lithium salt may be one type alone or two or more types. Examples of non-aqueous solvents include ethylene carbonate, fluoroethylene carbonate, chloroethylene carbonate, propylene carbonate, butylene carbonate, vinylene carbonate, cyclopentanone, cyclohexylbenzene, sulfolane, propane sultone, 3-methyl sulfolane, 2,4-dimethyl sulfolane, 3-methyl-1,3-oxazolidin-2-one, γ-butyrolactone, dimethyl carbonate, diethyl carbonate, ethyl methyl carbonate, methyl propyl carbonate, butyl methyl carbonate, ethyl propyl carbonate, butyl ethyl carbonate, dipropyl carbonate, 1,2-dimethoxyethane, tetrahydrofuran, 2-methyltetrahydrofuran, 1,3-dioxolane, methyl acetate, ethyl acetate, trimethyl phosphate, triethyl phosphate, etc. The non-aqueous solvents may be used alone or in combination of two or more.

[0080] The state of the positive electrode and the negative electrode in the lithium ion secondary battery is not particularly limited. For example, the positive electrode, the negative electrode, and a separator disposed between the positive electrode and the negative electrode as needed may be spirally wound or may be stacked in the form of flat plates.

[0081] The separator is not particularly limited, and may be, for example, a resin nonwoven fabric, cloth, microporous film, or a combination thereof. Resins include those primarily composed of polyolefins such as polyethylene and polypropylene. If the structure of the lithium-ion secondary battery does not allow the positive electrode and negative electrode to come into direct contact with each other, a separator may not be used.

[0082] The shape of the lithium ion secondary battery is not particularly limited, and examples thereof include laminated type batteries, paper type batteries, button type batteries, coin type batteries, stacked type batteries, cylindrical type batteries, and prismatic type batteries.

[0083] The lithium ion secondary battery of the present disclosure has excellent output characteristics and is therefore suitable as a large-capacity lithium ion secondary battery for use in electric vehicles, power tools, power storage devices, etc. In particular, it is suitable as a lithium ion secondary battery for use in electric vehicles (EVs), hybrid electric vehicles (HEVs), plug-in hybrid electric vehicles (PHEVs), etc., which require large current charging and discharging to improve acceleration performance and brake regeneration performance. [Example]

[0084] The present invention will be described in more detail below with reference to the following examples, but the present invention is not limited to these examples.

[0085] (Production of negative electrode material) Example 1 Spherical natural graphite particles with an average particle size (D50) of 8 μm were subjected to isotropic dry pressure treatment. The spherical natural graphite particles were packed into a rubber mold and pressure was applied from the periphery at 100 MPa. The average particle size (D50) of the spherical natural graphite particles after pressure treatment was 10.7 μm. Some of the spherical natural graphite particles after pressure treatment had aggregated to form composite particles.

[0086] 100 parts by mass of the pressure-treated spherical natural graphite particles and 3.2 parts by mass of coal tar pitch (softening point 90°C, residual carbon rate (carbonization rate) 50% by mass) were mixed. The mixture was then heated to 1050°C at a heating rate of 250°C / hour under a nitrogen flow and held at 1050°C (the calcination temperature) for 1 hour to obtain carbon layer-coated graphite particles (carbon material). The obtained carbon layer-coated carbon particles were crushed using a cutter mill and then sieved through a 350-mesh sieve. The undersized portion was used as the negative electrode material.

[0087] The average particle size (D50), micropore volume, linseed oil absorption, macropore volume, and specific surface area of ​​the obtained negative electrode material were measured by the following methods. Each physical property value is shown in Table 1.

[0088] [Measurement of average particle size (D50)] A solution prepared by dispersing a negative electrode material sample in purified water with 0.2% by mass of a surfactant (trade name: Liponol T / 15, manufactured by Lion Corporation) was placed in the sample water tank of a laser diffraction particle size analyzer (SALD-3000J, manufactured by Shimadzu Corporation). The solution was then circulated with a pump while applying ultrasound (pump flow rate was set to 65% of the maximum), and the amount of water was adjusted so that the absorbance was between 0.10 and 0.15. The particle size at 50% cumulative volume (D50) of the resulting particle size distribution was taken as the average particle size. The results are shown in Table 1.

[0089] [Micropore volume] The micropore volume of the negative electrode material was measured by the method described above, and the results are shown in Table 1.

[0090] [Linseed oil absorption amount (oil absorption amount)] The linseed oil absorption of the negative electrode material was measured using the method described above. The results are shown in Table 1.

[0091] [Macropore volume] The macropore volume of the negative electrode material was measured by the method described above, and the results are shown in Table 1.

[0092] [Measurement of specific surface area] The nitrogen adsorption of the negative electrode material samples was measured at liquid nitrogen temperature (77 K) using a high-speed specific surface area / pore distribution analyzer (FlowSorb III, manufactured by Shimadzu Corporation) by the single-point method, and the specific surface area was calculated by the BET method. The results are shown in Table 1.

[0093] Example 2 An anode material was produced in the same manner as in Example 1, except that the spherical natural graphite particles used as the raw material were changed to those with an average particle diameter (D50) of 9.8 μm and the dry pressure treatment was not performed. The various physical properties of the produced anode material were measured in the same manner as in Example 1. The various physical properties are shown in Table 1.

[0094] Example 3 An anode material was produced in the same manner as in Example 1, except that the spherical natural graphite particles used as the raw material were changed to those with an average particle diameter (D50) of 8.7 μm and the dry pressure treatment was not performed. The various physical properties of the produced anode material were measured in the same manner as in Example 1. The various physical properties are shown in Table 1.

[0095] Example 4 An anode material was produced in the same manner as in Example 1, except that the spherical natural graphite particles used as the raw material were changed to those with an average particle size (D50) of 8.8 μm and a reduced linseed oil absorption, and the dry pressure treatment was not performed. The various physical properties of the produced anode material were measured in the same manner as in Example 1. The various physical properties are shown in Table 1.

[0096] Example 5 A negative electrode material was produced in the same manner as in Example 1, except that the spherical natural graphite particles used as the raw material were changed to those with an average particle size (D50) of 8.8 μm and an even lower linseed oil absorption, and the dry pressure treatment was not performed. The various physical properties of the produced negative electrode material were measured in the same manner as in Example 1. The various physical properties are shown in Table 1.

[0097] Example 6 An anode material was produced in the same manner as in Example 1, except that the spherical natural graphite particles used as the raw material were changed to those with an average particle size (D50) of 7.9 μm and the dry pressure treatment was not performed. The various physical properties of the produced anode material were measured in the same manner as in Example 1. The various physical properties are shown in Table 1.

[0098] Comparative Example 1 An anode material was produced in the same manner as in Example 1, except that the spherical natural graphite particles used as the raw material were changed to those with an average particle size (D50) of 10.4 μm and the dry pressure treatment was not performed. The various physical properties of the produced anode material were measured in the same manner as in Example 1. The various physical properties are shown in Table 1.

[0099] (Fabrication of lithium-ion secondary batteries for input characteristic evaluation) Using the negative electrode materials prepared in each example, lithium ion secondary batteries for evaluating input characteristics were prepared according to the following procedure. First, an aqueous solution (CMC concentration: 2% by mass) of CMC (carboxymethyl cellulose, manufactured by Daicel FineChem Co., Ltd., product number 2200) as a thickener was added to 98 parts by mass of the negative electrode material so that the solid content of CMC was 1 part by mass, and the mixture was kneaded for 10 minutes. Next, purified water was added so that the total solid content of the negative electrode material and CMC was 40% to 50% by mass, and the mixture was kneaded for 10 minutes. Next, an aqueous dispersion (SBR concentration: 40% by mass) of styrene-butadiene copolymer rubber SBR (BM400-B, Zeon Corporation) was added as a binder so that the solid content of SBR was 1 part by mass, and the mixture was mixed for 10 minutes to prepare a paste-like negative electrode material composition. Next, the negative electrode material composition was applied to an 11 μm-thick electrolytic copper foil at a coating amount per unit area of ​​5.9 mg / cm. 2 The negative electrode material layer was formed by applying the coating with a comma coater with the clearance adjusted so that the coating density was 1.2 g / cm. 3 The electrode density was adjusted to 16 mm. The electrolytic copper foil on which the negative electrode material layer was formed was punched into a disk shape with a diameter of 16 mm to prepare a sample electrode (negative electrode).

[0100] The prepared sample electrode (negative electrode), separator, and counter electrode (positive electrode) were placed in a coin-type battery container in this order, and an electrolyte solution was poured into it to prepare a coin-type lithium-ion secondary battery. The electrolyte solution used was a mixed solvent of ethylene carbonate (EC) and ethyl methyl carbonate (EMC) (volume ratio of EC to EMC was 3:7), to which 0.5 mass% of vinylene carbonate (VC) was added relative to the total amount of the mixed solution, and LiPF6 was dissolved to a concentration of 1 mol / L. The counter electrode (positive electrode) was LiNi 0.5 Mn 0.3 Co 0.2 O2 (NMC532) was used. A 20 μm thick polyethylene microporous membrane was used as the separator. Using the fabricated lithium ion secondary battery, the input characteristics were evaluated by the following method.

[0101] (Evaluation of input characteristics) The direct current resistance (DCR) of the fabricated lithium ion secondary battery was measured to determine the input characteristics of the battery. Specifically, the characteristics are as follows. The lithium-ion secondary battery was placed in a thermostatic chamber set at 25°C and charged at a constant current / constant voltage (CC / CV) of 0.2 C to 4.2 V with a cut-off current of 0.02 C, followed by three cycles of constant current (CC) discharge at 0.2 C to 2.5 V. Next, the battery was charged at a constant current of 0.2 C to an SOC of 60%. The lithium-ion secondary battery was placed in a thermostatic chamber set at -10°C and charged at constant currents of 0.2C, 0.5C, and 1C for 10 seconds each, and the voltage drop (ΔV) at each constant current was measured, followed by the measurement of direct current resistance (DCR) using the formula below. The results are shown in Table 1. The lower the direct current resistance (DCR), the better the input characteristics. DCR [Ω] = {(0.5C voltage drop △V - 0.2C voltage drop △V) + (1C voltage drop △V - 0.5C voltage drop △V)} / 0.8

[0102] Table 1 shows the direct current resistance (DCR) of the lithium ion secondary battery using the negative electrode material of each example, when the direct current resistance (DCR) of the lithium ion secondary battery using the negative electrode material of Comparative Example 1 is set to 100. A lower direct current resistance (DCR) value indicates better life characteristics.

[0103] (Evaluation of storage characteristics) The charge and discharge characteristics of the fabricated lithium ion secondary battery were measured, and the storage characteristics of the battery were determined as follows. The lithium-ion secondary battery was placed in a thermostatic chamber set at 25°C and charged / discharged by constant current / constant voltage (CC / CV) charging at 0.2 C, 4.2 V, and a cut-off current of 0.02 C, followed by three cycles of constant current (CC) discharge at 0.2 C to 2.5 V. Next, constant current charging was performed at a current value of 0.2 C to 100% SOC. The lithium-ion secondary battery was placed in a thermostatic chamber set at 60°C and left for 7 days, after which it was placed in another thermostatic chamber set at 25°C and discharged at a constant current (CC) of 0.2 C to 2.5 V. The storage characteristics were measured using the following formula. The results are shown in Table 1. The higher the storage characteristic value, the less likely it was to deteriorate and the better the storage characteristics. Storage characteristics = (discharge capacity after 7 days storage at 60°C with SOC 100%) / (discharge capacity at 3rd cycle)

[0104] Table 1 shows the storage characteristics of the lithium ion secondary batteries using the negative electrode material of each example, with the storage characteristics of the lithium ion secondary battery using the negative electrode material of Comparative Example 1 set at 100. A higher value for storage characteristics indicates less deterioration and more excellent storage characteristics.

[0105] (Hand press pressure evaluation) In the production of the lithium ion secondary battery, the electrode density of the negative electrode was set to 1.2 g / cm 3Regarding the hand press pressure required to achieve the same electrode density, the hand press pressure for the lithium ion secondary battery using the negative electrode material of each Example is shown in Table 1, where the hand press pressure for the lithium ion secondary battery using the negative electrode material of Comparative Example 1 is set to 100. This indicates that the higher the value of the hand press pressure, the greater the force required to achieve the same electrode density, and the greater the load on the electrode.

[0106] [Table 1]

Claims

1. The graphite particle contains at least one selected from the group consisting of spherical natural graphite particles and composite particles which are aggregates of the spherical natural graphite particles, the spherical natural graphite particles and the composite particles have an average particle size (D50) of 12 μm or less and a linseed oil absorption of 45 mL / 100 g to 65 mL / 100 g; The spherical natural graphite particles and the composite particles have an integrated pore volume of 0.59 mL / g to 0.80 mL / g in a pore diameter range of 0.003 μm to 90 μm.

2. The graphite particle contains at least one selected from the group consisting of spherical natural graphite particles and composite particles which are aggregates of the spherical natural graphite particles, The spherical natural graphite particles and the composite particles have an average particle diameter (D50) of 12 μm or less, and an integrated pore volume in a pore diameter range of 0.003 μm to 90 μm of 0.59 mL / g to 0.80 mL / g.

3. The spherical natural graphite particles and the composite particles have an average particle diameter (D50) of 12 μm or less, and an integrated pore volume in the range of pore diameters of 2 nm or less of 1.15×10 －３ cm ３ / g to 1.40 x 10 －３ cm ３ The negative electrode material for a lithium ion secondary battery according to claim 1 or claim 2, wherein the SiO2 content is 1 / g.

4. The negative electrode material for a lithium ion secondary battery according to any one of claims 1 to 3, wherein at least a portion of the surface of the spherical natural graphite particles and the composite particles is coated with a carbon material.

5. A negative electrode for a lithium ion secondary battery, comprising: a negative electrode material layer containing the negative electrode material for a lithium ion secondary battery according to any one of claims 1 to 4; and a current collector.

6. A lithium ion secondary battery comprising the negative electrode for a lithium ion secondary battery according to claim 5, a positive electrode, and an electrolyte solution.

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