JP2003173774A - Anode material for lithium ion secondary battery and its manufacturing method and lithium ion secondary battery using same anode material - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide an anode material for a lithium ion secondary battery of high capacity, heavy load characteristics and excellent handling whose decomposition can be restrained even under existence of propylene carbonate used for portable equipment or the like such as a cellular phone, a PDA, and a personal computer, and its manufacturing method, as well as a lithium ion secondary battery using the anode material. <P>SOLUTION: The anode material for the lithium ion secondary battery wholly consists of graphite with its core material made of graphite particles, covered with a basal surface (100) and/or an amorphous coated part formed of a graphite skeleton. As the manufacturing method of an anode material for the lithium ion secondary battery, an amorphous pitch or crystalline pitch is first coated on a particle surface of a core material of carbon or graphite nature by a mechanochemical method, and then, is made unfusible, carbonized and graphitized so that a whole part covered with a basal face (100) with a particle surface formed of a carbon skeleton and/or an amorphous coated part is composed of graphite. <P>COPYRIGHT: (C)2003,JPO

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a negative electrode material for a lithium ion secondary battery used in portable equipment such as mobile phones, personal digital assistants, video cameras, personal computers, etc., a method for producing the same, and a method for producing the same. The present invention relates to a lithium ion secondary battery using the negative electrode material obtained by.

[0002]

2. Description of the Related Art Lithium ion secondary batteries have high power,
It is widely used as a high-capacity secondary battery in portable devices such as mobile phones, personal computers, and personal digital assistants (PDAs), and it is expected that the demand for it will further increase in the future. In response to the trend toward miniaturization of such portable devices, lithium ion secondary batteries are also required to be compact and lightweight.

Therefore, the performance of parts and materials constituting a lithium-ion secondary battery has been actively improved. The carbon-based negative electrode material that influences battery performance is no exception.

In recent years, a lithium polymer secondary battery using a polymer to gel an electrolyte and a thin and lightweight aluminum laminate film instead of a can has been put on the market, which contributes to further thinning and weight saving of the battery. It became so.

Among these secondary batteries, a lithium polymer secondary battery is a propylene carbonate (hereinafter referred to as P) as a plasticizer added to a gelled polymer electrolyte.
There are many examples of using C).

[0006] However, most of the graphite-based negative electrode materials currently used in the mainstream accelerate the decomposition of PC on the surface thereof, and in most cases, PC cannot be used for battery preparation. For example, G.I. C. Chung et al. Ele
c. Soc. 146 (5) 1664 (1999) and G.I. C. Chung et al. Elec. S
oc. 147 (12) 4391 (2000), the interaction between PC and the edge structure of the graphite surface is discussed in detail. In addition, M. Yoshio et a
1, J.I. Elec. Soc. 147 (4) 12
45 (2000), it was introduced that the PC resistance can be improved by coating the surface of natural graphite with carbon by CVD treatment, and it is now on the market.

However, since a costly method called CVD is used, it is unreasonable in that it is an inexpensive material required by battery manufacturers.

At present, for lithium polymer secondary batteries, MCMB, which has relatively good PC resistance, among the existing negative electrode materials.
It seems that (mesocarbon microbeads) are mainly used, but the capacity is about 300 to 310 mAh / g, which is insufficient in capacity for future high capacity batteries. In addition, the price is high, and it is difficult to reduce the cost of battery production.

[0009]

From such a situation,
As a negative electrode material for lithium-ion secondary batteries, it is possible to suppress the decomposition of propylene carbonate even in the presence of propylene carbonate, and has a high capacity, high load characteristics, and excellent handleability. Development is desired.

Therefore, an object of the present invention is to provide a mobile phone, a PD.
A, Lithium-ion secondary batteries used in portable equipment such as personal computers, which can suppress decomposition even in the presence of propylene carbonate, have high capacity, high load characteristics, and are easy to handle. It is to provide a negative electrode material.

Another object of the present invention is to provide a method for producing a negative electrode material for a lithium ion secondary battery having such excellent characteristics.

Further, another object of the present invention is to provide a lithium ion secondary battery using the negative electrode material obtained by the manufacturing method of the present invention.

[0013]

Means for Solving the Problems As a result of various studies to solve the above problems, the present inventors have found that a basal surface formed of a graphite skeleton on the surface of graphitized carbonaceous base material (core material) particles. By forming the entire surface covered with the (100) plane and / or the amorphous film portion with graphite,
The present invention has been completed by finding that a negative electrode material for a lithium ion secondary battery and a method for producing the same that can achieve the above object are obtained.

That is, in the present invention, a carbonaceous or graphitic base material (core material) is coated with an amorphous pitch or a crystalline pitch by a mechanochemical method, and after lightly infusible, carbonization and further graphite The difference in heat shrinkage between the core portion and the coating portion (skin portion) causes the skin portion, which has a larger heat shrinkage, to be tensioned in the circumferential direction of the core particles during carbonization, and as a result, the skin portion is made of graphite. Base of skeleton (1
The (00) plane and / or the plane of mixed state of the plane entirely covered with the amorphous coating portion is made of graphite.

As a result, even in the presence of PC (propylene carbonate), the interaction between the PC and the graphite edge structure is unlikely to occur, and the lithium ion battery having a high capacity capable of suppressing the decomposition of PC, a high load characteristic, and an excellent handleability. Carbon negative electrode materials for secondary batteries and lithium polymer secondary batteries can be prepared.

According to the method of the present invention, it is not necessary to use a material such as a solvent or a gas simply by performing a mechanochemical treatment after mixing in a dry system. Therefore, a facility for treating a solvent or a gas produced as a by-product. Moreover, it is not necessary to spend money on various environmental measures, and the manufacturing cost can be kept low.

When the negative electrode material of the present invention having excellent PC resistance obtained by the treatment as described above is used, a lithium ion secondary battery using an electrolytic solution containing PC having a high capacity and a small amount of gas generation. It is possible to manufacture a lithium polymer secondary battery using PC as a plasticizer.

As described above, in the lithium ion secondary battery negative electrode material of the present invention, the particle surface of the graphite core material is the basal plane (100) surface and / or the amorphous coating film portion formed of the graphite skeleton. The whole covered is made of graphite.

The method for producing a negative electrode material for a lithium ion secondary battery according to the present invention comprises a carbonaceous or graphitic core material (base material) having a grain surface formed of amorphous pitch or a skin material by a mechanochemical method. After coating the crystalline pitch, further infusibilization, carbonization and graphitization treatment is carried out, and the particle surface is formed of graphite skeleton. It is characterized by becoming.

Further, the lithium ion secondary battery of the present invention is characterized by using the negative electrode material obtained by the manufacturing method of the present invention.

[0021]

BEST MODE FOR CARRYING OUT THE INVENTION Hereinafter, a negative electrode material for a lithium ion secondary battery of the present invention, a method for producing the same, and a lithium ion secondary battery using the negative electrode material obtained by the production method will be described in detail. .

1. The core material carbonaceous particles are not particularly limited as long as the ratio a / b of the major axis a and the minor axis b of the particles is 2 or less and the orientation is small. Specifically, (1) a petroleum-based and coal-based calcined coke powder or raw coke powder having a needle-like portion (N ratio) of a crystalline portion of 50% or less in observation under a polarization microscope, ( 2) Any carbonized or graphitized mesophase pitch powder particles having a / b of 2 or less may be used. When the ratio a / b is greater than 2,
The coating of the pitch due to mechanochemical treatment becomes uneven, and the edge structure on the surface of the core material cannot be sufficiently covered,
It is not preferable because the PC resistance cannot be sufficiently exhibited. Further, the coke-based particles having an N ratio of more than 50% have a large orientation, and if this lump is crushed, it is easy for the coke-based particles to be exfoliated and crushed on the orientation surface, and the a / b exceeds 3 And similarly, the coating becomes non-uniform, which is not preferable.

2. Particle size of the core material If the average particle diameter of the core material is about the same as the commercially available negative electrode material,
It doesn't matter. Specifically, the average particle size of the core material is 5 to
It is preferably 50 μm. If the average particle diameter of the core material is 5 μm or less, the specific surface area becomes large, and as a result, even if it is used as a negative electrode material, the irreversible capacity during charging and discharging becomes large, which is not preferable. On the other hand, if the average particle size of the core material is 50 μm or more, it is not preferable because many particles exceeding the thickness of the negative electrode sheet, that is, particles of 80 μm or more are included in the particle size distribution. Even if the average particle size of the core material is 5 to 50 μm, the proportion of particles having a particle size of 3 μm or less needs to be 3% by volume or less, preferably 1% by volume or less.
If the abundance ratio of particles having a particle size of 3 μm or less is larger than this, it is not preferable because it remains as fine particles that are not deposited in the mechanochemical treatment.

3. Conditions for infusibilizing and carbonizing core material When using pitch as the core material, infusibilizing core material,
Carbonization is necessary, and for infusibilization, the core material is pulverized, then oxidized in air at 280 to 320 ° C. to be infusibilized, and the particles are sized and used. Carbonization of the core material thus obtained by infusibilization is preferably carried out in a non-oxidizing atmosphere such as carbon dioxide gas or nitrogen gas in order to prevent oxidative wear of the object to be treated, and the firing temperature is 700 The temperature may be higher than or equal to 0 ° C, but the temperature is preferably 1,200 ° C or lower. Baking temperature is 700 ℃
If it is less than 1, thermal decomposition is not sufficient in terms of carbonization, and 1
Temperatures over 200 ° C are not realistic in terms of furnace durability and manufacturing cost. The carbonaceous material thus obtained by firing in a non-oxidizing atmosphere is further subjected to 2800 to 3200 ° C.
It may be graphitized beforehand in the range of. At 2800 ° C or lower, crystallization of graphite does not proceed sufficiently, which is not preferable. Three
Substantially no treatment is possible at temperatures above 200 ° C.

4. Material of skin part The material of the skin part covering the surface of the carbonaceous material or the graphitized carbonaceous core material particles is optically isotropic or anisotropic, that is, having a softening point of 200 ° C. or more in mesophase pitch, 4
Those having a temperature of 00 ° C. or less and finely pulverized to have an average particle size of the core material or less are selected. If the softening point is 200 ° C or lower, it cannot be used for this purpose because it is difficult to infusibilize in the subsequent process, and if the softening point is 400 ° C or higher, there is virtually no softening point and the mechanochemical treatment is applied. It is not possible because it is not possible. Further, if the particle size of the material used for the skin portion is larger than the average particle size of the core material, the mechanochemical treatment time becomes long and uniform coating cannot be achieved, which is not preferable.

5. Mechanochemical treatment In general, mechanochemical treatment uses a crusher and the weight ratio of core material and skin material is 100/10 to 30.
However, in the present invention, since it is important to completely cover the surface of the core material, it is preferable to use a commercially available mechanochemical treatment device. Examples of commercially available devices include mechanofusion systems AM series and AMS series manufactured by Hosokawa Micron Co., Ltd., and a hybridizer NHS series manufactured by Nara Machinery Co., Ltd. By using these devices, a uniform coating can be formed on the core material surface in a few minutes to a few tens of minutes. When using a crushing machine, the grain size of the skin material should be at least 3 times the average grain size of the core material.
It is necessary to reduce the processing time to one-third or less and the processing time to at least four hours or more.

6. Insolubilization of skin part The mechanochemically treated product thus obtained is infusibilized by heat treatment in air. The temperature of infusibilization is not particularly limited, but it is usually 320 ° C. or lower for the purpose of preventing combustion of the processed material.

7. Firing of the skin portion Firing is performed in an inert gas atmosphere or a reducing atmosphere to remove volatile components in the infusibilized product. The firing temperature is not particularly limited, but 600 ° C. or higher is usually sufficient.

8. Graphitization of Skin Part The fired product obtained by the above treatment is graphitized in an inert gas or a reducing atmosphere to produce a negative electrode material for a lithium ion secondary battery. The graphitization temperature is 2800 ° C. or higher. When the graphitization temperature is lower than 2800 ° C, the discharge capacity is lowered, which is not preferable. In the process of graphitizing the skin portion, the carbonaceous core material used is also graphitized.

By such graphitization treatment, a mixed surface of the basal plane (100) plane and / or the amorphous plane formed of the graphite skeleton is selectively formed on the surface of the carbonaceous base material particles.

Next, a lithium ion secondary battery can be manufactured using the negative electrode material obtained by the manufacturing method of the present invention. The structure itself of this secondary battery is conventionally known, and for example, a solvent such as N-methyl-2-pyrrolidone in which a binder such as polyvinylidene fluoride is dissolved is added to the negative electrode material and sufficiently mixed to form a paste. . The mixing ratio (weight ratio) of the negative electrode material and the binder is 100: 5 to 100: depending on the particle size and the specific surface area of the negative electrode material.
It is desirable to set it to 15. In addition to PVDF, known materials such as EPDM (ethylene propylene diene monomer), styrene butadiene rubber (SBR), and polytetrafluoroethylene (PTFE) can be used for the binder. The paste thus obtained is applied to the surface of the copper foil using a doctor blade or the like, and this is dried at, for example, about 150 ° C. for about 1 hour and then rolled to form an electrode sheet.

The positive electrode material is not particularly limited, but in addition to the metal Li known in the art, LiCoO ₂ , L
Lithium-containing compounds such as iNiO ₂ or LiMn ₂ O ₄ or mixtures thereof can be used. Also, the separator is not particularly limited, and conventionally known materials can be used.

As the electrolyte, LiCl, LiBr, L
iCiO_Four , LiPF₆ , LiBF _Four , LiB (C₆ H
_Five )_Four Lithium salts such as
Can be used as a mixture.

Further, as an electrolytic solution, a lithium salt is dissolved, for example, propylene carbonate (PC), ethylene carbonate (EC), dimethyl carbonate (DM).
A known aprotic solvent having a low dielectric constant such as C) or methyl ethyl carbonate (MEC) may be used alone or in combination of two or more kinds thereof.

[0035]

According to the method for producing a negative electrode material for a lithium ion secondary battery of the present invention, the skin portion formed on the surface of the graphite base material has a base surface (100) surface of the graphite skeleton and / or
Alternatively, a mixed surface of amorphous surfaces is selectively formed, and as a result, even in the presence of PC (propylene carbonate), the interaction between PC and the graphite edge structure is unlikely to occur, and decomposition of PC can be suppressed. It is possible to prepare a carbon negative electrode material for a lithium ion secondary battery, which has high load characteristics and excellent handleability.

[0036]

EXAMPLES The present invention will be described in detail below with reference to examples and comparative examples. Example 1 A mesophase pitch having an average particle diameter of 18.4 μm and a softening point of 360 ° C. and a mesophase amount of 95% was heated in air at a maximum temperature of 300 ° C. for 1 hour for infusibilization.

After crushing the mesophase pitch obtained by infusibilization, it was heat-treated at 1000 ° C. for 1 hour in a nitrogen atmosphere,
Furthermore, it moved to the graphitization furnace and heat-processed at 3000 degreeC for 0.5 hour in argon atmosphere.

The graphite powder thus obtained was sized by dry classification so that 0% of particles having a size of 3 μm or less were obtained. The obtained graphite powder had an average particle size of 15.1 measured by using a particle size distribution analyzer LMS-30 manufactured by Seishin Enterprise Co., Ltd.
μm, X-ray diffraction measurement device (Rod B manufactured by Rigaku Corporation)
The Cu-Kα ray was monocolored with Ni using a system type), and the average inter-layer spacing (hereinafter referred to as d (002)) measured according to the "Japan Society for the Promotion of Science" was 0.3363n.
m, and the ratio a / b of the major axis a and the minor axis b of this particle was 1.51.

To 100 parts by weight of this graphite powder, 25 parts by weight of mesophase pitch, which is the same raw material as this graphite, was charged into a blender, treated for 5 minutes, and uniformly mixed. Further, mechanochemical treatment was performed for 0.25 hours using Mechanofusion AM80F manufactured by Hosokawa Micron Co., Ltd., and mesophase pitch was coated around the graphite powder. The thus coated mesophase portion was infusibilized at a maximum temperature of 300 ° C. for 1 hour while heating in air, and then the whole was crushed.

The powder thus obtained was calcined in a nitrogen atmosphere at 1000 ° C. for 1 hour, and then further heat-treated in an argon atmosphere at 3000 ° C. for 0.5 hour to obtain lithium ions having an average particle diameter of 15.6 μm. A hybrid carbon material for a negative electrode material of a secondary battery was obtained.

Example 2 Using the graphite powder obtained in the first half of the treatment step of Example 1, 25 parts by weight of an optically isotropic pitch was charged into a blender with respect to 100 parts by weight of this graphite powder. Similarly, a treatment was carried out for 5 minutes to uniformly mix them. Further, the same mechanochemical treatment as in Example 1 was carried out to coat the graphite powder with the optically isotropic pitch. This was air-oxidized at 300 ° C. for the pitch portion coated in air in the same manner as in Example 1, and then the whole was crushed. This powder was fired at 1000 ° C. in a nitrogen atmosphere and further heat-treated at 3000 ° C. in an argon atmosphere to obtain a hybrid carbon material for a lithium ion secondary battery negative electrode material having an average particle diameter of 15.9 μm.

Example 3 As a result of observation under a polarizing microscope, the ratio of needle-like portions (N ratio) in the crystalline portion was 48% and the average particle diameter was 18.9 μm.
25 parts by weight of the mesophase pitch used in Example 1 was charged in a blender for 5 minutes with respect to 100 parts by weight of the coal-based coke of m, and the mixture was uniformly mixed. Further, mechanochemical treatment was performed in exactly the same manner as in Example 1 to coat the coke powder with mesophase pitch. The pitch portion coated with this was further air-oxidized at 300 ° C. in air in the same manner as in Example 1, and then the whole was crushed. This powder is fired at 1000 ° C. in a nitrogen atmosphere, and further 3000 times in an argon atmosphere.
Heat treatment was performed at 0 ° C. to obtain a hybrid type carbon material for a lithium ion secondary battery negative electrode material having an average particle diameter of 16.3 μm.

Example 4 Example 1 was repeated except that the mechanochemical treatment was carried out for 4 hours by using a large-scale grinding machine manufactured by Ishikawa Plant Co., Ltd.
The treatment was carried out in exactly the same manner as in 1. to obtain a hybrid type carbon material for a lithium ion secondary battery negative electrode material having an average particle diameter of 15.9 μm.

Example 5 An average particle diameter of 15 was obtained by treating in exactly the same manner as in Example 1 except that the graphite powder and the mesophase pitch of Example 1 were mixed in an amount of 15 parts by weight of mesophase pitch with respect to 100 parts by weight of the graphite powder. A hybrid carbon material for a negative electrode material of a lithium ion secondary battery having a thickness of 1 μm was obtained.

Comparative Example 1 Softening point 3 with an average particle size of 18.4 μm used in Example 1
Mesophase pitch at 60 ° C and 95% mesophase amount was heat-treated at a maximum temperature of 300 ° C for 1 hour while heating in air to infusibilize, and after crushing, 10 minutes in an inert atmosphere.
It was heat-treated at 00 ° C. for 1 hour, transferred to a graphitizing furnace, and further heat-treated at 3000 ° C. for 0.5 hour in an argon atmosphere. This is sized by dry classification so that the particle size of 3 μm or less becomes 0%,
A carbon material for a negative electrode material of a lithium ion secondary battery having an average particle diameter of 15.2 μm was obtained.

Comparative Example 2 100 parts by weight of the graphite powder used in Example 1 was treated in exactly the same manner as in Example 1 except that 40 parts by weight of the mesophase pitch used in Example 1 was used. A 15.8 μm hybrid type carbon material for a lithium ion secondary battery negative electrode material was obtained.

Comparative Example 3 The same treatment as in Example 1 was carried out except that the final treatment temperature in Example 1 was set to 1000 ° C., and the average particle size was 15.7.
A hybrid carbon material for a lithium ion secondary battery having a thickness of μm was obtained.

Comparative Example 4 Example 1 was repeated except that the mechanochemical treatment was carried out for 1 hour using a large-scale grinding machine manufactured by Ishikawa Factory Co., Ltd.
The treatment was carried out in exactly the same manner as above to obtain a hybrid carbon material for a lithium ion secondary battery negative electrode material having an average particle diameter of 15.7 μm.

Comparative Example 5 A pitch containing no quinoline insoluble matter having a softening point of 82 ° C.
Heat-treated at 500 ° C. for 36 hours under a nitrogen stream to remove volatile matter 4.
5% coke was obtained. After crushing this, under a nitrogen stream 10
It was fired at 00 ° C., transferred to a graphitization furnace, and graphitized at 3000 ° C. in an argon atmosphere. This is 3 by dry classification
The particle size was adjusted so that the particle size of less than μm was 0%. The obtained graphite powder had an average particle size of 16.1 μm and d (002) of 0.33.
57 nm and a / b = 3.20. Thereafter, a mechanochemical treatment and a heat treatment were performed in the same manner as in Example 1 to obtain a hybrid carbon material for a lithium ion battery having an average particle diameter of 17.1 μm.

Comparative Example 6 100 parts by weight of the same graphite powder as in Example 1 was treated in exactly the same manner as in Example 1 except that 20 parts by weight of novolac type straight phenol resin was used, and the average particle size was 16.
A 9 μm hybrid type carbon material for a negative electrode material of a lithium ion battery was obtained. The results obtained in each of these Examples and Comparative Examples are summarized in Table 1.

Battery Performance Test N-methyl-2-pyrrolidone was mixed with 100 parts by weight of the carbon powders obtained in each of the examples and comparative examples and 10 parts by weight of polyvinylidene fluoride to form a paste. After applying this paste onto copper foil using a doctor blade, 1
After drying at 50 ° C. for 1 hour, it was pressed at 1 t / cm ² to obtain an electrode sheet having a thickness of 80 μm. Li metal was used for the counter electrode and the reference electrode, and 1M-LiClO ₄ / EC: ME was used as the electrolytic solution.
C (volume ratio 1: 1), and 1M-LiClO ₄ / PC:
Using two types of EC: MEC (volume ratio 1: 1: 2),
Each three-electrode type beaker cell was constructed and a charge / discharge test was conducted. The charge / discharge test was performed under the conditions described below. The charging condition was that the current density was 0.5 mA / cm ² until it reached 10 mV, and when the voltage reached 10 mV, it was switched to constant voltage charging and the current value reached 0.001 mA. The discharge conditions were a current density of 0.5 mA / cm ² and discharge to 1.5 V. Measurement environment temperature is 30 ℃, measurement range is 0.0
It is 1 to 1.5V. The average inter-layer spacing of the obtained carbon powder was determined by X-ray diffraction (in accordance with "Japan Society for the Promotion of Science"). Table 1 also shows each measurement result.

[0052]

[Table 1]

As is clear from the measurement results shown in Table 1, in all the examples of the present invention, the electrolytic solution was PC: E.
Also in the evaluation of C: MEC = 1: 1: 2, the discharge capacity was 320 mAh / g or more, and the charge / discharge efficiency was 90% or higher, which was good.

[0054]

According to the present invention, after the amorphous or crystalline pitch is coated on the particle surface of the carbonaceous or graphitic core material by the mechanochemical method, the infusibilization, carbonization,
The graphitization has an advantage that the initial charge / discharge capacity in the electrolytic solution containing PC is good and the usable range of the lithium ion secondary battery is widened.

   ─────────────────────────────────────────────────── ─── Continued front page    (72) Inventor Kyoko Kataoka             4-2-2 Minami, Takakaicho, Omihachiman City, Shiga Prefecture F-term (reference) 4G046 EA02 EB06 EC02 EC06                 5H029 AJ03 AJ07 AK03 AL07 AM03                       AM07 AM16 DJ16 DJ17 DJ18                       HJ05 HJ13                 5H050 AA08 AA13 BA17 CA07 CB08                       DA03 DA09 EA08 FA17 FA18                       FA19 FA20 GA02 GA22 GA27                       HA05 HA13 HA14

Claims (10)

[Claims] 1. Lithium characterized in that the surface of particles of a core material made of graphite is entirely covered with a basal plane (100) surface formed of a graphite skeleton and / or an amorphous coating film portion and is made of graphite. Negative electrode material for ionic secondary batteries. 2. The lithium ion secondary particle according to claim 1, wherein the core material particles are carbonaceous particles having a ratio a / b of a major axis a and a minor axis b of 2 or less. Negative electrode material for batteries. 3. The lithium ion secondary battery according to claim 1, wherein the core material has a particle size of 5 to 50 μm, and the abundance ratio of particles of 3 μm or less is 3% by volume or less. Negative electrode material. 4. The particles of a carbonaceous or graphitic core material are coated with amorphous pitch or crystalline pitch as a skin material by a mechanochemical method, and then subjected to infusibilization, carbonization and graphitization. A method for producing a negative electrode material for a lithium ion secondary battery, wherein the surface is a basal plane (100) surface formed of a graphite skeleton and / or the whole is covered with an amorphous coating film part made of graphite. 5. The lithium ion secondary particle according to claim 4, wherein the core material particles are carbonaceous particles having a ratio a / b of a major axis a and a minor axis b of 2 or less. Manufacturing method of negative electrode material for battery. 6. The carbon of petroleum-based and coal-based calcined coke powder, raw coke powder, and mesophase pitch powder, wherein the core material has a needle-like portion of a crystalline portion of 50% or less when observed under a polarization microscope. 7. The method for producing a negative electrode material for a lithium ion secondary battery according to claim 4, which is selected from a compound and a graphitized product. 7. The lithium according to claim 4, wherein the core material has a particle size of 5 to 50 μm, and the existence ratio of particles of 3 μm or less is 3% by volume or less. A method for manufacturing a negative electrode material for an ionic secondary battery. 8. The skin material according to claim 4, wherein the skin material has an optically isotropic or anisotropic mesophase pitch and a softening point of 200 ° C. or higher and 400 ° C. or lower. Item 8. A method for producing a negative electrode material for a lithium ion secondary battery according to item. 9. The lithium according to any one of claims 4 to 8, wherein the mechanochemical treatment is a mixing and grinding treatment with a weight ratio of the core material and the skin material of 100: 10 to 30. A method for manufacturing a negative electrode material for an ionic secondary battery. 10. A lithium ion secondary battery using the negative electrode material obtained by the manufacturing method according to claim 4.