JP2014132562A - Negative electrode material, negative electrode active material, negative electrode for lithium ion battery, and lithium ion battery - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a negative electrode material for a lithium ion battery which has good storage characteristics while having average layer surface space of (002) plane being larger than that of a graphite material.SOLUTION: The negative electrode material is a carbonaceous negative electrode material for a lithium ion battery, and its average layer surface space dof (002) plane determined by X-ray diffraction by using CuKα ray as a radiation source is 0.340 nm or more. In the negative electrode material, a ratio (ρ/ρ) of a density (ρ) measured by using helium gas as the replacing medium to a density (ρ) measured by using butanol as the replacing medium is more than 1.05 and less than 1.25.

Description

  The present invention relates to a negative electrode material, a negative electrode active material, a negative electrode for a lithium ion battery, and a lithium ion battery.

As a negative electrode material for a lithium ion battery, a graphite material is generally used.
However, since the graphite material expands and contracts between the crystallite layers due to lithium doping and dedoping, the crystallites are likely to be distorted. For this reason, the graphite material is likely to break the crystal structure due to repeated charge and discharge, and the lithium ion battery using the graphite material as the negative electrode material is inferior in charge and discharge cycle characteristics.

Patent Document 1 (Japanese Patent Laid-Open No. 8-115723) discloses that helium with respect to the density (ρ _B ) measured by using butanol as a substitution medium having an average layer spacing of (002) plane of 0.365 nm or more determined by X-ray diffraction method. A carbonaceous material for a secondary battery electrode is described in which the ratio (ρ _H / ρ _B ) of density (ρ _H ) measured using gas as a replacement medium is 1.15 or more.
Such a carbonaceous material is said to have excellent charge / discharge cycle characteristics because the crystallite layer is larger than the graphite material and the crystal structure is not easily destroyed by repeated charge / discharge compared to the graphite material. (See Patent Documents 1 and 2).

JP-A-8-115723 International Publication No. 2007/040007 Pamphlet

  However, as described in Patent Documents 1 and 2, a carbonaceous material having a larger crystallite layer than a graphite material has, for example, the following problems.

  A carbonaceous material having a larger crystallite layer than a graphite material is more susceptible to deterioration in the atmosphere than a graphite material and has poor storage characteristics. For this reason, it has been necessary to store in an inert gas atmosphere immediately after production, and it has been difficult to handle compared to a graphite material.

  Therefore, the first object of the present invention is to provide a negative electrode material for a lithium ion battery having an excellent (002) average layer spacing as compared with a graphite material and having excellent storage characteristics.

  In addition, a carbonaceous material having a larger crystallite layer than a graphite material has a reduced charge / discharge capacity when a part of the pores is closed in order to improve storage characteristics (for example, patents). Reference 2). Therefore, there was a trade-off relationship between improvement in storage characteristics and improvement in charge / discharge capacity.

  Accordingly, a second object of the present invention is to provide a negative electrode material for a lithium ion battery that has a large (002) plane average layer spacing as compared with a graphite material and is excellent in storage characteristics and charge / discharge capacity. And

  Further, the carbonaceous material having a larger crystallite layer than the graphite material has a disadvantage that its irreversible capacity is larger than that of the graphite material.

  Therefore, a third object of the present invention is to provide a negative electrode material for a lithium ion battery that has an average layer spacing of (002) planes that is larger than that of a graphite material and that has a reduced irreversible capacity.

According to the first invention of the present invention,
A negative electrode material for a lithium ion battery having an average layer spacing d _{002 of} (002) planes of 0.340 nm or more determined by an X-ray diffraction method using CuKα rays as a radiation source,
The ratio (ρ ^H / ρ ^B ) of the density (ρ ^H ) measured with helium gas as the replacement medium to the density (ρ ^B ) measured with butanol as the replacement medium is more than 1.05 and less than 1.25 A negative electrode material for an ion battery is provided.

According to the second invention of the present invention,
A negative electrode material for a lithium ion battery having an average layer spacing d _{002 of} (002) planes of 0.340 nm or more determined by an X-ray diffraction method using CuKα rays as a radiation source,
Provided is a negative electrode material for a lithium ion battery, wherein the carbon dioxide adsorption amount is less than 10 ml / g.

According to the third aspect of the present invention,
A negative electrode material for a lithium ion battery having an average layer spacing d _{002 of} (002) planes of 0.340 nm or more determined by an X-ray diffraction method using CuKα rays as a radiation source,
A negative electrode material for a lithium ion battery having a halogen content of less than 50 ppm is provided.

According to the fourth aspect of the present invention,
A negative electrode material for a lithium ion battery having an average layer spacing d _{002 of} (002) planes of 0.340 nm or more determined by an X-ray diffraction method using CuKα rays as a radiation source,
Contains nitrogen and sulfur atoms,
The nitrogen atom content is 1 ppm or more and 30000 ppm or less,
Provided is a negative electrode material for a lithium ion battery, wherein the sulfur atom content is 1 ppm or more and 30000 ppm or less.

According to the fifth aspect of the present invention,
A negative electrode material for a lithium ion battery having an average layer spacing d _{002 of} (002) planes of 0.340 nm or more determined by an X-ray diffraction method using CuKα rays as a radiation source,
Provided is a negative electrode material for lithium ion batteries having a pore volume of 0.003 μm to 5 μm determined by a mercury intrusion method and having a pore volume of less than 0.55 ml / g.

According to the sixth aspect of the present invention,
A negative electrode material for a lithium ion battery having an average layer spacing d _{002 of} (002) planes of 0.340 nm or more determined by an X-ray diffraction method using CuKα rays as a radiation source,
A negative electrode material for a lithium ion battery having a sphericity of less than 0.8 is provided.

According to the seventh aspect of the present invention,
A negative electrode material for a lithium ion battery having an average layer spacing d _{002 of} (002) planes of 0.340 nm or more determined by an X-ray diffraction method using CuKα rays as a radiation source,
Provided is a negative electrode material for a lithium ion battery having at least one exothermic peak at less than 650 ° C. in a differential thermal analysis measured under an air stream.

Furthermore, according to the present invention,
A negative electrode active material comprising the negative electrode material according to any one of the first invention to the seventh invention of the present invention is provided.

Furthermore, according to the present invention,
There is provided a negative electrode for a lithium ion battery comprising the negative electrode active material.

Furthermore, according to the present invention,
There is provided a lithium ion battery comprising at least the negative electrode for a lithium ion battery, an electrolyte, and a positive electrode.

  According to the first invention of the present invention, it is possible to provide a negative electrode material for a lithium ion battery having an excellent (002) plane average layer spacing as compared with a graphite material, and having excellent storage characteristics and charge / discharge capacity. it can.

  According to the second invention of the present invention, it is possible to provide a negative electrode material for a lithium ion battery having an excellent average storage distance and charge / discharge capacity while having an average layer spacing of (002) planes larger than that of a graphite material. it can.

  According to the third aspect of the present invention, it is possible to provide a negative electrode material for a lithium ion battery having excellent storage characteristics while having an average layer spacing of (002) planes larger than that of a graphite material.

  According to the fourth aspect of the present invention, it is possible to provide a negative electrode material for a lithium ion battery in which the irreversible capacity is suppressed while having an average layer spacing of (002) planes larger than that of a graphite material.

  According to the fifth aspect of the present invention, it is possible to provide a negative electrode material for a lithium ion battery in which the irreversible capacity is suppressed while having an average layer spacing of (002) planes larger than that of a graphite material.

  According to the sixth aspect of the present invention, it is possible to provide a negative electrode material for a lithium ion battery excellent in production efficiency while having an average layer spacing of (002) planes larger than that of a graphite material.

  According to the seventh invention of the present invention, it is possible to provide a negative electrode material for a lithium ion battery having an excellent (002) plane average layer spacing as compared with a graphite material, and having excellent storage characteristics and charge / discharge capacity. it can.

It is a schematic diagram which shows an example of the lithium ion battery which concerns on this embodiment.

  Hereinafter, embodiments of the present invention will be described with reference to the drawings. In addition, the figure is a schematic diagram and does not necessarily match the actual dimensional ratio.

[First invention]
Hereinafter, an embodiment according to the first invention will be described.
<Negative electrode material>
The negative electrode material according to the present embodiment is a negative electrode material for a lithium ion battery, and an average layer spacing d ₀₀₂ (hereinafter referred to as “d ₀₀₂ ”) of (002) planes obtained by an X-ray diffraction method using CuKα rays as a radiation source. Is also 0.340 nm or more, preferably 0.350 nm or more, and more preferably 0.365 nm or more. When d ₀₀₂ is equal to or greater than the lower limit, the crystal structure is prevented from being destroyed by repeated lithium doping and dedoping, so that the charge / discharge cycle characteristics of the negative electrode material can be improved.
The upper limit of the average layer surface distance d ₀₀₂ is not particularly limited, but is usually 0.400 nm or less, preferably 0.395 nm or less, and more preferably 0.390 nm or less. When d ₀₀₂ is less than or equal to the above upper limit, the irreversible capacity of the negative electrode material can be suppressed.

Further, the negative electrode material according to the present embodiment has a ratio (ρ ^H / ρ ^B ) of the density (ρ ^H ) measured using helium gas as the replacement medium to the density (ρ ^B ) measured using butanol as the replacement medium, and 1.05. It is super, preferably 1.07 or more, more preferably 1.10 or more.
Moreover, (rho) ^H / (rho) ^B is less than 1.25, Preferably it is less than 1.20, More preferably, it is less than 1.15.

When the ρ ^H / ρ ^B is equal to or higher than the lower limit, the charge capacity of lithium can be improved. Moreover, the irreversible capacity | capacitance of lithium can be reduced as the said (rho) ^H / (rho) ^B is below the said upper limit.

The value of ρ ^H / ρ ^B is one index of the pore structure of the negative electrode material, and the larger the value, the larger the number of pores that can penetrate butanol but not helium. That is, a large ρ ^H / ρ ^B means that a large number of fine pores exist. Further, if there are many pores into which helium cannot enter, ρ ^H / ρ ^B becomes small.

The negative electrode material according to the present embodiment, from the viewpoint of control of the pore size, [rho ^B is preferably not 1.50 g / cm ³ or more 1.80 g / cm ³ or less, more preferably 1.55 g / cm ³ or more 1.75 g / cm ^3, more preferably not more than 1.60 g / cm ³ or more 1.70 g / cm ^3.
The negative electrode material according to the present embodiment, from the viewpoint of control of the pore size, [rho ^H is preferably not more than 1.80 g / cm ³ or more 2.10 g / cm ^3, more preferably 1.85 g / cm ³ or more 2.05 g / cm ^3, more preferably not more than 1.90 g / cm ³ or more 2.00 g / cm ^3.

(Crystallite size)
The negative electrode material according to the present embodiment preferably has a crystallite size in the c-axis direction obtained by X-ray diffraction (hereinafter sometimes abbreviated as “Lc ₍₀₀₂₎ ”) of 5 nm or less. More preferably, it is 3 nm or less, More preferably, it is 2 nm or less.

(Average particle size)
The negative electrode material according to this embodiment preferably has a 50% cumulative particle size (D ₅₀ , average particle size) in a volume-based cumulative distribution of 1 μm to 50 μm, and more preferably 2 μm to 30 μm. preferable. Thereby, a high-density negative electrode can be produced.

(Specific surface area)
The negative electrode material according to the present embodiment preferably has a specific surface area of 1 m ² / g or more and 15 m ² / g or less, more preferably 3 m ² / g or more and 8 m ² / g or less, according to the BET three-point method in nitrogen adsorption. preferable.
When the specific surface area by the BET three-point method in nitrogen adsorption is not more than the above upper limit value, the irreversible reaction between the negative electrode material and the electrolytic solution can be further suppressed.
Moreover, appropriate permeability to the negative electrode material of electrolyte solution can be obtained because the specific surface area by the BET three point method in nitrogen adsorption is more than the said lower limit.

The calculation method of the specific surface area is as follows.
The monomolecular adsorption amount W _m is calculated from the following formula (1), the total surface area S _total is calculated from the following formula (2), and the specific surface area S is obtained from the following formula (3).
1 / [W · {(P _o / P) −1}] = {(C−1) / (W _m · C)} (P / P _o ) (1 / (W _m · C) (1)

In the above formula (1), P: pressure of an adsorbate gas in adsorption equilibrium, P _o : saturated vapor pressure of the adsorbate at the adsorption temperature, W: adsorption amount at the adsorption equilibrium pressure P, W _m : monolayer adsorption Amount, C: constant related to the magnitude of the interaction between the solid surface and the adsorbate (C = exp {(E ₁ -E ₂ ) RT}) [E ₁ : heat of adsorption of the first layer (kJ / mol), E ₂ : Heat of liquefaction at measurement temperature of adsorbate (kJ / mol)]

S _total = (W _m NA _cs ) M (2)
In the above formula (2), N: Avogadro number, M: molecular weight, A _cs : adsorption cross section

S = S _total / w (3)
In formula (3), w: sample weight (g)

(Discharge capacity)
The negative electrode material of the present embodiment has a discharge capacity of 360 mAh / g or more, more preferably 380 mAh / g or more, when charging / discharging under the charge / discharge conditions described later for a half cell manufactured under the conditions described later. More preferably, it is 400 mAh / g or more, and particularly preferably 420 mAh / g or more. The upper limit of the discharge capacity is not particularly limited and is preferably as many as possible. However, in reality, it is 700 mAh / g or less, and usually 500 mAh / g or less. In the present specification, “mAh / g” indicates a capacity per 1 g of the negative electrode material.

(Half cell manufacturing conditions)
The conditions for producing the above-described half cell will be described.
The negative electrode used is formed of the negative electrode material. More specifically, an electrode is formed using a composition in which a negative electrode material, carboxymethyl cellulose, styrene-butadiene rubber, and acetylene black are mixed at a weight ratio of 100: 1.5: 3.0: 2.0. The formed one is used.
The counter electrode uses metallic lithium.
As the electrolytic solution, a solution obtained by dissolving LiPF ₆ in a carbonate solvent (a mixed solvent in which ethylene carbonate and diethyl carbonate are mixed at a volume ratio of 1: 1) at a ratio of 1 M is used.

The negative electrode can be produced, for example, as follows.
First, a predetermined amount of negative electrode material, carboxymethylcellulose, styrene-butadiene rubber, acetylene black, and water are mixed with stirring to prepare a slurry. The obtained slurry is applied onto a copper foil as a current collector, preliminarily dried at 60 ° C. for 2 hours, and then vacuum dried at 120 ° C. for 15 hours. Subsequently, the negative electrode comprised with the negative electrode material can be obtained by cutting out to a predetermined magnitude | size.

In addition, the negative electrode has a disk shape with a diameter of 13 mm, the negative electrode active material layer (a portion obtained by removing the current collector from the negative electrode) has a disk shape with a thickness of 50 μm, and the counter electrode (an electrode made of metallic lithium) It can be a disk with a diameter of 12 mm and a thickness of 1 mm.
Further, the shape of the half cell can be a 2032 type coin cell shape.

(Charge / discharge conditions)
The charging / discharging conditions of the half cell described above are as follows.
Measurement temperature: 25 ° C
Charging method: constant current constant voltage method, charging current: 25 mA / g, charging voltage: 0 mV, charging end current: 2.5 mA / g
Discharge method: constant current method, discharge current: 25 mA / g, final discharge voltage: 2.5 V

  Note that “charging” for a half cell refers to moving lithium ions from an electrode made of metallic lithium to an electrode made of a negative electrode material by applying a voltage. “Discharge” refers to a phenomenon in which lithium ions move from an electrode made of a negative electrode material to an electrode made of metallic lithium.

<Method for producing negative electrode material>
Next, the manufacturing method of the negative electrode material according to the present embodiment will be described.
The negative electrode material according to the present embodiment can be produced, for example, by carbonizing a specific resin composition as a raw material under appropriate conditions.
The production of the anode material using the resin composition as a raw material itself has been performed in the prior art. However, in the present embodiment, factors such as (1) the composition of the resin composition, (2) the conditions for the carbonization treatment, and (3) the ratio of the raw material to the space where the carbonization treatment is performed are highly controlled. In order to obtain the negative electrode material according to the present embodiment, it is important to highly control these factors.
In particular, in order to obtain the negative electrode material according to the present embodiment, the present inventors set the above conditions (1) and (2) appropriately, and (3) the raw material for the space to be carbonized. It was found that it is important to set the occupation ratio lower than the conventional standard.
Hereinafter, an example of the manufacturing method of the negative electrode material which concerns on this embodiment is shown. However, the manufacturing method of the negative electrode material according to the present embodiment is not limited to the following example.

(Resin composition)
First, (1) a resin composition to be carbonized is selected as a raw material for the negative electrode material.
Examples of the resin contained in the resin composition that is the raw material of the negative electrode material according to the present embodiment include a thermosetting resin; a thermoplastic resin; a petroleum-based tar and pitch that are by-produced during ethylene production, and a coal produced by dry distillation. Coal tar, heavy components or pitch obtained by distilling off low boiling components of coal tar, petroleum-based or coal-based tar or pitch such as tar or pitch obtained by coal liquefaction; And the like subjected to crosslinking treatment. Among these, one kind or a combination of two or more kinds can be used. Among these, a thermosetting resin is preferable because it can be purified at the raw material stage, a negative electrode material with few impurities can be obtained, and the steps required for purification can be greatly shortened, leading to cost reduction.

Examples of the thermosetting resin include: phenol resins such as novolak type phenol resins and resol type phenol resins; epoxy resins such as bisphenol type epoxy resins and novolac type epoxy resins; melamine resins; urea resins; aniline resins; Examples include furan resins; ketone resins; unsaturated polyester resins; urethane resins. In addition, modified products obtained by modifying these with various components can also be used.
Among these, phenol resins such as novolac type phenol resin and resol type phenol resin; melamine resin; urea resin; aniline resin, which are resins using formaldehyde, are preferable because of the high residual carbon ratio.

Moreover, when using a thermosetting resin, the hardening | curing agent can be used together.
As the curing agent used, for example, hexamethylenetetramine, resol type phenol resin, polyacetal, paraformaldehyde and the like can be used in the case of a novolak type phenol resin. In the case of a resol type phenol resin, melamine resin, urea resin, aniline resin, hexamethylenetetramine or the like can be used.
The compounding quantity of a hardening | curing agent is 0.1 to 50 mass parts normally with respect to 100 mass parts of said thermosetting resins.

Moreover, in the resin composition as a raw material of negative electrode material, an additive can be mix | blended other than the said thermosetting resin and a hardening | curing agent.

Although it does not specifically limit as an additive used here, For example, the carbon material precursor carbonized at 200 to 800 degreeC, an organic acid, an inorganic acid, a nitrogen-containing compound, an oxygen-containing compound, an aromatic compound, nonferrous A metal element etc. can be mentioned. These additives can be used alone or in combination of two or more depending on the type and properties of the resin used.

  The method for preparing the resin composition is not particularly limited. For example, (1) a method in which the above resin and other components are melt-mixed, (2) the above resin and other components are dissolved in a solvent. (3) The resin and other components may be pulverized and mixed.

The apparatus for preparing the resin composition is not particularly limited. For example, when melt mixing is performed, a kneading apparatus such as a kneading roll, a single screw or a twin screw kneader can be used. When performing dissolution and mixing, a mixing device such as a Henschel mixer or a disperser can be used. When performing pulverization and mixing, for example, an apparatus such as a hammer mill or a jet mill can be used.

The resin composition thus obtained may be one obtained by physically mixing a plurality of types of components, or is applied during mixing (stirring, kneading, etc.) during preparation of the resin composition. A part of the material may be chemically reacted with mechanical energy and thermal energy converted from the mechanical energy. Specifically, a mechanochemical reaction using mechanical energy or a chemical reaction using thermal energy may be performed.

(Carbonization treatment)
Next, the obtained resin composition is carbonized.
Here, as the conditions for the carbonization treatment, for example, the temperature is raised from normal temperature to 1 ° C./hour to 200 ° C./hour, 800 ° C. to 3000 ° C., 0.01 Pa to 101 kPa (1 atm), The reaction can be performed for 1 hour to 50 hours, preferably 0.5 hours to 10 hours. The atmosphere during carbonization is preferably an inert atmosphere such as nitrogen or helium gas; a substantially inert atmosphere in which a trace amount of oxygen is present in the inert gas; a reducing gas atmosphere, or the like. . By doing in this way, thermal decomposition (oxidative decomposition) of resin can be suppressed and a desired negative electrode material can be obtained.

Conditions such as temperature and time during the carbonization treatment can be appropriately adjusted in order to optimize the characteristics of the negative electrode material.

In addition, you may perform a pre carbonization process before performing the said carbonization process.
Here, the conditions for the pre-carbonization treatment are not particularly limited. Thus, even if the resin composition is infusibilized by performing pre-carbonization treatment before carbonization treatment and pulverization treatment of the resin composition or the like is performed before the carbonization treatment step, the resin composition after pulverization can be obtained. It is possible to prevent re-fusion during carbonization and to obtain a desired negative electrode material efficiently.

Moreover, you may perform the hardening process of a resin composition before this pre carbonization process.
Although it does not specifically limit as a hardening processing method, For example, it can carry out by the method of giving heat quantity which can perform hardening reaction to a resin composition, the method of thermosetting, or the method of using together a thermosetting resin and a hardening | curing agent. . As a result, the pre-carbonization treatment can be performed substantially in the solid phase, so that the carbonization treatment or the pre-carbonization treatment can be performed while maintaining the structure of the thermosetting resin to some extent, and the structure and characteristics of the negative electrode material are controlled. Will be able to.

In addition, when performing the carbonization treatment or the pre-carbonization treatment, a metal, a pigment, a lubricant, an antistatic agent, an antioxidant, or the like is added to the resin composition to impart desired characteristics to the negative electrode material. You can also.

When the said hardening process or pre carbonization process is performed, you may grind | pulverize a processed material before the said carbonization process after that. In such a case, variation in the thermal history during carbonization can be reduced, and the uniformity of the surface state of the obtained negative electrode material can be increased. And the handleability of a processed material can be improved.

(Occupation ratio of raw materials in the space for carbonization)
Moreover, in order to obtain the negative electrode material according to the present embodiment, it is important to appropriately adjust the occupation ratio of the raw material in the space where the carbonization treatment is performed. Specifically, the occupation ratio of the raw material with respect to the space for carbonization is preferably set to 10.0 kg / m ³ or less, more preferably 5.0 kg / m ³ or less, and particularly preferably 1.0 kg / m ³ or less. . Here, the space for performing the carbonization treatment usually represents the furnace volume of the heat treatment furnace used for the carbonization treatment.
The reason why the negative electrode material according to the present embodiment can be obtained by setting the occupation ratio of the raw material in the space for performing the carbonization treatment to be equal to or less than the above upper limit value is not necessarily clear. This is probably because the generated gas is efficiently removed from the system.

The negative electrode material according to this embodiment can be obtained by the above procedure.

<Negative electrode active material>
Hereinafter, the negative electrode active material according to the present embodiment will be described.
The negative electrode active material refers to a material capable of taking in and out lithium ions in a lithium ion secondary battery. The negative electrode active material according to the present embodiment includes the negative electrode material according to the present embodiment described above.

The negative electrode active material according to the present embodiment may further include a type of negative electrode material different from the negative electrode material described above. Examples of such a negative electrode material include generally known negative electrode materials such as silicon, silicon monoxide, and graphite materials.

  Among these, the negative electrode active material according to the present embodiment preferably includes a graphite material in addition to the negative electrode material according to the present embodiment described above. Thereby, the charge / discharge capacity of the obtained lithium ion battery can be improved. Therefore, the obtained lithium ion battery can be made particularly excellent in the balance between charge / discharge capacity and charge / discharge efficiency.

The particle size (average particle size) at the time of 50% accumulation in the volume-based cumulative distribution of the graphite material used is preferably 2 μm or more and 50 μm or less, and more preferably 5 μm or more and 30 μm or less. Thereby, a high-density negative electrode can be produced while maintaining high charge / discharge efficiency.

<Anode for lithium ion battery, lithium ion battery>
Hereinafter, the negative electrode for lithium ion batteries and the lithium ion battery according to this embodiment will be described.

The negative electrode for a lithium ion battery according to the present embodiment (hereinafter sometimes simply referred to as a negative electrode) is produced using the negative electrode active material according to the present embodiment described above. Thereby, the negative electrode excellent in storage characteristics and charge / discharge capacity can be provided.
In addition, the lithium ion battery according to the present embodiment is manufactured using the negative electrode according to the present embodiment. Thereby, a lithium ion battery excellent in storage characteristics and charge / discharge capacity can be provided.

Hereinafter, preferred embodiments of a negative electrode for a lithium ion battery and a lithium ion battery according to the present embodiment will be described.
FIG. 1 is a schematic view showing an example of a lithium ion battery according to this embodiment.

As shown in FIG. 1, the lithium ion battery 10 includes a negative electrode 13, a positive electrode 21, an electrolytic solution 16, and a separator 18.

As shown in FIG. 1, the negative electrode 13 includes a negative electrode active material layer 12 and a negative electrode current collector 14.
The negative electrode current collector 14 is not particularly limited, and generally known negative electrode current collectors can be used. For example, copper foil or nickel foil can be used.

The negative electrode active material layer 12 is composed of the negative electrode active material according to the present embodiment described above.
The negative electrode 13 can be manufactured as follows, for example.

For 100 parts by weight of the negative electrode active material, generally known organic polymer binders (for example, fluorine-based polymers such as polyvinylidene fluoride and polytetrafluoroethylene; styrene / butadiene rubber, butyl rubber, butadiene rubber, etc.) 1 to 30 parts by weight and an appropriate amount of a viscosity adjusting solvent (N-methyl-2-pyrrolidone, dimethylformamide, etc.) or water is added and kneaded to prepare a negative electrode slurry. Prepare.
The negative electrode active material layer 12 can be obtained by molding the obtained slurry into a sheet shape, a pellet shape, or the like by compression molding, roll molding, or the like. And the negative electrode 13 can be obtained by laminating | stacking the negative electrode active material layer 12 and the negative electrode collector 14 which were obtained in this way.
Moreover, the negative electrode 13 can also be manufactured by apply | coating the obtained negative electrode slurry to the negative electrode collector 14, and drying.

The electrolyte solution 16 fills the space between the positive electrode 21 and the negative electrode 13 and is a layer in which lithium ions move by charge / discharge.

The electrolytic solution 16 is not particularly limited, and a generally known electrolytic solution can be used. For example, a solution obtained by dissolving a lithium salt serving as an electrolyte in a non-aqueous solvent is used.

Examples of the non-aqueous solvent include cyclic esters such as propylene carbonate, ethylene carbonate, and γ-butyrolactone; chain esters such as dimethyl carbonate and diethyl carbonate; chain ethers such as dimethoxyethane; or a mixture thereof. Can be used.

Is not particularly limited as electrolytes generally be a known electrolyte, for example, it may be used lithium metal salt such as LiClO _4, LiPF _6. Further, the above salts can be mixed with polyethylene oxide, polyacrylonitrile, etc. and used as a solid electrolyte.

It does not specifically limit as the separator 18, Generally a well-known separator can be used, For example, porous films, nonwoven fabrics, etc., such as polyethylene and a polypropylene, can be used.

As illustrated in FIG. 1, the positive electrode 21 includes a positive electrode active material layer 20 and a positive electrode current collector 22.
It does not specifically limit as the positive electrode active material layer 20, Generally, it can form with a well-known positive electrode active material. Is not particularly limited as the cathode active material include lithium cobalt oxide (LiCoO _2), lithium nickel oxide (LiNiO _2), composite oxides such as lithium manganese oxide (LiMn ₂ O _4); polyaniline, polypyrrole, etc. Or the like can be used.

The positive electrode current collector 22 is not particularly limited, and generally known positive electrode current collectors can be used. For example, an aluminum foil can be used.
And the positive electrode 21 in this embodiment can be manufactured with the manufacturing method of a well-known positive electrode generally.

[Second invention]
Hereinafter, an embodiment according to the second invention will be described.
<Negative electrode material>
The negative electrode material according to the present embodiment is a negative electrode material for a lithium ion battery, and an average layer spacing d ₀₀₂ (hereinafter referred to as “d ₀₀₂ ”) of (002) planes obtained by an X-ray diffraction method using CuKα rays as a radiation source. Is also 0.340 nm or more, preferably 0.350 nm or more, and more preferably 0.365 nm or more. When d ₀₀₂ is equal to or greater than the lower limit, the crystal structure is prevented from being destroyed by repeated lithium doping and dedoping, so that the charge / discharge cycle characteristics of the negative electrode material can be improved.
The upper limit of the average layer surface distance d ₀₀₂ is not particularly limited, but is usually 0.400 nm or less, preferably 0.395 nm or less, and more preferably 0.390 nm or less. When d ₀₀₂ is less than or equal to the above upper limit, the irreversible capacity of the negative electrode material can be suppressed.

In the negative electrode material according to this embodiment, the amount of carbon dioxide adsorbed is less than 10 ml / g, preferably 8 ml / g or less, and more preferably 6 ml / g or less. When the adsorption amount of carbon dioxide gas is not more than the above upper limit value, the storage characteristics of the negative electrode material can be further improved.
In addition, the negative electrode material according to the present embodiment preferably has an adsorption amount of carbon dioxide gas of 0.05 ml / g or more, and more preferably 0.1 ml / g or more. When the adsorption amount of carbon dioxide gas is equal to or more than the lower limit, the charge capacity of lithium can be further improved.
The amount of carbon dioxide adsorbed is measured by using an ASAP-2000M manufactured by Micromeritics Instrument Corporation, which is obtained by vacuum drying a negative electrode material at 130 ° C. for 3 hours or more using a vacuum dryer. It can be carried out.

(Crystallite size)
In the negative electrode material according to the present embodiment, the crystallite size in the c-axis direction obtained by the X-ray diffraction method is preferably 5 nm or less, more preferably 3 nm or less, and further preferably 2 nm or less.

(Average particle size)
The negative electrode material according to this embodiment preferably has a 50% cumulative particle size (D ₅₀ , average particle size) in a volume-based cumulative distribution of 1 μm to 50 μm, and more preferably 2 μm to 30 μm. preferable. Thereby, a high-density negative electrode can be produced.

(Specific surface area)
The negative electrode material according to the present embodiment preferably has a specific surface area of 1 m ² / g or more and 15 m ² / g or less, more preferably 3 m ² / g or more and 8 m ² / g or less, according to the BET three-point method in nitrogen adsorption. preferable.
When the specific surface area by the BET three-point method in nitrogen adsorption is not more than the above upper limit value, the irreversible reaction between the negative electrode material and the electrolytic solution can be further suppressed.
Moreover, appropriate permeability to the negative electrode material of electrolyte solution can be obtained because the specific surface area by the BET three point method in nitrogen adsorption is more than the said lower limit.

Since the calculation method of the specific surface area is the same as that of the negative electrode material according to the first invention described above, description thereof is omitted.

(Discharge capacity)
In the negative electrode material of the present embodiment, the discharge capacity when charging / discharging under the charge / discharge conditions described in the first invention is preferably 360 mAh / g or more for the half cell produced under the conditions described in the first invention. More preferably, it is 380 mAh / g or more, More preferably, it is 400 mAh / g or more, Most preferably, it is 420 mAh / g or more. The upper limit of the discharge capacity is not particularly limited and is preferably as many as possible. However, in reality, it is 700 mAh / g or less, and usually 500 mAh / g or less. In the present specification, “mAh / g” indicates a capacity per 1 g of the negative electrode material.

<Method for producing negative electrode material>
The negative electrode material which concerns on 2nd invention can be manufactured according to the manufacturing method of the negative electrode material which concerns on 1st invention. Details are omitted here.

<Negative electrode active material>
Hereinafter, the negative electrode active material according to the present embodiment will be described.
The negative electrode active material refers to a material capable of taking in and out lithium ions in a lithium ion secondary battery. The negative electrode active material according to the present embodiment includes the negative electrode material according to the present embodiment described above.

The negative electrode active material according to the present embodiment may further include a type of negative electrode material different from the negative electrode material described above. Examples of such a negative electrode material include generally known negative electrode materials such as silicon, silicon monoxide, and graphite materials.

  Among these, the negative electrode active material according to the present embodiment preferably includes a graphite material in addition to the negative electrode material according to the present embodiment described above. Thereby, the charge / discharge capacity of the obtained lithium ion battery can be improved. Therefore, the obtained lithium ion battery can be made particularly excellent in the balance between charge / discharge capacity and charge / discharge efficiency.

The particle size (average particle size) at the time of 50% accumulation in the volume-based cumulative distribution of the graphite material used is preferably 2 μm or more and 50 μm or less, and more preferably 5 μm or more and 30 μm or less. Thereby, a high-density negative electrode can be produced while maintaining high charge / discharge efficiency.

<Anode for lithium ion battery, lithium ion battery>
The negative electrode for lithium ion batteries and the lithium ion battery according to the second invention can be produced according to the negative electrode for lithium ion batteries and the lithium ion battery according to the first invention. Details are omitted here.

[Third invention]
Hereinafter, an embodiment according to the third invention will be described.
<Negative electrode material>
The negative electrode material according to the present embodiment is a negative electrode material for a lithium ion battery, and an average layer spacing d ₀₀₂ (hereinafter referred to as “d ₀₀₂ ”) of (002) planes obtained by an X-ray diffraction method using CuKα rays as a radiation source. Is also 0.340 nm or more, preferably 0.350 nm or more, and more preferably 0.365 nm or more. When d ₀₀₂ is equal to or greater than the lower limit, the crystal structure is prevented from being destroyed by repeated lithium doping and dedoping, so that the charge / discharge cycle characteristics of the negative electrode material can be improved.
The upper limit of the average layer surface distance d ₀₀₂ is not particularly limited, but is usually 0.400 nm or less, preferably 0.395 nm or less, and more preferably 0.390 nm or less. When d ₀₀₂ is less than or equal to the above upper limit, the irreversible capacity of the negative electrode material can be suppressed.

  The negative electrode material according to this embodiment has a halogen content of less than 50 ppm, preferably 30 ppm or less, and more preferably 10 ppm or less. When the halogen content is less than or less than the above upper limit value, the storage characteristics of the negative electrode material can be improved. The halogen content can be controlled by adjusting the halogen gas concentration in the processing gas used for the carbonization treatment and the halogen amount contained in the raw material of the negative electrode material. The halogen content is calculated by burning the negative electrode material, absorbing the halogen hydrogen gas in the generated combustion gas into sodium hydroxide, and then quantifying the halogen content in this solution with an ion chromatography analyzer. it can.

(Crystallite size)
In the negative electrode material according to the present embodiment, the crystallite size in the c-axis direction obtained by the X-ray diffraction method is preferably 5 nm or less, more preferably 3 nm or less, and further preferably 2 nm or less.

(Average particle size)
The negative electrode material according to this embodiment preferably has a 50% cumulative particle size (D ₅₀ , average particle size) in a volume-based cumulative distribution of 1 μm to 50 μm, and more preferably 2 μm to 30 μm. preferable. Thereby, a high-density negative electrode can be produced.

(Specific surface area)
The negative electrode material according to the present embodiment preferably has a specific surface area of 1 m ² / g or more and 15 m ² / g or less, more preferably 3 m ² / g or more and 8 m ² / g or less, according to the BET three-point method in nitrogen adsorption. preferable.
When the specific surface area by the BET three-point method in nitrogen adsorption is not more than the above upper limit value, the irreversible reaction between the negative electrode material and the electrolytic solution can be further suppressed.
Moreover, appropriate permeability to the negative electrode material of electrolyte solution can be obtained because the specific surface area by the BET three point method in nitrogen adsorption is more than the said lower limit.

Since the calculation method of the specific surface area is the same as that of the negative electrode material according to the first invention described above, description thereof is omitted.

(Discharge capacity)
In the negative electrode material of the present embodiment, the discharge capacity when charging / discharging under the charge / discharge conditions described in the first invention is preferably 360 mAh / g or more for the half cell produced under the conditions described in the first invention. More preferably, it is 380 mAh / g or more, More preferably, it is 400 mAh / g or more, Most preferably, it is 420 mAh / g or more. The upper limit of the discharge capacity is not particularly limited and is preferably as many as possible. However, in reality, it is 700 mAh / g or less, and usually 500 mAh / g or less. In the present specification, “mAh / g” indicates a capacity per 1 g of the negative electrode material.

<Method for producing negative electrode material>
The negative electrode material which concerns on 3rd invention can be manufactured according to the manufacturing method of the negative electrode material which concerns on 1st invention. Details are omitted here.

<Negative electrode active material>
Hereinafter, the negative electrode active material according to the present embodiment will be described.
The negative electrode active material refers to a material capable of taking in and out lithium ions in a lithium ion secondary battery. The negative electrode active material according to the present embodiment includes the negative electrode material according to the present embodiment described above.

The negative electrode active material according to the present embodiment may further include a type of negative electrode material different from the negative electrode material described above. Examples of such a negative electrode material include generally known negative electrode materials such as silicon, silicon monoxide, and graphite materials.

  Among these, the negative electrode active material according to the present embodiment preferably includes a graphite material in addition to the negative electrode material according to the present embodiment described above. Thereby, the charge / discharge capacity of the obtained lithium ion battery can be improved. Therefore, the obtained lithium ion battery can be made particularly excellent in the balance between charge / discharge capacity and charge / discharge efficiency.

The particle size (average particle size) at the time of 50% accumulation in the volume-based cumulative distribution of the graphite material used is preferably 2 μm or more and 50 μm or less, and more preferably 5 μm or more and 30 μm or less. Thereby, a high-density negative electrode can be produced while maintaining high charge / discharge efficiency.

<Anode for lithium ion battery, lithium ion battery>
The negative electrode for lithium ion batteries and the lithium ion battery according to the third invention can be manufactured according to the negative electrode for lithium ion batteries and the lithium ion battery according to the first invention. Details are omitted here.

[Fourth Invention]
The embodiment according to the fourth invention will be described below.
<Negative electrode material>
The negative electrode material according to the present embodiment is a negative electrode material for a lithium ion battery, and an average layer spacing d ₀₀₂ (hereinafter referred to as “d ₀₀₂ ”) of (002) planes obtained by an X-ray diffraction method using CuKα rays as a radiation source. Is also 0.340 nm or more, preferably 0.350 nm or more, and more preferably 0.365 nm or more. When d ₀₀₂ is equal to or greater than the lower limit, the crystal structure is prevented from being destroyed by repeated lithium doping and dedoping, so that the charge / discharge cycle characteristics of the negative electrode material can be improved.
The upper limit of the average layer surface distance d ₀₀₂ is not particularly limited, but is usually 0.400 nm or less, preferably 0.395 nm or less, and more preferably 0.390 nm or less. When d ₀₀₂ is less than or equal to the above upper limit, the irreversible capacity of the negative electrode material can be suppressed.

Moreover, the negative electrode material according to the present embodiment includes a nitrogen atom and a sulfur atom.
The content of nitrogen atoms in the negative electrode material according to this embodiment is 1 ppm or more and 30000 ppm or less, preferably 100 ppm or more and 25000 ppm or less, from the viewpoint of reducing irreversible capacity.
Moreover, content of the sulfur atom in the negative electrode material which concerns on this embodiment is 1 ppm or more and 30000 ppm or less from a viewpoint of reduction of an irreversible capacity | capacitance, Preferably it is 5 ppm or more and 1000 ppm or less.
The content of nitrogen atoms in the negative electrode material according to the present embodiment can be quantified using elemental analysis. Moreover, content of the sulfur atom in the negative electrode material which concerns on this embodiment can be quantified using an ion chromatography method.

(Crystallite size)
In the negative electrode material according to the present embodiment, the crystallite size in the c-axis direction obtained by the X-ray diffraction method is preferably 5 nm or less, more preferably 3 nm or less, and further preferably 2 nm or less.

(Average particle size)
The negative electrode material according to this embodiment preferably has a 50% cumulative particle size (D ₅₀ , average particle size) in a volume-based cumulative distribution of 1 μm to 50 μm, and more preferably 2 μm to 30 μm. preferable. Thereby, a high-density negative electrode can be produced.

(Specific surface area)
The negative electrode material according to the present embodiment preferably has a specific surface area of 1 m ² / g or more and 15 m ² / g or less, more preferably 3 m ² / g or more and 8 m ² / g or less, according to the BET three-point method in nitrogen adsorption. preferable.
When the specific surface area by the BET three-point method in nitrogen adsorption is not more than the above upper limit value, the irreversible reaction between the negative electrode material and the electrolytic solution can be further suppressed.
Moreover, appropriate permeability to the negative electrode material of electrolyte solution can be obtained because the specific surface area by the BET three point method in nitrogen adsorption is more than the said lower limit.

Since the calculation method of the specific surface area is the same as that of the negative electrode material according to the first invention described above, description thereof is omitted.

(Discharge capacity)
In the negative electrode material of the present embodiment, the discharge capacity when charging / discharging under the charge / discharge conditions described in the first invention is preferably 360 mAh / g or more for the half cell produced under the conditions described in the first invention. More preferably, it is 380 mAh / g or more, More preferably, it is 400 mAh / g or more, Most preferably, it is 420 mAh / g or more. The upper limit of the discharge capacity is not particularly limited and is preferably as many as possible. However, in reality, it is 700 mAh / g or less, and usually 500 mAh / g or less. In the present specification, “mAh / g” indicates a capacity per 1 g of the negative electrode material.

<Method for producing negative electrode material>
The negative electrode material according to the fourth invention can be produced according to the production method of the negative electrode material according to the first invention. Details are omitted here.

<Negative electrode active material>
Hereinafter, the negative electrode active material according to the present embodiment will be described.
The negative electrode active material refers to a material capable of taking in and out lithium ions in a lithium ion secondary battery. The negative electrode active material according to the present embodiment includes the negative electrode material according to the present embodiment described above.

The negative electrode active material according to the present embodiment may further include a type of negative electrode material different from the negative electrode material described above. Examples of such a negative electrode material include generally known negative electrode materials such as silicon, silicon monoxide, and graphite materials.

  Among these, the negative electrode active material according to the present embodiment preferably includes a graphite material in addition to the negative electrode material according to the present embodiment described above. Thereby, the charge / discharge capacity of the obtained lithium ion battery can be improved. Therefore, the obtained lithium ion battery can be made particularly excellent in the balance between charge / discharge capacity and charge / discharge efficiency.

The particle size (average particle size) at the time of 50% accumulation in the volume-based cumulative distribution of the graphite material used is preferably 2 μm or more and 50 μm or less, and more preferably 5 μm or more and 30 μm or less. Thereby, a high-density negative electrode can be produced while maintaining high charge / discharge efficiency.

<Anode for lithium ion battery, lithium ion battery>
The negative electrode for lithium ion batteries and the lithium ion battery according to the fourth invention can be manufactured according to the negative electrode for lithium ion batteries and the lithium ion battery according to the first invention. Details are omitted here.

[Fifth invention]
The embodiment according to the fifth invention will be described below.
<Negative electrode material>
The negative electrode material according to the present embodiment is a negative electrode material for a lithium ion battery, and an average layer spacing d ₀₀₂ (hereinafter referred to as “d ₀₀₂ ”) of (002) planes obtained by an X-ray diffraction method using CuKα rays as a radiation source. Is also 0.340 nm or more, preferably 0.350 nm or more, and more preferably 0.365 nm or more. When d ₀₀₂ is equal to or greater than the lower limit, the crystal structure is prevented from being destroyed by repeated lithium doping and dedoping, so that the charge / discharge cycle characteristics of the negative electrode material can be improved.
The upper limit of the average layer surface distance d ₀₀₂ is not particularly limited, but is usually 0.400 nm or less, preferably 0.395 nm or less, and more preferably 0.390 nm or less. When d ₀₀₂ is less than or equal to the above upper limit, the irreversible capacity of the negative electrode material can be suppressed.

In addition, the negative electrode material according to the present embodiment has a pore volume of 0.003 μm to 5 μm and a pore volume of less than 0.55 ml / g, preferably 0, from the viewpoint of improving packing density. 0.53 ml / g or less, more preferably 0.50 ml / g or less.
In addition, the negative electrode material according to the present embodiment preferably has a pore volume of 0.003 μm to 5 μm, which is obtained by a mercury intrusion method, from the viewpoint of reducing irreversible capacity, and is preferably 0.10 ml / g or more. More preferably, it is 0.20 ml / g or more, More preferably, it is 0.30 ml / g or more.
Here, the pore volume by the mercury intrusion method can be measured by using Autopore III9420 manufactured by MICROMERITICS.

(Crystallite size)
In the negative electrode material according to the present embodiment, the crystallite size in the c-axis direction obtained by the X-ray diffraction method is preferably 5 nm or less, more preferably 3 nm or less, and further preferably 2 nm or less.

(Average particle size)
The negative electrode material according to this embodiment preferably has a 50% cumulative particle size (D ₅₀ , average particle size) in a volume-based cumulative distribution of 1 μm to 50 μm, and more preferably 2 μm to 30 μm. preferable. Thereby, a high-density negative electrode can be produced.

(Specific surface area)
The negative electrode material according to the present embodiment preferably has a specific surface area of 1 m ² / g or more and 15 m ² / g or less, more preferably 3 m ² / g or more and 8 m ² / g or less, according to the BET three-point method in nitrogen adsorption. preferable.
When the specific surface area by the BET three-point method in nitrogen adsorption is not more than the above upper limit value, the irreversible reaction between the negative electrode material and the electrolytic solution can be further suppressed.
Moreover, appropriate permeability to the negative electrode material of electrolyte solution can be obtained because the specific surface area by the BET three point method in nitrogen adsorption is more than the said lower limit.

Since the calculation method of the specific surface area is the same as that of the negative electrode material according to the first invention described above, description thereof is omitted.

(Discharge capacity)
In the negative electrode material of the present embodiment, the discharge capacity when charging / discharging under the charge / discharge conditions described in the first invention is preferably 360 mAh / g or more for the half cell produced under the conditions described in the first invention. More preferably, it is 380 mAh / g or more, More preferably, it is 400 mAh / g or more, Most preferably, it is 420 mAh / g or more. The upper limit of the discharge capacity is not particularly limited and is preferably as many as possible. However, in reality, it is 700 mAh / g or less, and usually 500 mAh / g or less. In the present specification, “mAh / g” indicates a capacity per 1 g of the negative electrode material.

<Method for producing negative electrode material>
The negative electrode material which concerns on 5th invention can be manufactured according to the manufacturing method of the negative electrode material which concerns on 1st invention. Details are omitted here.

<Negative electrode active material>
Hereinafter, the negative electrode active material according to the present embodiment will be described.
The negative electrode active material refers to a material capable of taking in and out lithium ions in a lithium ion secondary battery. The negative electrode active material according to the present embodiment includes the negative electrode material according to the present embodiment described above.

The negative electrode active material according to the present embodiment may further include a type of negative electrode material different from the negative electrode material described above. Examples of such a negative electrode material include generally known negative electrode materials such as silicon, silicon monoxide, and graphite materials.

  Among these, the negative electrode active material according to the present embodiment preferably includes a graphite material in addition to the negative electrode material according to the present embodiment described above. Thereby, the charge / discharge capacity of the obtained lithium ion battery can be improved. Therefore, the obtained lithium ion battery can be made particularly excellent in the balance between charge / discharge capacity and charge / discharge efficiency.

The particle size (average particle size) at the time of 50% accumulation in the volume-based cumulative distribution of the graphite material used is preferably 2 μm or more and 50 μm or less, and more preferably 5 μm or more and 30 μm or less. Thereby, a high-density negative electrode can be produced while maintaining high charge / discharge efficiency.

<Anode for lithium ion battery, lithium ion battery>
The negative electrode for lithium ion batteries and the lithium ion battery according to the fifth invention can be manufactured according to the negative electrode for lithium ion batteries and the lithium ion battery according to the first invention. Details are omitted here.

[Sixth Invention]
Embodiments according to the sixth invention will be described below.
<Negative electrode material>
The negative electrode material according to the present embodiment is a negative electrode material for a lithium ion battery, and an average layer spacing d ₀₀₂ (hereinafter referred to as “d ₀₀₂ ”) of (002) planes obtained by an X-ray diffraction method using CuKα rays as a radiation source. Is also 0.340 nm or more, preferably 0.350 nm or more, and more preferably 0.365 nm or more. When d ₀₀₂ is equal to or greater than the lower limit, the crystal structure is prevented from being destroyed by repeated lithium doping and dedoping, so that the charge / discharge cycle characteristics of the negative electrode material can be improved.
The upper limit of the average layer surface distance d ₀₀₂ is not particularly limited, but is usually 0.400 nm or less, preferably 0.395 nm or less, and more preferably 0.390 nm or less. When d ₀₀₂ is less than or equal to the above upper limit, the irreversible capacity of the negative electrode material can be suppressed.

The negative electrode material according to the present embodiment has a sphericity of less than 0.8, preferably 0.7 or less, more preferably 0.6 or less, from the viewpoint of improving production efficiency.
The sphericity is determined by burying the negative electrode material in an epoxy resin, polishing, observing with an optical microscope, particles having an average particle diameter D ₅₀ ± 50%, and overlapping and contact with other particles. The plane image analysis of the particles is performed on the 30 non-existing particles by a high-functional image analysis system (“IP-500PC” manufactured by Asahi Engineering Co., Ltd.), and the average value of the circularity C according to the following formula is set as the sphericity.
Circularity C = 4 · π · S / l ²
Here, l: circumference length, S: area.

(Crystallite size)
In the negative electrode material according to the present embodiment, the crystallite size in the c-axis direction obtained by the X-ray diffraction method is preferably 5 nm or less, more preferably 3 nm or less, and further preferably 2 nm or less.

(Average particle size)
The negative electrode material according to this embodiment preferably has a 50% cumulative particle size (D ₅₀ , average particle size) in a volume-based cumulative distribution of 1 μm to 50 μm, and more preferably 2 μm to 30 μm. preferable. Thereby, a high-density negative electrode can be produced.

(Specific surface area)
The negative electrode material according to the present embodiment preferably has a specific surface area of 1 m ² / g or more and 15 m ² / g or less, more preferably 3 m ² / g or more and 8 m ² / g or less, according to the BET three-point method in nitrogen adsorption. preferable.
When the specific surface area by the BET three-point method in nitrogen adsorption is not more than the above upper limit value, the irreversible reaction between the negative electrode material and the electrolytic solution can be further suppressed.
Moreover, appropriate permeability to the negative electrode material of electrolyte solution can be obtained because the specific surface area by the BET three point method in nitrogen adsorption is more than the said lower limit.

Since the calculation method of the specific surface area is the same as that of the negative electrode material according to the first invention described above, description thereof is omitted.

(Discharge capacity)
In the negative electrode material of the present embodiment, the discharge capacity when charging / discharging under the charge / discharge conditions described in the first invention is preferably 360 mAh / g or more for the half cell produced under the conditions described in the first invention. More preferably, it is 380 mAh / g or more, More preferably, it is 400 mAh / g or more, Most preferably, it is 420 mAh / g or more. The upper limit of the discharge capacity is not particularly limited and is preferably as many as possible. However, in reality, it is 700 mAh / g or less, and usually 500 mAh / g or less. In the present specification, “mAh / g” indicates a capacity per 1 g of the negative electrode material.

<Method for producing negative electrode material>
The negative electrode material according to the sixth invention can be manufactured according to the method for manufacturing a negative electrode material according to the first invention. Details are omitted here.

<Negative electrode active material>
Hereinafter, the negative electrode active material according to the present embodiment will be described.
The negative electrode active material refers to a material capable of taking in and out lithium ions in a lithium ion secondary battery. The negative electrode active material according to the present embodiment includes the negative electrode material according to the present embodiment described above.

The negative electrode active material according to the present embodiment may further include a type of negative electrode material different from the negative electrode material described above. Examples of such a negative electrode material include generally known negative electrode materials such as silicon, silicon monoxide, and graphite materials.

  Among these, the negative electrode active material according to the present embodiment preferably includes a graphite material in addition to the negative electrode material according to the present embodiment described above. Thereby, the charge / discharge capacity of the obtained lithium ion battery can be improved. Therefore, the obtained lithium ion battery can be made particularly excellent in the balance between charge / discharge capacity and charge / discharge efficiency.

The particle size (average particle size) at the time of 50% accumulation in the volume-based cumulative distribution of the graphite material used is preferably 2 μm or more and 50 μm or less, and more preferably 5 μm or more and 30 μm or less. Thereby, a high-density negative electrode can be produced while maintaining high charge / discharge efficiency.

<Anode for lithium ion battery, lithium ion battery>
The negative electrode for lithium ion batteries and the lithium ion battery according to the sixth invention can be manufactured according to the negative electrode for lithium ion batteries and the lithium ion battery according to the first invention. Details are omitted here.

[Seventh invention]
Hereinafter, an embodiment according to the seventh invention will be described.
<Negative electrode material>
The negative electrode material according to the present embodiment is a negative electrode material for a lithium ion battery, and an average layer spacing d ₀₀₂ (hereinafter referred to as “d ₀₀₂ ”) of (002) planes obtained by an X-ray diffraction method using CuKα rays as a radiation source. Is also 0.340 nm or more, preferably 0.350 nm or more, and more preferably 0.365 nm or more. When d ₀₀₂ is equal to or greater than the lower limit, the crystal structure is prevented from being destroyed by repeated lithium doping and dedoping, so that the charge / discharge cycle characteristics of the negative electrode material can be improved.
The upper limit of the average layer surface distance d ₀₀₂ is not particularly limited, but is usually 0.400 nm or less, preferably 0.395 nm or less, and more preferably 0.390 nm or less. When d ₀₀₂ is less than or equal to the above upper limit, the irreversible capacity of the negative electrode material can be suppressed.

  Further, the negative electrode material according to the present embodiment has at least one exothermic heat of less than 650 ° C., preferably 550 ° C. or more and 645 ° C. or less, more preferably 590 ° C. or more and 640 ° C. or less, in differential thermal analysis measured under an air stream. Has a peak. Thereby, storage characteristics and charge / discharge capacity can be improved.

(Crystallite size)
In the negative electrode material according to the present embodiment, the crystallite size in the c-axis direction obtained by the X-ray diffraction method is preferably 5 nm or less, more preferably 3 nm or less, and further preferably 2 nm or less.

(Average particle size)
The negative electrode material according to this embodiment preferably has a 50% cumulative particle size (D ₅₀ , average particle size) in a volume-based cumulative distribution of 1 μm to 50 μm, and more preferably 2 μm to 30 μm. preferable. Thereby, a high-density negative electrode can be produced.

(Specific surface area)
The negative electrode material according to the present embodiment preferably has a specific surface area of 1 m ² / g or more and 15 m ² / g or less, more preferably 3 m ² / g or more and 8 m ² / g or less, according to the BET 3-point method in nitrogen adsorption. preferable.
When the specific surface area by the BET three-point method in nitrogen adsorption is not more than the above upper limit value, the irreversible reaction between the negative electrode material and the electrolytic solution can be further suppressed.
Moreover, appropriate permeability to the negative electrode material of electrolyte solution can be obtained because the specific surface area by the BET three point method in nitrogen adsorption is more than the said lower limit.

Since the calculation method of the specific surface area is the same as that of the negative electrode material according to the first invention described above, description thereof is omitted.

(Discharge capacity)
In the negative electrode material of the present embodiment, the discharge capacity when charging / discharging under the charge / discharge conditions described in the first invention is preferably 360 mAh / g or more for the half cell produced under the conditions described in the first invention. More preferably, it is 380 mAh / g or more, More preferably, it is 400 mAh / g or more, Most preferably, it is 420 mAh / g or more. The upper limit of the discharge capacity is not particularly limited and is preferably as many as possible. However, in reality, it is 700 mAh / g or less, and usually 500 mAh / g or less. In the present specification, “mAh / g” indicates a capacity per 1 g of the negative electrode material.

<Method for producing negative electrode material>
The negative electrode material according to the seventh invention can be produced according to the production method of the negative electrode material according to the first invention. Details are omitted here.

<Negative electrode active material>
Hereinafter, the negative electrode active material according to the present embodiment will be described.
The negative electrode active material refers to a material capable of taking in and out lithium ions in a lithium ion secondary battery. The negative electrode active material according to the present embodiment includes the negative electrode material according to the present embodiment described above.

The negative electrode active material according to the present embodiment may further include a type of negative electrode material different from the negative electrode material described above. Examples of such a negative electrode material include generally known negative electrode materials such as silicon, silicon monoxide, and graphite materials.

  Among these, the negative electrode active material according to the present embodiment preferably includes a graphite material in addition to the negative electrode material according to the present embodiment described above. Thereby, the charge / discharge capacity of the obtained lithium ion battery can be improved. Therefore, the obtained lithium ion battery can be made particularly excellent in the balance between charge / discharge capacity and charge / discharge efficiency.

The particle size (average particle size) at the time of 50% accumulation in the volume-based cumulative distribution of the graphite material used is preferably 2 μm or more and 50 μm or less, and more preferably 5 μm or more and 30 μm or less. Thereby, a high-density negative electrode can be produced while maintaining high charge / discharge efficiency.

<Anode for lithium ion battery, lithium ion battery>
The negative electrode for lithium ion batteries and the lithium ion battery according to the seventh invention can be manufactured according to the negative electrode for lithium ion batteries and the lithium ion battery according to the first invention. Details are omitted here.

  As mentioned above, although embodiment of each invention of this invention was described, these are illustrations of this invention and can employ | adopt various structures other than the above.

  Needless to say, the present inventions described above can be combined within a range in which the contents do not conflict with each other.

  Hereinafter, although an example and a comparative example explain the present invention, the present invention is not limited to these. In the examples, “part” means “part by weight”.

[1] Evaluation Method for Negative Electrode Material First, an evaluation method for negative electrode materials obtained in Examples and Comparative Examples described later will be described.

1. Particle size distribution The particle size distribution of the negative electrode material was measured by a laser diffraction method using a laser diffraction particle size distribution measuring apparatus LA-920 manufactured by Horiba. From the measurement results, the particle size (D ₅₀ , average particle size) at 50% accumulation in the volume-based cumulative distribution was determined for the negative electrode material.

2. The specific surface area was measured by the BET three-point method in nitrogen adsorption using a Nova-1200 device manufactured by Yuasa. The specific calculation method is as described above.

3. Negative electrode material d ₀₀₂ and Lc ₍₀₀₂₎
Using an X-ray diffractometer “XRD-7000” manufactured by Shimadzu Corporation, the average layer spacing d ₀₀₂ of the (002) plane was measured.
From the spectrum obtained from the X-ray diffraction measurement of the negative electrode material, the average layer spacing d ₀₀₂ of the (002) plane was calculated from the following Bragg equation.
λ = 2d _hkl sinθ Bragg equation (d _hkl = d ₀₀₂ )
λ: wavelength of characteristic X-ray K _α1 output from the cathode θ: reflection angle of spectrum Lc ₍₀₀₂₎ was measured as follows.
It was determined from the half width of the 002 plane peak and the diffraction angle in the spectrum obtained from the X-ray diffraction measurement using the following Scherrer equation.
Lc ₍₀₀₂₎ = 0.94 λ / (βcos θ) (Scherrer equation)
Lc ₍₀₀₂₎ : Crystallite size λ: Wavelength of characteristic X-ray K _α1 output from the cathode β: Half width of peak (radian)
θ: Spectral reflection angle

4). Carbon dioxide gas adsorption amount Carbon dioxide gas adsorption amount was measured using a vacuum drier with a negative electrode material vacuum-dried at 130 ° C. for 3 hours or more as a measurement sample, using ASAP-2000M manufactured by Micromeritics Instrument Corporation. Done using.
A measurement sample tube (0.5 g) was placed in a measurement sample tube and dried under reduced pressure at 300 ° C. for 3 hours or more under a reduced pressure of 0.2 Pa or less. Thereafter, the amount of carbon dioxide adsorbed was measured.
The adsorption temperature is 0 ° C., the pressure is reduced until the pressure of the sample tube containing the measurement sample becomes 0.6 Pa or less, carbon dioxide gas is introduced into the sample tube, and the equilibrium pressure in the sample tube is 0.11 MPa (relative pressure). The amount of carbon dioxide adsorbed until it reached (corresponding to 0.032) was determined by the constant volume method and expressed in ml / g. The adsorption amount is a value converted to a standard state (STP).

5. Content of Chlorine The negative electrode material was burned using an oxyhydrogen flame combustion apparatus, and HCl in the produced combustion gas was absorbed in 0.01 mol NaOH aqueous solution. Next, the chlorine content in the aqueous solution was quantified with an ion chromatography analyzer. The calibration curve of the ion chromatography analyzer was prepared by analyzing a solution prepared by diluting a chloride ion standard solution for ion chromatography (sodium chloride aqueous solution, chloride ion concentration 1000 ppm, manufactured by Kanto Chemical Co., Inc.). .

6). Measurement of density ρ ^B : Measured by the butanol method according to the method defined in JIS R7212.
ρ ^H : Using a dry density meter Accupic 1330 manufactured by Micromeritics, the sample was measured after drying at 120 ° C. for 2 hours. The measurement was performed at 23 ° C. All pressures are gauge pressures, and are the pressures obtained by subtracting the ambient pressure from the absolute pressure.

The measuring device has a sample chamber and an expansion chamber, and the sample chamber has a pressure gauge for measuring the pressure in the chamber. The sample chamber and the expansion chamber are connected by a connecting pipe having a valve. A helium gas introduction pipe having a stop valve is connected to the sample chamber, and a helium gas distribution pipe having a stop valve is connected to the expansion chamber.
The measurement was performed as follows. Using a standard sphere, the volume of the sample chamber (V _CELL ) and the volume of the expansion chamber (V _EXP ) are measured in advance.

A sample is put into the sample chamber, and helium gas is allowed to flow for 2 hours through the helium gas inlet tube, the connecting tube in the sample chamber, and the helium gas discharge tube in the expansion chamber, and the inside of the apparatus is replaced with helium gas. Next, the valve between the sample chamber and the expansion chamber and the valve of the helium gas discharge pipe from the expansion chamber are closed, and helium gas is introduced from the helium gas introduction tube of the sample chamber to 134 kPa. Thereafter, the stop valve of the helium gas introduction pipe is closed. Measure the pressure (P ₁ ) in the sample chamber 5 minutes after closing the stop valve. Next, the valve between the sample chamber and the expansion chamber is opened to transfer helium gas to the expansion chamber, and the pressure (P ₂ ) at that time is measured.
The volume of the sample (V _SAMP ) was calculated by the following formula.
V _SAMP = V _CELL −V _EXP / [(P ₁ / P ₂ ) −1]
Therefore, if the weight of the sample is W _SAMP , the density is ρ ^H = W _SAMP / V _SAMP .

7). Sphericality Negative electrode material embedded in epoxy resin, polished and observed with an optical microscope, 30 particles having an average particle diameter D ₅₀ ± 50% and no overlap with other particles and no contact A plane image analysis of particles was performed with a high-function image analysis system (“IP-500PC” manufactured by Asahi Engineering Co., Ltd.), and an average value of circularity C according to the following formula was used as a sphericity.
Circularity C = 4 · π · S / l ²
Here, l: circumference length, S: area.

8). Exothermic peak temperature measurement by differential thermal analysis 2.0 mg of negative electrode material was weighed in a platinum pan and placed in a differential thermal analyzer (TG / DTA6200, manufactured by SII Nanotechnology Inc.), and dried air at a flow rate of 100 ml / min. (Dew point −50 ° C. or lower) was flowed, and held at 200 ° C. for 1 hour. Thereafter, the temperature was increased at a rate of temperature increase of 10 ° C./min, the exothermic curve of the negative electrode material was measured, and the temperature showing the maximum calorific value was defined as the exothermic peak temperature.

9. Pore volume The pore volume by the mercury intrusion method was measured using Autopore III9420 manufactured by MICROMERITICS.
The negative electrode material is put in a sample container and deaerated at a pressure of 2.67 Pa or less for 30 minutes. Next, mercury is introduced into the sample container and gradually pressurized to press the mercury into the pores of the negative electrode material (maximum pressure 414 MPa). From the relationship between the pressure at this time and the amount of mercury injected, the pore volume distribution of the negative electrode material is measured using the following equation. The volume of mercury that was pressed into the negative electrode material from a pressure corresponding to a pore diameter of 5 μm (0.25 MPa) to a maximum pressure (414 MPa: equivalent to a pore diameter of 3 nm) was defined as a pore volume having a pore diameter of 5 μm or less. The calculation of the pore diameter is based on the assumption that when mercury is pressed into a cylindrical pore having a diameter D at a pressure P, the surface tension of the surface tension and the pore are given by the surface tension γ of mercury and the contact angle between mercury and the pore wall as θ. From the balance of pressure acting on the cross section, the following equation holds.
−πDγcos θ = π (D / 2) ² · P
D = (− 4γcos θ) / P
Here, the surface tension of mercury is 484 dyne / cm, the contact angle between mercury and carbon is 130 degrees, the pressure P is expressed in MPa, and the pore diameter D is expressed in μm. Sought a relationship.
D = 1.27 / P

10. Content of Nitrogen A nitrogen content was measured by a combustion method using a Sumika graph manufactured by Sumika Chemical Analysis.

11. Sulfur Atom Content The sulfur content was measured by ion chromatography using ICS2000 manufactured by Dionex.

12 Storage characteristics The initial efficiency of each of the negative electrode material immediately after production and the negative electrode material after the following storage test was measured according to the following method. Next, the change rate of the initial efficiency was calculated.

(Preservation test)
1 g of the negative electrode material was held for 7 days under conditions of a temperature of 40 ° C. and a relative humidity of 90% RH in a small environmental tester (SH-241 manufactured by ESPEC). The negative electrode material was spread in a container having a length of 5 cm, a width of 8 cm, and a height of 1.5 cm so as to be as thin as possible, and then left in the apparatus. Thereafter, the negative electrode material was dried by holding at a temperature of 130 ° C. for 1 hour under a nitrogen atmosphere.

(1) Production of half cell With respect to 100 parts of negative electrode materials obtained in Examples and Comparative Examples described later, 1.5 parts of carboxymethyl cellulose (manufactured by Daicel Finechem, CMC Daicel 2200), styrene-butadiene rubber (manufactured by JSR, TRD) -2001) 3.0 parts, 2.0 parts of acetylene black (manufactured by Denki Kagaku, Denka Black) and 100 parts of distilled water were added and stirred and mixed with a rotating / revolving mixer to prepare a negative electrode slurry.

The prepared negative electrode slurry was applied to one side of a 14 μm-thick copper foil (Furukawa Electric, NC-WS), then pre-dried in air at 60 ° C. for 2 hours, and then vacuumed at 120 ° C. for 15 hours. Dried. After vacuum drying, the electrode was pressure-formed by a roll press. This was cut into a disk shape having a diameter of 13 mm to produce a negative electrode. The thickness of the negative electrode active material layer was 50 μm.

Metallic lithium was formed in a disk shape with a diameter of 12 mm and a thickness of 1 mm to produce a counter electrode. In addition, a polyolefin porous film (manufactured by Celgard, trade name: Celgard 2400) was used as a separator.

Using the negative electrode, the counter electrode, and the separator described above, a mixed solvent obtained by mixing ethylene carbonate and diethyl carbonate at a volume ratio of 1: 1 as an electrolytic solution and adding LiPF ₆ at a ratio of 1 M was used in an argon atmosphere. A 2032 type coin cell-shaped bipolar half cell was manufactured in the glove box, and the evaluation described below was performed on the half cell.

(2) Charging / discharging of a half cell Charging / discharging was performed on the following conditions.
Measurement temperature: 25 ° C
Charging method: constant current constant voltage method, charging current: 25 mA / g, charging voltage: 0 mV, charging end current: 2.5 mA / g
Discharge method: constant current method, discharge current: 25 mA / g, final discharge voltage: 2.5 V

Further, the charge capacity and discharge capacity [mAh / g] per gram of the negative electrode material were determined based on the charge capacity and discharge capacity values obtained under the above conditions. Further, the initial efficiency and the rate of change of the initial efficiency were obtained from the following formula.
Initial efficiency [%] = 100 x (Discharge capacity) / (Charge capacity)
Rate of change in initial efficiency [%] = 100 x (initial efficiency after storage test) / (initial efficiency immediately after production)

[2] Production of negative electrode material (Example 1)
An oxidized pitch was prepared according to the method described in paragraph 0051 of JP-A-8-279358. Next, using this oxidized pitch as a raw material, the following steps (a) to (f) were carried out in order, whereby a negative electrode material 1 was obtained.

(A) In a heat treatment furnace having a furnace internal volume of 60 L (length 50 cm, width 40 cm, height 30 cm), 510 g of oxidation pitch was spread and allowed to stand as thin as possible. Thereafter, the temperature was raised from room temperature to 500 ° C. at 100 ° C./hour without any of reducing gas replacement, inert gas replacement, reducing gas flow, and inert gas flow.

(B) Next, degreasing treatment was performed at 500 ° C. for 2 hours without cooling gas replacement, inert gas replacement, reducing gas flow, and inert gas flow, and then cooled.

(C) The obtained powder was finely pulverized with a vibration ball mill.
(D) Thereafter, 204 g of the obtained powder was spread and allowed to stand as thin as possible in a heat treatment furnace having a furnace volume of 24 L (length 40 cm, width 30 cm, height 20 cm). Subsequently, the temperature was raised from room temperature to 1200 ° C. at 100 ° C./hour under inert gas (nitrogen) substitution and circulation.

(E) Under an inert gas (nitrogen) flow, it was kept at 1200 ° C. for 8 hours and carbonized.
(F) Under natural gas (nitrogen) circulation, the mixture was naturally cooled to 600 ° C., and then cooled from 600 ° C. to 100 ° C. at 100 ° C./hour.

In addition, the occupation ratio of the raw material with respect to the space which carbonizes is 8.5 kg / m < ³ >.

(Example 2)
Using the phenol resin PR-55321B (manufactured by Sumitomo Bakelite Co., Ltd.), which is a thermosetting resin, as a raw material, the following steps (a) to (f) were performed in order, and the negative electrode material 2 was obtained.

(A) 510 g of thermosetting resin was spread and allowed to stand as thin as possible in a heat treatment furnace having a furnace internal volume of 60 L (length 50 cm, width 40 cm, height 30 cm). Thereafter, the temperature was raised from room temperature to 500 ° C. at 100 ° C./hour without any of reducing gas replacement, inert gas replacement, reducing gas flow, and inert gas flow.

(B) Next, degreasing treatment was performed at 500 ° C. for 2 hours without cooling gas replacement, inert gas replacement, reducing gas flow, and inert gas flow, and then cooled.

(C) The obtained powder was finely pulverized with a vibration ball mill.
(D) Thereafter, 204 g of the obtained powder was spread and allowed to stand as thin as possible in a heat treatment furnace having a furnace volume of 24 L (length 40 cm, width 30 cm, height 20 cm). Subsequently, the temperature was raised from room temperature to 1200 ° C. at 100 ° C./hour under inert gas (nitrogen) substitution and circulation.

(E) Under an inert gas (nitrogen) flow, it was kept at 1200 ° C. for 8 hours and carbonized.
(F) Under natural gas (nitrogen) circulation, the mixture was naturally cooled to 600 ° C., and then cooled from 600 ° C. to 100 ° C. at 100 ° C./hour.

In addition, the occupation ratio of the raw material with respect to the space which carbonizes is 8.5 kg / m < ³ >.

(Example 3)
A negative electrode material 3 was produced in the same manner as in Example 2 except that the occupation ratio of the raw material with respect to the space to be carbonized was changed to 3.5 kg / m ³ .

(Example 4)
A negative electrode material 4 was produced in the same manner as in Example 2 except that the occupation ratio of the raw material to the space for carbonization treatment was changed to 0.9 kg / m ³ .

(Example 5)
A negative electrode material 5 was produced in the same manner as in Example 2 except that the occupation ratio of the raw material with respect to the space to be carbonized was changed to 0.5 kg / m ³ .

(Comparative Example 1)
A negative electrode material 6 was produced in the same manner as in Example 1 except that the occupation ratio of the raw material with respect to the space to be carbonized was changed to 16 kg / m ³ .

(Comparative Example 2)
A negative electrode material 7 was produced in the same manner as in Example 2 except that the occupation ratio of the raw material to the space for carbonization was changed to 16 kg / m ³ .

  Various evaluations described above were performed on the negative electrode materials 1 to 7 obtained in the above examples and comparative examples. The results are shown in Table 1.

DESCRIPTION OF SYMBOLS 10 Lithium ion battery 12 Negative electrode active material layer 13 Negative electrode 14 Negative electrode collector 16 Electrolyte 18 Separator 20 Positive electrode active material layer 21 Positive electrode 22 Positive electrode collector

Claims (12)

A negative electrode material for a lithium ion battery having an average layer spacing d _{002 of} (002) planes of 0.340 nm or more determined by an X-ray diffraction method using CuKα rays as a radiation source,
The ratio (ρ ^H / ρ ^B ) of the density (ρ ^H ) measured with helium gas as the replacement medium to the density (ρ ^B ) measured with butanol as the replacement medium is more than 1.05 and less than 1.25 Negative electrode material for ion batteries. A negative electrode material for a lithium ion battery having an average layer spacing d _{002 of} (002) planes of 0.340 nm or more determined by an X-ray diffraction method using CuKα rays as a radiation source,
A negative electrode material for a lithium ion battery, wherein an adsorption amount of carbon dioxide gas is less than 10 ml / g. A negative electrode material for a lithium ion battery having an average layer spacing d _{002 of} (002) planes of 0.340 nm or more determined by an X-ray diffraction method using CuKα rays as a radiation source,
A negative electrode material for a lithium ion battery, wherein the halogen content is less than 50 ppm. A negative electrode material for a lithium ion battery having an average layer spacing d _{002 of} (002) planes of 0.340 nm or more determined by an X-ray diffraction method using CuKα rays as a radiation source,
Contains nitrogen and sulfur atoms,
The nitrogen atom content is 1 ppm or more and 30000 ppm or less,
A negative electrode material for a lithium ion battery, wherein the sulfur atom content is 1 ppm or more and 30000 ppm or less. A negative electrode material for a lithium ion battery having an average layer spacing d _{002 of} (002) planes of 0.340 nm or more determined by an X-ray diffraction method using CuKα rays as a radiation source,
A negative electrode material for a lithium ion battery, having a pore volume of 0.003 μm to 5 μm determined by a mercury intrusion method and less than 0.55 ml / g. A negative electrode material for a lithium ion battery having an average layer spacing d _{002 of} (002) planes of 0.340 nm or more determined by an X-ray diffraction method using CuKα rays as a radiation source,
A negative electrode material for a lithium ion battery having a sphericity of less than 0.8. A negative electrode material for a lithium ion battery having an average layer spacing d _{002 of} (002) planes of 0.340 nm or more determined by an X-ray diffraction method using CuKα rays as a radiation source,
A negative electrode material for a lithium ion battery having at least one exothermic peak at less than 650 ° C. in a differential thermal analysis measured under an air stream.   The negative electrode active material containing the negative electrode material as described in any one of Claims 1 thru | or 7. The negative electrode active material according to claim 8,
A negative electrode active material further comprising a negative electrode material of a type different from the negative electrode material. The negative electrode active material according to claim 9,
A negative electrode active material, wherein the different types of negative electrode materials are graphite materials.   The negative electrode for lithium ion batteries containing the negative electrode active material as described in any one of Claims 8 thru | or 10.   A lithium ion battery comprising at least the negative electrode for a lithium ion battery according to claim 11, an electrolyte, and a positive electrode.

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