TWI271382B - Graphitic material and method for manufacturing the same, and anode material and anode lithium ion secondary battery, and lithium secondary battery - Google Patents

Abstract

Protuberances having height of at least 1 mum are scattered on a graphitic material. The graphitic material is suitable for an anode or an anode material of a lithium-ion secondary battery. By use of the anode, a lithium-ion secondary battery having large capacity, high initial charge-discharge effects, excellent rapid charge-discharge behavior and distinguished recyclability can be obtained. The present invention further provides a method for manufacturing the graphitic material, easily at a low cost.

Description

1271382 IX. The invention relates to a graphite material and a method for producing the same, a negative electrode material for a lithium ion secondary battery containing the graphite material, a negative electrode containing the negative electrode material, and a negative electrode using the same Lithium ion secondary battery. [Prior Art] In recent years, with the miniaturization or high performance of electronic equipment, the demand for increasing the energy density of batteries has become higher and higher. In particular, lithium ion secondary batteries are more likely to achieve higher voltage density than other Φ secondary batteries, and thus have attracted attention. The lithium ion secondary battery is mainly composed of a negative electrode, a positive electrode, and a nonaqueous electrolyte. The lithium ion generated from the nonaqueous electrolyte moves between the negative electrode and the positive electrode during the discharge process and the charging process, thereby forming an m secondary battery.

Generally, a carbon material is used as a negative electrode material of a lithium ion secondary battery. Such a carbon material is considered to be advantageous in the case of graphite having excellent charge and discharge characteristics and exhibiting high discharge capacity and potential flatness, as described in Japanese Patent Publication No. Sho 62-2233. The graphite or graphite material used as the negative electrode material can be exemplified as follows. That is, graphite particles such as natural graphite or artificial graphite. Blocky mesophase graphite particles or mesophase small spherical graphite particles obtained by heat treatment of meso-phase pitch or mesophase microspheres using tar (t a r) and/or pitch as raw materials. The mesophase graphite particles or the mesophase graphite fibers obtained by heat treatment after the granules of the particulate or fibrous intermediate phase are oxidized and not melted. After the tar, asphalt, etc. are covered with natural graphite or artificial graphite, the composite graphite particles obtained by heat treatment according to the 5 3 26\patent specification (supplement) \94-11 \94127847 1271382. In addition, for the purpose of improving the rapid charge and discharge characteristics or the cycle characteristics, a negative electrode material for a lithium ion secondary battery obtained by blending a conductive material with the above various graphite materials to be composited is reviewed. For example, Japanese Laid-Open Patent Publication No. Hei. No. Hei. No. Hei. Japanese Patent Laid-Open No. Hei 6- 1 i 1 8 1 8 and Japanese Patent Publication No. Hei 1 1 - 1 7 6 4 4 2 disclose a carbon fiber of 3 to 30% by mass mixed with vapor phase growth in mesophase small spherical graphite. In the case of the granule graphite or the flaky graphite, the fibrous graphite is contained in the spheroidal graphite or the scaly graphite. The negative electrode material is a lithium ion secondary battery, and the discharge capacity or initial charge and discharge efficiency is not greatly deteriorated, and the rapid charge and discharge characteristics or the cyclic scaly property can be improved. However, in the negative electrode material in which only carbon fiber or fibrous graphite is blended, In some cases, since the discharge capacity or the initial charge and discharge efficiency of the graphitized carbon fiber itself is lower than that of the parent graphite, the discharge capacity of the negative electrode material may be caused or

The problem of reduced charge and discharge efficiency. Moreover, these fibers have less chance of contact with the parent graphite, and most do not contribute to the improvement of conductivity. As a result, it is difficult to achieve a sufficient level of rapid charge/discharge characteristics or cycle characteristics. Further, since the carbon fiber grown in the vapor phase is relatively expensive and requires a large amount of mixing of 3 to 20% by mass, the manufacturing cost is increased. Further, in the case of producing a negative electrode, a method of preparing a negative electrode mixture paste by mixing a negative electrode material, a solvent and a binder to prepare a current collector is generally employed. However, if a negative electrode material blended with carbon fiber is used, there is a problem that the viscosity of the negative electrode mixture paste is unstable due to the large amount of carbon fiber mixed. In Japanese Patent Laid-Open Publication No. Hei. No. 2000-196, the disclosure of the utility model discloses a negative electrode material in which a metal catalyst is dispersed on a surface of a carbon material, whereby a catalyst is used to make a carbon fiber or a carbon nanotube. Vapor phase growth is carried out and used directly as a negative electrode active material. In the case of the negative electrode material, a carbon fiber or a carbon nanotube is formed using the catalyst as a starting point, whereby the conductivity between the graphite materials can be improved. However, since the formed carbon nanotubes or carbon fibers are grown from a catalytic metal (which is present on the surface of the Φ graphite material or on the surface of the amorphous carbon film), it is liable to be detached from the graphite material or easily broken. Therefore, the effect of improving the charge and discharge efficiency or the cycle characteristics is sometimes small. Further, since the catalyst metal remains in the negative electrode material obtained by _, the battery characteristics may be adversely affected. In addition, the cost of the industry is increased due to the complicated manufacturing steps and low yield. The mother particles of the mesophase small spheres and the like shown in Japanese Patent Laid-Open Publication No. Hei No. 1 1 - 2 6 5 7 1 6 are embedded in the amorphous carbon by mechanical force.

Particles. In the case of the negative electrode material, amorphous carbon or the like having an average particle diameter as small as 100 nm or less is attached to the surface to increase the specific surface area of the negative electrode material and increase the specific surface area of the contact with the electrolyte, thereby improving Reactivity. However, even if the average particle diameter of the child particles which may adhere to the mother particles is less than 100 nm due to mechanochemical treatment, the child particles of the formed composite particles are easily detached due to the stirring force when preparing the negative electrode mixture paste. . Moreover, in this method, it is difficult to attach a sub-particle of an average particle diameter of more than 1 0 0 nm (= 0. 1 // m ) to 7 326\patent specification (supplement)\94-11 \94127847 127138.2, and The effect of rapid charge and discharge characteristics is insufficient. Japanese Laid-Open Patent Publication No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. This production method is characterized in that it promotes graphitization by a metal using the metal compound, and promotes the graphiteization of the low crystallinity portion to increase the capacity. However, if only the graphitization of the graphite for the negative electrode is increased, the effect of improving the conductivity or the reactivity is inferior to that of the prior art described above, which cannot meet the requirements of the recent south-level rapid charge/discharge characteristic or cycle characteristics. The present invention has been made in view of the above circumstances. In other words, it is an object of the invention to provide a graphite material which is excellent in rapid charge and discharge characteristics and cycle characteristics when a negative electrode material for a lithium ion secondary battery is used, which has a high discharge capacity and high initial charge and discharge efficiency. Further, it is also an object of the invention to provide a method for producing the graphite material which is simple and inexpensive. Further, the object of the invention is to provide a negative electrode material for a lithium ion secondary battery using the graphite material, a negative electrode containing the negative electrode material, and a lithium ion secondary battery using the negative electrode.

SUMMARY OF THE INVENTION The present invention is a graphite material in which ridges having a height of 1 // m or more are dispersed. Further, the average ratio of the height (h) of the ridge height (h) to the length (g) of the substrate (h / g) is preferably 0.1 to 1.5. Further, these graphite materials preferably have an average particle diameter of 3 to 1 0 0 # m. Further, any of the above graphite materials is preferably a graphite of a mesophase small sphere. Further, the present invention provides a method of ion-containing 8 326 \ patent specification (supplement) \94-11\94127847 1271382 containing any of the above-mentioned graphite materials. Or, in order to disperse the precursor on the precursor, in addition to at least a part of any of the above-mentioned manufacturers, having an optical isotropic, the present invention provides a property of producing a carbon-reactive material and a soluble metal material. After the graphitization, the carbon source material of the 'crystalline structure is used as a negative electrode material for secondary batteries. Further, the present invention also provides a negative electrode for a lithium ion secondary battery containing a material. Further, the present invention also provides a lithium ion secondary battery. Furthermore, the present invention is also a ridge having a height of 1/im or more in addition to the stone. In addition, the present invention also provides a system for making a metal material having a property capable of reacting with carbon in a non-solution contact so that the metal The material is heated at a temperature at which it is dispersed. r* is again pressed, and the precursor is mixed with the precursor in this manufacturing method to make the method. Or, in order to mix the gold, remove the dispersion medium, and

In the negative electrode material for an ion secondary battery, the ink material for the negative electrode for a lithium ion secondary battery is characterized in that the method for producing a graphite material on the surface is in the nature of the substance and the property of dissolving carbon. In at least the state, the precursor of the graphite material is attached to the precursor, and at 150 ° C, preferably, the metal material of the metal material is dispersed in the precursor material and the precursor The metal material in the dispersion medium is dispersed in the precursor. The metal material is preferably a PVD method or a CVD method. In the method, the crystal structure of the precursor on the surface is preferred. The method of the graphite material is characterized in that at least one of the properties of the carbon-decomposing property is capable of forming an optical isotropic mixture at least in part, so that the mixture adheres to the graphite 9 326\patent specification (supplement)\94-11 94127 847 1271382 The material is preferred. Furthermore, the sphere is more than [the implementation of the following lithium separation 10 ^ very different ^ lithium ionization of electricity (graphite on this hair from 3 points 2 drums

3 and the parent system, for example, is not substantially higher, and the size of the graphite ink between the precursors is heated at a temperature above 1 500 °C.

In any of the production methods, the heating temperature is 1,500 to 3,300 ° C. In any of the above production methods, the precursor is preferably an intermediate phase. Means] The present invention will be further specifically described. The sub-secondary battery usually has a non-aqueous electrolyte, a negative electrode, and a positive electrode as its main elements. These elements are for example enclosed in a battery can. The negative electrode and the carrier that is acting as a lithium ion function. This is based on the fact that during charging, the ions are trapped in the negative electrode, and during discharge, lithium ions are removed from the negative electrode. Ten materials) If the graphite material is clearly viewed as shown in Fig. 1, it is present on the surface 2 of the base material 1. The ridge 3 is formed in a state of being formed from the base material 1 and is substantially homogeneous with the base material 1 . There is no material interface or boundary between the ridges. The ridge 3 has a hemispherical shape to a spherical shape and/or a cylindrical shape in which the head is spherical, and is a spherical or curved body in which no ridge line exists. However, it is here. However, the shape of the ridge 3 is in a hemispherical to spherical ratio, and the higher the ratio of the spherical shape, the better. Because of the formation of such a shape, when the material is used in a negative electrode material for a lithium ion secondary battery, the joints of the stones increase each other, and the point of energization also increases, so that the formed space reaches a suitable electrolyte (hereinafter, the electrolyte solution is also It is called electrolyte) 10 326 \ patent specification (supplement) \94-11\94127847 1271382 permeability. This ridge 3 is different from the wavy continuous wrinkle 4 (which is usually formed on the surface of the material when it is produced by graphitization), and is dispersed in some cases. However, the ridge 3 may be formed on the wrinkle 4. Further, the base material referred to in the present invention is also known from Fig. 1. When one of the graphite materials is individually viewed, it is assumed that the portion where the residual portion reaches the maximum volume is removed when it is considered to be a portion such as a bulge, a wrinkle, and/or an adhering matter. The height of the ridge is from the height of the base of each ridge to the highest point (h) and is '1//πι or more. When the graphite material φ material is used for the negative electrode material of the lithium ion secondary battery, the contact points of the graphite materials are increased, and the space formed is moderately increased, which can be increased as follows. The improvement effect of the battery characteristics described above. The height of the ridge is preferably 2 to 1 5 // m, and more preferably 3 to 10 / / m. Further, the average ratio (h / g) of the height (h) from the substrate to the highest point to the base length (g) of the ridge is preferably from 0.1 to 15. The average value is further preferably from 0.2 to 5, and more preferably from 0.5 to 3. When such a value is set, the aforementioned effects are further increased, and the battery characteristics are further improved. The base length (g) of the ridge is the length at which the lowermost portion of the ridge is in contact with the base material when the profile of the ridge is observed. The substrate length (g) is preferably from 1 to 10 // m. Further, the height of the ridge (h), the length of the substrate (g), and the ratio (h/g) were measured by observing the cross section of the scanning electron microscope, and the average value of the values of the complex ridges was measured. In particular, h / g is the average of the complex number h / g obtained for each ridge. A schematic cross-sectional view of the embossed graphite material is shown in FIG. In this figure, h and g are shown. Furthermore, the meaning of dispersion exists as a plurality of ridges 3 dispersed and present on the surface of the base material of the 11 326 \patent specification (supplement) \94-11\94127847 1271382. This dispersion may be regular or irregular, but it is preferable to have no deviation. The number of ridges of the graphite material is preferably in the range of several to several tens of degrees per 1 Ο Ο μ m 2 of the surface. It is preferable that the ridges are present without deviation on the surface of the graphite material and dispersed in the density range.

The size of the base material is preferably from 1 to 1 0 0 // m, and preferably from 2 to 4 5 // m. If the size of the base material is within such a range, the ratio of the average particle diameter of the graphite material to the height of the ridges becomes a preferable range, and when the graphite material is used for the anode material of the lithium ion secondary battery, the battery characteristics (especially The improvement effect of the rapid charge/discharge characteristics or the cycle characteristics) becomes large. Further, the average particle diameter referred to herein is based on a cross-sectional observation using a scanning electron microscope, and the maximum major axis length of the base material particles (excluding the ridge) and the length of the axis orthogonal thereto are measured, and the average value thereof is The particle size of the particles is then measured by a plurality of particles to obtain an average value. The average particle diameter of the graphite material of the present invention is an average particle diameter in terms of volume of 3 to 100 / / m, and particularly preferably 3 to 50 # m. When the ratio is 3/m or more, the initial charge and discharge efficiency of the lithium ion secondary battery using the material is improved, and when it is below 1.00 m, the rapid charge and discharge characteristics and the cycle characteristics are advanced. The volume-converted average particle size is the particle diameter at which the cumulative degree of particle size distribution becomes 50% by volume under the use of a laser diffraction type particle size distribution meter. In the present invention, unless otherwise specified, only "average particle diameter" is used, and means the particle diameter measured in accordance with this method. The ratio of the height of the ridge (h) to the average particle size (d) of the graphite material is preferably 12 326\patent specification (supplement)\94-llWl27847 1271382 The range is h / d = Ο . Ο 5~Ο . When it is within such a range, it is effective in improving the battery characteristics by taking into consideration the mutual contact of the graphite materials and the space formation. The graphite material of the present invention is not particularly limited in shape, but may be any shape such as a granular shape, a massive shape, a spherical shape, an ellipsoidal shape, a plate shape, a fibrous shape, a film shape, or a scale shape, but with an aspect ratio. 3 or less is preferable, and 2 or less is more preferable. It is particularly suitable for a spherical shape, that is, a spherical shape or a granular shape having an aspect ratio close to 1. When the aspect ratio is 3 or less, the rapid charge and discharge characteristics and cycle characteristics of the lithium ion secondary battery using the graphite material are improved. When the negative electrode is formed, the graphite material is not aligned in one direction, and the electrolyte is liable to permeate inside. Here, the aspect ratio represents the ratio of the maximum major axis length of the graphite material to the length of the axis orthogonal thereto, based on the average of the ratios of the respective measured graphite materials based on the cross-sectional observation using the scanning electron microscope.

The term "graphite material" as used in the present invention means a material mainly composed of carbon of a graphite structure. Here, the meaning of "main" is not particularly limited as long as the object of the invention can be attained, and the graphite material itself according to the present invention usually has a carbon content of about 80% or more. Therefore, the graphite material referred to in the present invention also includes the graphite itself, and includes a graphite material before the precursor is graphitized (hereinafter, also referred to as graphitized material). The graphite material precursor is a carbon material that is easily graphitized when subjected to heat treatment at a temperature of 150 ° C or higher. In addition, the carbon material referred to in this case also contains the carbon material itself. However, since the graphitization treatment is carried out at a high temperature, in order to remove the intermediate material, as long as the graphite material of the present invention can be obtained, the carbon content of the precursor is not required. 13 326\Patent specification (supplement)\94-11\94127847 1271382 The average lattice plane d " 2 of the (Ο Ο 2 ) plane of the graphite material of the present invention at the X-ray wide-angle diffraction is 0. 3 4 Below nm, particularly preferably 0.33 7 nm or less, further preferably 0.33 3 5 5 nm or less. This indicates that the crystallinity is high, and when used as a negative electrode material for a lithium ion secondary battery, a high discharge capacity can be obtained, and high conductivity can be obtained. In the present invention, the ridges are integrated with the base material, and the two are substantially homogeneous. It is difficult to separate the ridge from the base material to evaluate the crystallinity, but the groove spacing d is measured when the ridge is only removed from the base material. . 2 is preferably 0. 3 4 n m or less.

Here, the average lattice surface interval d of the (0 0 2 ) plane at the time of X-ray wide-angle diffraction is called d. . The 2 series X-rays use the C u Κ α line, and the standard material uses high-purity 矽, and the diffraction peak of the (0 0 2 ) plane of the graphite material particles is measured, and is calculated from the position _ of the peak. The calculation method is in accordance with the Xue Zhen method (measurement method determined by the 17th Committee of the Japan Society for the Promotion of Science), specifically, based on "carbon fiber" [Otani Shiro, 7 3 3 - 7 4 2 pages (1 9 8) The value measured by the method described in the Modern Compilation Society, March 6). The graphite material of the present invention is compared with a graphite material without bulging

The specific surface area is large, and the value is preferably 0.5 to 2 0 m 2 /g, particularly preferably 1 to 10 m 2 /g. If it is below 20 m2 / g, the viscosity of the negative electrode mixture paste will be stabilized, and the viscosity will be easily adjusted to improve the bonding strength by the binder. When it is 0.5 m 2 /g or more, the number and/or size of the ridges is increased, and the desired effect of the present invention can be easily achieved. The specific surface area was determined in accordance with the BET method using nitrogen adsorption. The ridge of the graphite material of the present invention is integrated with the base material, and the composite particles thereof are combined with the prior art (by mechanical force imparting/embedding microparticles, or by bonding 14 326\patent specification (supplement)\94-11\ In the case of the external mechanical force, the bulge is hard to fall off from the base material. Further, since the ridge of the present invention is larger than the composite particles of the prior art, the joint between the graphite materials can be increased, and the void of the electrolyte penetration can be ensured. Since these characteristics complement each other, the battery characteristics of the negative electrode for a lithium ion secondary battery can be improved as will be described later. The graphite material of the present invention may be mixed, encapsulated, coated or laminated with a dissimilar graphite material, a carbon material (non-φ crystalline hard carbon, etc.), an organic substance, and a graphite of the present invention within a range not impairing the object of the present invention. The material is subjected to liquid treatment, heat treatment, physical treatment, and the graphite material of the present invention is characterized by rapid charge and discharge characteristics and cycle characteristics. However, when the negative electrode is inferred as follows, the ridges do not fall off the joints of the materials, and the resistance increases. The improvement in the productivity of the graphite material increases the packing density when it is charged with the base material having a high degree of graphitization, so that a high energy density is obtained. Further, since the quality is very permeable, the diffusibility of the electrolyte is improved, and the specific surface area of the rapid discharge rate is increased, which may cause a rapid discharge rate of lithium ions, a rapid charge rate, a metal compound, and the like. Further, various chemical oxidation treatments in the phase, gas phase, and solid phase may be used. As a negative electrode material, it can be improved. As for its mechanism, it has not yet been explained. That is, the bulge is integrated with the base metal. Further, due to the bulging, the graphite is reduced and the conductivity is improved. As the conduction becomes higher, the discharge capacity increases. Since the ridge is soft and flexible, the discharge capacity in the volume unit is increased, and the gap formed by the ridge is large, and the amount of holding of the electrolysis is increased. Therefore, the strontium ion is improved. Moreover, due to the existence of the uplift and the increase in access points, this will also help to improve. In addition, since the specific surface is increased by 15 326\patent specification (supplement)\94-11\94127847 1271382, the bonding force to the adhesive during the manufacture of the negative electrode becomes large, so that the graphite material can be maintained even if the charge and discharge are repeated. Contact with each other can also show excellent cycle characteristics. (Manufacturing of Graphite Material) The graphite material of the present invention can be produced by any method which can produce a graphite material having a bulge on the surface. However, the method of imparting the mechanical material to the base material to embed the fine particle portion corresponding to the bulging or the method of adhering the adhesive component is excluded, and the obtained graphite material cannot sufficiently exhibit the effects of the present invention. - A representative production method of the present invention is exemplified below. _ Step (1)··Graphite material precursor (hereinafter, simply referred to as precursor). It is adjusted to the specified shape and size by pulverization, classification, etc. in advance. Step (2): contacting a metal material having a property reactive with carbon and/or having a property of dissolving carbon with the adjusted precursor in a non-solution state, so that the metal material is dispersed in the The precursor is on the outer surface. In addition, the term "metal material" as used herein refers to a metal and/or metal compound. Also, the reaction with carbon is usually a carbonization reaction. Step (3): The precursor obtained by dispersing the metal material obtained in the step (2) on the outer surface is heated at a temperature of 1,500 ° C or higher to carry out graphitization to obtain a graphite material. Next, the above steps will be described in detail. The graphite material precursor used in the step (1) can be formed into a graphite structure by at least a part of which has an easily graphitizable property, that is, when it is heat-treated at a temperature of 1,500 ° C or higher. 16 326\Patent specification (supplement) \94-11\94127847 1271382 As the precursor, a mesophase small carbon body or a mesophase fired body (also referred to as a bulk intermediate phase) may be exemplified as the intermediate phase carbon material. And mesophase fibers, etc., and coke-based carbon materials such as petroleum coke, needle coke, raw coke, green coke, pitch coke, and the like. Further, for example, the mesophase carbon material is formed by heat treatment from a petroleum system containing a free carbon or a coal-based tar or pitch in an inert gas atmosphere at a temperature of 350 to 450 ° C. The heat-treated product of the phase small sphere can be obtained by removing the matrix. The graphite material precursor of the present invention is preferably the above-described mesophase-based carbon material, and particularly preferably a mesophase small sphere which can easily achieve the above-described preferred longitudinal φ aspect ratio. Further, in order to prevent the graphite material precursor of the present invention from being melted when it is heat-treated at a temperature of not less than 1,500 ° C, the precursor is preferably used in a preliminary heat treatment. The final temperature of the preliminary heat treatment is less than 1 500 ° C, preferably less than 80 ° C. After the preliminary heat treatment, it is preferred to adjust the shape and size of the graphitized graphite material in advance. example

For example, it is preferable to apply a preliminary heat treatment to a mesophase small sphere having an average particle diameter of 1 to 1 0 0 // m at a temperature of 800 ° C or less, and directly (or after pulverizing) to obtain an average particle diameter. Small blocky particles. The method of pulverization and classification is not particularly limited. Furthermore, the preliminary heat treatment can be carried out twice or more. The metal material having the property of reacting with carbon and/or having the property of dissolving carbon used in the step (2) may, for example, be a metal such as Na, K or the like; an alkaline earth metal such as Mg or Ca; Ti, V, Cr, Mn, Fe, Co, Ni, Zr, Nb,

Transition metals such as Mo, Tc, Ru, Rh, Pd, Hf, Ta, W, Re, Os, Ir, P t; metals such as Al and Ge; and semimetals such as B and Si. In addition, the hydroxides and oxides of the metal exemplified above can also be exemplified. 17 326\Patent Specification (Supplement)\94-11\94127847 1271382 Nitrogen can be dissolved

The melting of the substance

The total material is a metal compound such as a sample, chloride and/or sulfide. These metal compounds may be used singly or in combination of two or more. It is also possible to mix a metal with a metal compound. In particular, at least one selected from the group consisting of compounds of metals such as Ti, Fe, Co, Ni, Ru, Rh, Pd, Os, Ir, and Pt is preferred. These gold materials are kept stable until they react with the carbon of the precursor, or are easily decomposed, and are all evaporated in the graphitization treatment of the step (3) described later, and are removed from the obtained graphite material. In the step (2), such a metal material is dispersed and present on the outer surface of the graphite material precursor. In this case, the metal material is brought into contact with the precursor in a non-solution state. In the case where the metal material is brought into contact with the precursor in a solution state, the metal material expands in the film form to the precursor, resulting in insufficient dispersion, or no bulging, or too small bulging. Representative examples of the non-solution state include a solid phase state and/or a gas phase state of the metal compound. Further, the metal compound may be melted and dispersed in a liquid phase state on the outer surface of the precursor. In other words, the purpose of specifying the non-solution state is to exclude contact with the precursor using only the solution of the metal. For example, even if the metal compound is partially dissolved in a solvent, it is equivalent to the non-solution state of the present invention as long as the insoluble portion is utilized. After adjusting the saturated solution of the metal compound, the suspension obtained by the insoluble solution of the metal compound by the operation is also equivalent to the non-solution state of the present invention. Further, in the case where a suspension in which a gold compound is added to a saturated solution of a metal compound is used, the suspended portion corresponds to a non-solution state, and is included in the technique 326 of the present invention (patent) (94) \94127847 18 1271382 Within the scope of surgery. As used herein, "outer surface" means the surface of each of the outer sides of the precursor, i.e., the surface of the plurality of graphite material precursors that are in contact with each other. Therefore, even if the precursor of the graphite material is porous, the void surface existing inside each of the precursors is not included.

The size of the adhered metal material is preferably 5 #m or less, more preferably 0. 0 1 to 5 vm, and more preferably 0.01 to l//m. Below 5/m, the ridges (i.e., the features of the graphite material of the present invention) are too large to maintain a suitable substrate length. Further, when the thickness is 0.01 or more, the size of the ridge is moderate, and the effects of the present invention can be easily obtained. Here, the size of the attached metal material is measured for the metal material in contact with the graphite material precursor, and the average length of each of the plurality of metal materials is measured under a scanning electron microscope. Further, the adhesion amount of the metal material is converted according to the amount of the metal, and the amount of the graphite material precursor is 0.1 to 30% by mass, preferably 0.5 to 5% by mass, and 1 to 1% by mass. 10% by mass is better. When it is at least 0.1% by mass, the effects of the present invention can be sufficiently obtained. On the other hand, when it exceeds 30% by mass, the effect of the present invention tends to be saturated, and economically, it may be 30% by mass or less. Further, the amount of adhesion of the metal material can be converted into a metal amount by means of I C P luminescence spectrometry or the like. Specific examples of the method for dispersing such a metal material on the outer surface of the precursor of the graphite material are given. (a) A method of mixing the precursor with a powdery metal material. (b) After the precursor is mixed with the metal material in a dispersion medium, the method of dispersing the medium of 19 326\patent specification (supplement)\94-11\94127847 1271382 is removed. (c) a method of attaching the metal material to the outer surface of the precursor by a PVD (Physical Vapor Deposition) method or a CVD (Chemical Vapor Deposition) method. In the method (a), the metal material in the form of a powder is used. Here, the average particle diameter of the metal material is preferably 0. 0 1 to 5 // m, and more preferably 0. 0 1 to 1 // m. Below 5 // m, the length of the base of the ridge (i.e., the feature of the graphite material of the present invention) is within a suitable range. Further, when it is 0.01//m or more, the size of the ridge Φ is also moderate, and the effect of the present invention can be increased. _ The mixing system may be a conventional mixer such as a reciprocating stirring type, a rotary stirring type, a vibration stirring type or the like. There is no special requirement for the stirring power, but it is more convenient to use the mechanical mechanical type. Regardless of the method employed, it is important to uniformly disperse the metal material in such a manner that the metal material is not agglomerated, and the metal material is attached in such a manner as to be dispersed on the outer surface of the precursor. Furthermore, the graphite material precursor is pulverized together with the metal material

When mixing, it is also possible to mix. The dispersing medium of the method (b) is preferably such that it does not dissolve the metal material or is soluble, but the solubility is low. It is preferred that the metal material be dispersed in accordance with the method of the present invention. Further, it is more preferable that the dispersion medium not only does not dissolve the metal material, but also does not dissolve the precursor. Such a dispersion medium is preferably an aqueous dispersion medium such as water, alcohol or acetone, and water is particularly suitable. This is because the above-mentioned dispersion medium has a smaller influence on the environment during drying and removal than the organic solvent-based dispersion medium, and is advantageous in terms of safety and cost. 326\Patent Specification (Repair)\94-11\94127847 20

1271382 The average particle size of the metal material to be introduced into the dispersion medium is preferably 5 // m, more preferably 1 // m or less. This is because when the average particle size is 5 //, uniform dispersion can be easily achieved, and the obtained graphite material can be easily or evenly dispersed, and can be easily controlled into a spherical shape. In the method (b), the graphite material precursor is first mixed with the metal in a dispersion medium. The order of the graphite material precursor and the metal material dispersion medium is not limited. For example, the metal material Φ is finally dispersed in the dispersion medium, and the precursor may be supplied to the second. As such a dispersion work, it is preferred to use a stirring device to mix the ink material precursor with the metal material until it is uniformly dispersed. At the time of _, it is preferable to perform a decompression operation or an ultrasonic treatment to remove the gas to promote contact of the metal material with the precursor. After the mixing, the aforementioned dispersion medium was removed. The removal method is not limited, and ordinary solid-liquid separation such as evaporation or steam filtration can be suitably employed. Of course, such removal of the workpiece may be carried out under reduced pressure under heating or under circulation of a gas. There may be mentioned a method in which a dispersion medium containing a genus material and the precursor is at a temperature of less than 1,500 °C. Further, in the step (3), the separation operation may be performed during the temperature rise of the temperature above 1 500 °C.

The method (c) attaches the metal material to the outer surface of the ink material precursor by a PVD method or a CVD method. Preferred examples of such a method include vacuum evaporation, sputtering, ion plating, molecular line crystallization, or atmospheric pressure CVD, vacuum CVD, plasma CVD 326, and patent specifications. Replenishment)\94-11\94127847 21 The following m is mixed with the powder of the hemispherical material. The stone is mixed with the foam, and the distillate, the lower or the gold is heated to the force. The stone is given the PVD method.

Refer to CVD method such as 1271382 MO (Magneto-Optic) CVD method or photo CVD method. Among them, sputtering is preferred in particular. As the sputtering method, a direct plating method, a magnetron sputtering method, a high-frequency sputtering method, a reactive sputtering method, a sputtering method, an ion beam sputtering method, or the like can be exemplified. As a representative example of the sputtering method, a gold material is provided on the cathode side, and in general, 1 to 1 (in a noble gas atmosphere of about T2Pa, an electric glow discharge is initiated to ionize the inert gas, and the target is used. a method of coating a metal provided on the anode side with the metal. A metal compound may be used instead of a metal, and two or more kinds of gold may be used to form an alloy on the outer surface of the precursor. The genus and the metal compound may be mixed and used as a target. Further, the above target may be used to perform sputtering twice or more so that the plurality of metals and/or compounds may be sequentially attached. A gas may be substituted for the inert gas. In this case, it is preferable to apply a vibration such as mechanical or ultrasonic waves to the precursor of the graphite material, or to perform a gas circulation method to impart dynamics to the front and to disperse the metal. In the present invention, on the outer surface of the precursor, the graphite material precursor is preferably a crystal structure having an optical isotropic property (also referred to as an optical isotropic phase) at least on the surface thereof. Because the optical isotropic phase is more optically anisotropic than the metal material, which is higher than the optical anisotropy (also known as optical anisotropic phase), the isotropic phase is used to observe the precursor using a polarizing microscope. It can be discerned. Press again, the precursor with the optically isotropic crystal structure is in the 326\ patent specification (supplement)\94-11\94127847 22, and the bias is out of the target. When two kinds of metal stirrer are used for heating, when the light profile is heated at a temperature of 1500 1271382 °c or more, the optically isotropic crystalline portion becomes a polycrystalline structure. Here, polycrystalline The structure is defined as a collection of crystals of crystallite size (crysta 1 1 ite ) having a size of 10 0 to 1 0 0 nm. Further, the size of the crystallites is defined as the observation of the crystallite profile using a transmission electron microscope. The length of the portion exposed to the surface. The preferred size of the crystallite is 30 to 80 nm, and further preferably the size is 30 to 60 nm.

A method of measuring the crystallite size is specifically exemplified. First, the graphite material precursor was placed in a graphite crucible, and heated at a temperature of 300 ° C in a non-oxidizing atmosphere for 6 hours to obtain a graphitized product. Next, the graphitized material is supported by a resin, and is thinned by focusing ion beam processing or the like. Then, it was observed with a penetrating microscope, and five or more crystallites were randomly selected, and the crystallite size was measured in accordance with the above definition. The surface of the graphite material obtained in the same manner was observed using a scanning electron microscope, whereby the crystallite size was also measured. In the case of the graphite material of the present invention, the graphite material is all optically isotropic, and it is preferable in terms of high discharge capacity in order to obtain a negative electrode material for a lithium ion secondary battery. The interior of the precursor consists of an optically anisotropic phase, and the exterior (i.e., the surface of the precursor) belongs to the optically isotropic phase. The optically isotropic phase in this case is preferably present in a film form in part or all of the surface of the precursor, and it is particularly preferable to cover more than 30% of the total surface area of the precursor. Further, it is particularly preferable to form a film-like optical isotropic phase and optical anisotropy to form the surface of the precursor. In 23 326\ patent specification (supplement)\94-11\94127847

1271382 Therefore, "fusion" means that there is no gap between the isotropic phase and the anisotropic phase. Further, the film-like optical isotropic phase has a thickness of 3 // m to be preferably 1 / m or less, and more preferably 0.5 / m or less. When the thickness of the optical isotropic is 3/m or less, it is suitable for the increase in the discharge capacity, and the lower limit is preferably 0. 0 1 // m. When it is above 0. 0 1 // m, the production of the graphite material of the present invention is sufficient. In the present invention, at least a portion of the surface has an optically isotropic phase. The precursor system may also be obtained from a surface of the precursor of the graphite material after at least a portion of the carbon source material capable of becoming a photo-neutral phase after graphitization. In other cases, the adhered graphite material precursor does not need to have optical isotropic properties. However, as the precursor of the adhered graphite material, a graphite material exhibiting photostability may be used. Such a carbon source material may exhibit optical properties at a temperature of not less than 150,000 °C, and examples thereof include an isotropic pitch such as a resin (phenol resin, decyl alcohol resin, etc.) (oxygen crosslinked petroleum pitch, etc.) )Wait. The resin may be in the state of the precursor before the polymerization or crosslinking reaction progresses. Namely, the present invention also provides a method of adhering a carbon source material having at least a part of an optically isotropic phase to a metal material after graphitization, and attaching the composition to a precursor of the graphite material. As an example of such a method, there are two new methods in which the metal material is dispersed on the outer surface of the precursor in the step (2). (d) A method of removing the dispersion medium after mixing the graphite precursor with the carbon source material and the metal material. 326\Patent specification (supplement)\94-11\94127847 24 and going down, sex is the same and then "that is, the school should wait for this kind of sentiment. Learn to be equal, photosynthetic, can be the mixed with the media. 1271382

(e) It is preferred that the melt of the carbon source material of the metal material of the graphite material is dispersed. Combine the mixture with the machine, the two-roller, etc. and the graphite. In the present invention, the outer surface is pressed again, after which, for example, carbon treatment or mechanical step (3) is applied: (Acheson) furnace I

method. Therefore, it is preferable to store it in the obtained stone at or below °C, and it is not possible to graphitize the negative electrode. The most time for graphitization is a method in which the molten material of the carbon source of the metal material adheres to the outer surface of the precursor. The method is such that the powder (average particle diameter 0 · 0 1 // m or more and 5 // m or less) is mixed with the melt, and the molten mixture is adhered to the powder of the metal material and the carbon source material before the graphite is adhered to the graphite. The mixing operation, in the mixing operation of the graphite precursor, various kneading machines using pressure kneading can be used. The metal powder and the melt are mixed. The adhesion of the precursor is carried out sequentially or simultaneously. The method of dispersing the metal material in the graphite material is not limited to the above (a) to (e). The metal material may be adhered to a material such as a coating of the outer surface of the graphite material, a gas treatment, a gas treatment, or an oxidation treatment, or the like. The graphitization method can be carried out by evaporating, decomposing or sublimating a metal material heated at a temperature of more than 150,000 °C using a known high temperature furnace of Acheson P, without residual ink. The heating temperature is preferably 2,500 ° C or more and 3 3 0 0 and more preferably 2 800 0 t: to 3 3 0 0 ° C. If it is less than 1 500 °C, the residual material of the metal material may occur, so that the discharge capacity is insufficient during use. In the case of more than 3,300 ° C, a part of the sublimation is caused, and the yield is lowered, so that it is not suitable for carrying out in a non-oxidizing environment. The need for graphitization is generally about 1 to 20 hours. 25 326\Patent Specification (Repair)\94-11\94127847 1271385 The obtained graphite material is pulverized and pulverized as needed, and the particle size is adjusted by gradation to be used as a negative electrode material.

When the metal material is dispersed and present on the precursor of the graphite material by the method as described above and heated, the graphite material of the present invention can be obtained. As for the mechanism, although it is not clear, it can be inferred that the edge material of the granular material having the granular or spherical shape dispersed on the outer surface thereof is graphitized (that is, heated to 1 500). During the process above 0 °C, a bulge is formed which is integrated with the base metal. The metal material seems to evaporate during the heating process and is rapidly dispersed, and does not substantially remain in the graphite material of the present invention of the final product. In the following, the mechanism is further speculated. The metal compound reacts with the carbon of the precursor to produce a metal carbide prior to the lower temperature graphitization process. At this time, the metal compound receives a supply of carbon from the precursor once the ridge of the metal carbide is formed. However, when the graphitization temperature rises to the vicinity of the boiling point of the metal forming the metal carbide, the carbon and the metal which form a chemical equilibrium with the metal carbide start to evaporate the metal. Then, as the temperature rises, the chemical equilibrium progresses favorably in the direction of the reverse reaction. Finally, the metal is completely evaporated and dispersed, and the same graphitization ridge as the base material remains. In the case of graphitization, the temperature rises to about 3,000 ° C, and it can be inferred that, for example, when the metal forming the metal compound is iron, at about 2800 ° C, the evaporation of iron is started. Therefore, the base material of the present invention usually takes up most of the residual portion of the graphite material precursor used in the step (1) after being graphitized. From the above, it is considered preferable to disperse the metal material on the outer surface of the precursor of the graphite material. Further, it is considered preferable that a metal or a metal compound can be used to form a carbide. 26 326\Patent Specification (Repair)\94-11\94127847 1271382 (Lithium Ion Secondary Battery) Lithium ion secondary batteries usually have a negative electrode, a positive electrode, and a nonaqueous electrolyte as their main battery components. The positive electrode and the negative electrode are each composed of a carrier of lithium ions. It is based on a battery mechanism in which lithium ions are occluded in a negative electrode during charging, and lithium ions are detached from the negative electrode at the time of discharge.

The lithium ion secondary battery of the present invention is not particularly limited except for containing the graphite material of the present invention as a negative electrode material. The other battery constituent elements of the present invention can be compared with the elements of a general ion secondary battery. Hereinafter, the negative electrode, the positive electrode, the electrolyte, and the like will be described. (Negative Electrode) The production of the negative electrode for a lithium ion secondary battery is a method for forming a negative electrode which can sufficiently exhibit the battery characteristics of the graphite material of the present invention and has high formability and is chemically and electrochemically stable. Generally, the graphite material and the binder of the present invention are mixed in a solvent and/or a dispersion medium (hereinafter, simply referred to as a solvent) to cause gelatinization, and the obtained negative electrode mixture paste is applied to a current collector to remove the solvent. A method of curing and/or shaping by means of a press or the like. Namely, first, the graphite material of the present invention is adjusted to a desired particle size by classification or the like, mixed with a binder, and the resultant composition is dispersed in a solvent to form a paste, thereby preparing a negative electrode mixture. Specifically, the water system can be exemplified as follows: a slurry obtained by mixing a graphite material of the present invention with a binder (such as carboxymethyl cellulose, styrene-butadiene rubber, etc.) in a solvent (such as water, alcohol, etc.) The mixture is stirred and mixed using a conventional mixer, a mixer, a mixing kneader, a kneader, or the like to prepare a negative electrode mixture paste. Further, regarding the preparation method of the non-aqueous system, for example, the 27 326\patent specification (supplement) \94-11\94127847 127138.2 the graphite material and the fluorine-based resin (such as polytetrafluoroethylene, polyfluorinated vinylidene) of the present invention. The powder is mixed with a solvent (e.g., isopropanol, N-decylpyrrolidone, dimethyl decylamine, etc.) to form a slurry, and the negative electrode mixture paste can also be obtained by the same stirring and mixing. The obtained paste is applied to one surface or both surfaces of the current collector, and dried to obtain a negative electrode which is uniformly and strongly adhered to the negative electrode mixture layer. The film thickness of the negative electrode mixture layer is 10 to 2 0 0 // m, preferably 3 0 to 1 0 0 // m. Further, the negative electrode mixture layer is obtained by dry-mixing the graphite material of the present invention and a resin (e.g., polyethylene, polyvinyl alcohol, etc.) powder in a metal mold to be hot-pressed. After the negative electrode mixture layer is formed, when press bonding such as press press is performed, the adhesion strength between the negative electrode mixture layer and the current collector can be further improved. The shape of the current collector for the negative electrode is not particularly limited, but is preferably in the form of a foil or a mesh (e.g., a square mesh or a square mesh). The material of the collector material is preferably copper, stainless steel or nickel. The thickness of the collector material is preferably 5 to 2 0 // m in the case of a box. (positive electrode)

The positive electrode is formed by, for example, applying a positive electrode mixture composed of a positive electrode material, a binder, and a conductive agent onto the surface of the current collector. As the positive electrode material (positive electrode active material), it is preferred to select a sufficient amount of lithium to be occluded/released. Such a material is compounded with a transition metal, c h a 1 〇 c 〇 g e η , wherein a composite oxide of lithium and a transition metal (also referred to as a lithium-containing transition metal oxide) is particularly suitable. The composite oxide may be one which has a solid solution and two or more transition metals.

The lithium-containing transition metal oxide system can be specifically obtained by the formula LiMS-xM^OK type X 28 326\patent specification (supplement)\94-11\94127847

1271382 is a value in the range of 0SXS1, Μ1, Μ2 are at least one transitional element) or a formula LiMS-yM^O〆 where Υ is a value in the range of 0$YS2, and Μ1 and M2 are at least one transition metal element ) said.过渡 The transition metal elements are Co, Ni, Μη, Cr, Ti, V, Fe, Zn, A1

In, Sn, etc. Preferred specific examples are LiCoCh, LiNiCh, LiMn〇2 LiNio.9Coo.1O2 λ LiNio.5Coo.5O2, etc. 0. The transition metal oxides are based on, for example, oxides and salts of transition metals and salts. The starting materials are mixed, and the starting materials are mixed and fired at a temperature of 60 to 1 0 0 ° C in an oxygen atmosphere. The positive electrode active material may be used singly or in combination of two or more kinds. For example, a carbonate such as lithium carbonate may be added to the positive electrode. When a positive electrode is formed, an additive such as a conventional conductive agent can be suitably used. In the positive electrode, a positive electrode mixture composed of a positive electrode material, a binder, and a conductive agent (for imparting conductivity) is applied to both surfaces of the current collector to form a positive electrode mixture layer. The binder can be used in the same manner as those used in the manufacture of the negative electrode. As the conductive agent, a conventional material such as a graphite compound can be used. The current collector is not particularly limited in shape, and a foil-like mesh (e.g., a square mesh, a square mesh, etc.) may be used. The material of the collector material is aluminum, stainless steel, nickel, and the like. Its thickness is preferably from 10 to 4 0 // m. Similarly to the negative electrode, the positive electrode mixture is dispersed in a solvent to form a paste, and the paste positive electrode mixture is applied to a current collector and dried to form a positive electrode mixture layer. Alternatively, after the positive electrode mixture layer is formed, a press-pressing treatment such as press pressurization may be further performed. Thereby, the positive electrode mixture 326\patent specification (supplement)\94-11 \94127847 29 gold is uniformly and strongly adhered to the current collector in the upper and lower layers of the upper layer 1271382. (Electrolyte) As the electrolyte used in the present invention, an organic electrolyte composed of a solvent and an electrolyte salt, or a polymer electrolyte composed of a polymer compound and an electrolyte salt can be used. As the electrolyte salt, for example, LiPF6, LiBF4, LiAsF6, LiCl〇4, LiB(C6H5)4, LiCl, LiBr, LiCF3S (h, LiCH3S〇3, LiN(CF3S〇2)2, LiC(CF3S〇2) can be used. 3) LiN(CF3CH2〇S〇2)2, LiN(CF3CF2〇S〇2)2, LiN(HCF2CF2CH2〇S〇2)2, •LiN[(CF3)2CHOS〇2]2, LiB[C6H3(CF3 2] 4, LiAlCL·, LiSiFe, etc., in particular, L i PF 6 and L i BF 4 are preferred from the viewpoint of oxidation stability. The electrolyte salt concentration in the organic electrolyte is 0.1 to 5 m. ο 1 / 1 is preferred, and more preferably 0.5 to 3.0 mol/l.

As the solvent of the organic electrolyte, ethylene glycol carbonate, propylene glycol carbonate, dinonyl carbonate, diethyl carbonate, ethyl decyl carbonate, 1,1- or 1,2-dimethoxyethane can be used. 1,2-diethoxyethane, tetrahydrofuran, 2-methyltetrahydrofuran, 7-butyrolactone, 1,3 - serotonin, 4-methyl-1,3 - slogan, sulfhydryl Phenyl ether, diethyl ether, sulfolane, decyl sulfolane, acetonitrile, chloronitrile, propionitrile, tridecyl borate, tetradecanoic acid citrate, nitrodecane, dimethyl decylamine, N-mercapto pyrrolidine Ketone, ethyl acetate, tridecyl phthalate, nifediene, benzoquinone, benzoquinone bromine, tetrahydrothiophene, disulfoxide, 3-mercapto-2-oxazolidinone, ethylene glycol An aprotic organic solvent such as dimethyl sulfite. In the case where the nonaqueous electrolyte is a polymer electrolyte, a matrix polymer compound gelled by a plasticizer (nonaqueous solvent) is included, and as the substrate 326\patent specification (supplement)\94-11\94127847 30 (§

1271382 Polymer compound, which can be ether resin (such as polycyclohexane or its cross-linking), polydecyl acrylate resin, polyacrylate resin, fluoroester (such as polyfluorinated b-baked, miscible) Ethylene-hexafluoropropylene copolymer, etc.) used alone or in combination. Among them, a polyfluorinated vinylidene fluoride or a fluorinated vinylidene-hexafluoropropylene copolymer fluoroindole resin can be used from the viewpoint of redox stability. The solvent ratio in the polymer electrolyte is preferably from 10 to 90% by mass, more preferably from 30 to 80% by mass. When it is in this range, the electrical conductivity is high, the machine is large, and the film is easily formed. The production of the polymer electrolyte is not particularly limited, and examples thereof include a polymer compound constituting a matrix, a lithium salt, and a non-aqueous solvent (plasticizing, heating, melting, and dissolving). The compound, the lithium salt, and the non-aqueous solvent are dissolved in the organic solvent for mixing, and the organic solvent is used in combination. The polymerizable single lithium salt and the non-aqueous solvent are mixed, and ultraviolet rays, electron beams, or fractions are irradiated thereto. A method of obtaining a polymer by polymerizing a polymerizable monomer, etc. In the lithium ion secondary battery of the present invention, a separator may be used. The separator is not particularly limited. For example, woven fabric may be used. A microporous film made of a synthetic resin, etc., preferably made of a synthetic resin, preferably a polyolefin microporous film, in terms of thickness, film strength, and film power. Specific examples thereof include polyethylene and polypropylene. The microporous membrane is a composite microporous membrane, etc. In the lithium ion secondary battery of the present invention, it is also possible to use a gelatin 326\patent specification (supplement)\94-11\94127847 31 Etc., and the intensity of the "mixed molecules" to make the mixture, the strand cloth, the film is more resistant, or the electrolytic 1271382 lithium ion secondary battery using the polymer electrolyte is generally called a polymer battery. A negative electrode (using the graphite material of the present invention), a positive electrode, and a polymer electrolyte. For example, the negative electrode, the polymer electrolyte, and the positive electrode are laminated in this order, and are housed in a battery exterior material, thereby being manufactured. It is also possible to arrange the polymer electrolyte on the outside of the negative electrode and the positive electrode.

Further, the structure of the lithium ion secondary battery of the present invention is arbitrary, and its shape and form are not particularly limited. As such a structure, it can be arbitrarily selected from a cylindrical type, a square type, a coin type, a button type, and the like. In order to obtain a sealed non-aqueous electrolyte battery having a higher degree of safety, it is preferable to provide a means for detecting an increase in the internal pressure of the battery and cutting off the current in an abnormal state such as overcharge. In the case of a polymer battery using a polymer electrolyte, a structure in which a laminated film is sealed can also be produced. [Examples] Hereinafter, the present invention will be specifically described based on examples, but the present invention is not limited by the examples. Further, in the following examples and comparative examples, a button type secondary battery for evaluation as shown in Fig. 2 was produced, and evaluation was performed thereby. The battery can be made in accordance with conventional methods for the purposes of the present invention. Further, in the following examples and comparative examples, the physical properties of the graphite material precursor and the graphite material of the present invention were measured by the following methods. The aspect ratio of the graphite material precursor and the graphite material was measured by a scanning electron microscope, and the magnification of the shape was confirmed, and 50 objects were measured. The aspect ratio is calculated from the maximum major axis length and the length of the axis orthogonal thereto, and the average value is displayed. 32 326\Patent specification (supplement)\94-11\94127847 1271382 The average particle size of the graphite material precursor and graphite material is the volume-converted average particle size, which is the accumulation of the particle size distribution measured by the laser diffraction particle size distribution meter. The particle size at a volume percentage of 50% by volume. The lattice surface spacing d 〇 2 of the graphite material is determined in accordance with the aforementioned X-ray diffraction method. The specific surface area of the graphite material is determined by the nitrogen adsorption BET method.

Regarding the height (h) of the ridge of the graphite material and the length (g) of the substrate, according to the cross-sectional observation of the scanning electron microscope, 50 ridges were measured according to the magnification of the shape, and the height (h) and the substrate length were determined. g) and the average of the ratio of height (h) to substrate length (g) (h/g). The average value of h/g is set to be an average of 50 points of h / g for each ridge. The identifiable magnification is usually about 3,000 times. Further, in the present invention, the base is a imaginary flat section in which the corresponding ridge is in contact with the base material, and the base length (g) is the longest imaginary line connected by two points on the outer circumference of the imaginary flat section. Further, the ridge south (h) is the southernmost vertical height from the base (the imaginary flat section). The number of ridges of the graphite material is measured by using a scanning electron microscope, and the number of ridges present in any of the 1000/m2 is measured, and the measurement is performed after 10 fields of view. , expressed as the average number of 1 0 0 A m2. (Example 1) (Graphite material precursor) A mesophase small sphere (manufactured by Jiefuyi Chemical Co., Ltd., average particle size 2 5 // m) obtained by heat treatment of coal tar pitch in a nitrogen atmosphere of 60 0 °C temperature 33 326\patent specification (supplement) \94-11\94127847 1271382 was fired for 3 hours to prepare a spherical graphite material precursor. Its aspect ratio The graphite material precursor produced by this method is used as a precursor (1). (Graphite material) After adding 100 parts by mass of the precursor (1) to 100 parts by mass of an aqueous solution (acidic acid) having a concentration of 5% by mass in terms of iron, an aqueous sodium hydroxide solution is added thereto. Neutralize to p Η 7. The resulting neutral liquid was obtained by dispersing the precursor (1) in a suspension of iron hydroxide (F e 0 ( Ο Η )). The dispersion was heated to 10,000 ° C to remove water, and then vacuum dried at 150 ° C for 5 hours to completely remove water. Thus, the precursor in which iron hydroxide is dispersed on the surface (hereinafter, also referred to as "iron hydroxide dispersed in the precursor") can be obtained.

After drying, a scanning electron microscope was used to observe the appearance of the precursor in which the iron hydroxide was dispersed. Therefore, it was found that the granular and acicular iron hydroxide were dispersed. Further, regarding the 50 dispersed iron hydroxides, the length of each major axis was measured using a scanning electron microscope, and the obtained measurement value was an average of 0.5 mM. Further, the iron hydroxide was dispersed in the presence of the precursor in a non-oxidizing atmosphere at a temperature of 300 ° C for 6 hours to obtain a graphite material (1 ). The graphite material (1) has a granular shape of an average particle diameter of 2 4 // m and has a structure having a hemispherical to spherical ridge of 6 / 1 0 0 / m 2 on its surface (refer to Fig. 1). The average height (h) of the ridge is 3.5//Π1, the average substrate length (g) is 3.0//m, and the average h/g is 1.2. The graphite material (1) had an average aspect ratio of 1.2, a specific surface area of 3.1 m2/g, and a lattice surface spacing d〇〇2 of 0.3356 nm. In Table 1, 34 3 26\patent specification (supplement)\94-11 \94127847

1271382 shows the characteristics of the precursor (1), the adhesion treatment of the metal material, the characteristics of the graphite material (1), and the characteristics of the bulge. Further, as for the obtained graphite material (1), analysis of the contained elements was carried out using an I CP luminescence analyzer, and as a result, iron was not detected. For the heat treatment in which the foregoing iron hydroxide is dispersed in a non-oxidizing atmosphere at a temperature of 1490 ° C for 4 hours, X-ray diffraction is performed to identify the result of the contained compound, F e 3 C is detected. From this, it is inferred that iron carbide is generated once during the temperature rise during the graphitization treatment. (Preparation of negative electrode mixture paste) 98 parts by mass of graphite material (1) is added to water together with 1 part by mass of carboxymethyl group-based fiber serving as a binder and 1 part by mass of styrene-butadiene rubber, and mixed Form a negative electrode mixture paste. (Production of Working Electrode) The foregoing negative electrode mixture paste is applied to a copper foil in a uniform thickness, and then, water is used as a dispersion medium to evaporate under vacuum and at a temperature of 90 ° C to be dried, and then coated on the copper. The negative electrode mixture on the foil is pressed by a roller press and punched into a circle having a diameter of 15.5 mm to form a negative electrode which is closely adhered to the collector material (thickness 16 6 m) composed of the foil. A working electrode composed of a mixture layer (thickness μ m ). (Manufacture of the opposite pole) The lithium metal foil is pressed against the nickel mesh to punch through a circle of 15.5 mm, and the current collector made of the nickel mesh and the lithium gold foil closely attached to the collector ( The thickness of 0 · 5 // m) is the opposite pole. 326\Patent specification (supplement)\94-11\94127847 35 The material is re-circulated and can be added to the copper. 60% is 1271382 (electrolyte/separator). Let Li PF 6 press 1 m ο 1 The concentration of /dm3 was dissolved in a mixed solvent of ethylene glycol carbonate 3 3 v ο 1 % and mercaptoethyl carbonate 6 7 v ο 1 % to prepare a nonaqueous electrolyte. A polypropylene porous body (thickness 20 0 / m) was immersed in the obtained nonaqueous electrolyte to prepare a separator in which an electrolyte was impregnated. (Evaluation of Manufacturing of Battery) As the evaluation battery, a button type secondary battery as shown in Fig. 2 was produced.

The working electrode 1 2 which is closely adhered to the current collector 1 7 b and the counter electrode 1 4 which is closely adhered to the current collector 1 7 a are sandwiched between the two sides with the separator 15 impregnated with the electrolyte, and laminated . Then, the side of the working electrode current collector 1 7 b can be accommodated in the outer cup 1 1 , and the side of the pole current collector 1 7 a can be accommodated in the outer can 1 3 so that the outer cup 1 1 It is fitted to the outer can 13 . At this time, the insulating spacer 16 is interposed between the outer peripheral cup 1 1 and the peripheral portion of the outer can 1 3, and the two peripheral edges are caulked to be sealed. With respect to the evaluation battery prepared above, the charge and discharge test shown below was carried out at a temperature of 25 ° C, and the discharge capacity, the initial charge and discharge rate, the rapid charge rate, the rapid discharge rate, and the cycle characteristics were evaluated. The evaluation results are shown in the table.

(Discharge capacity, initial charge and discharge efficiency) A constant current of 0.9 mA is applied until the circuit voltage reaches OmV, and then it is converted to constant voltage charge, and charging is continued until the current value reaches 2 0 //A. The charging capacity is obtained from the amount of energization therebetween. Then, stop for 1 20 minutes. Then, a constant current discharge is performed at a current value of 0.9 m A until the circuit voltage reaches 1.5 V, and the discharge capacity is obtained from the amount of energization therebetween. Take this as the 36 326\patent specification (supplement)\94-11\94127847 1271382 the first cycle. The initial charge and discharge efficiency is calculated by the following formula (i): Initial charge and discharge efficiency (%) = (discharge capacity of the first cycle / charge capacity of the first cycle) xl 〇〇 (I) Again, in this test, The process of occluding ions in the graphite material is used as a charge, and the process of detachment is used as a discharge. (Rapid Charging Rate) Next, the following high-speed charging is performed in the second cycle.

The current value is set to 4 times of the first cycle of 3. 6 m A, and the constant current is charged until the circuit voltage reaches OmV, and the charging capacity is obtained, and the rapid charging rate is calculated by the following formula (II): rapid charging Rate = (constant current charging capacity in the second cycle / discharge capacity in the first cycle) χ 100 (II) (rapid discharge rate) After the constant current charging in the second cycle described above, the following high-speed discharge was performed in the second cycle. As in the first cycle, it is converted to constant voltage charging, and after the charging is completed, the current value is set to 1 4 times of the first cycle, 4. 4 m A, and a constant current discharge is performed until the circuit voltage reaches 1.5. V so far. According to the obtained discharge capacity, the rapid discharge rate is calculated by the following formula (I I I ): rapid discharge rate = (discharge capacity of the second cycle / discharge capacity of the first cycle)

Xl 00 Press again, and the performance of the rapid charging rate and the rapid discharge rate may be collectively referred to as the rapid charging and discharging characteristics. (Cycle characteristics) Separately, another evaluation battery is manufactured separately from the evaluation battery for the evaluation of the discharge capacity, the initial charge and discharge rate, the rapid charge rate, and the rapid discharge rate of 37 326\patent specification (supplement)\94-11 \94127847 1271382 To perform the following assessment. Apply a constant current of 4.0 mA until the circuit voltage reaches OmV, then convert to constant voltage charging, continue charging until the current value reaches 2 0 // A, and then stop for 120 minutes. Next, the current is discharged according to the current value of 4.0 m A until the circuit voltage reaches 1.5 V. This charge and discharge is repeated 20 times, and the cycle characteristics are calculated using the following formula (IV) according to the obtained discharge capacity: Cycle characteristics = (discharge capacity of the 20th cycle / discharge capacity of the 1st cycle) φ xlOO (IV) As shown in Fig. 3, the graphite material (1) of Example 1 was used as the negative electrode material of the working electrode, and the obtained evaluation battery showed high discharge capacity and high initial charge and discharge efficiency. It also exhibits excellent rapid charge and discharge characteristics and excellent cycle characteristics. (Comparative Example 1) In Example 1, the metal material was not used, and only the precursor (1) was heated at a temperature of 300 ° C in a non-oxidizing atmosphere to prepare a graphite material stomach (1). 0). The obtained graphite material (10) was spherical particles having an average particle diameter of 2 4 // m and having no bulging. The average aspect ratio of the particles was 1.2, the specific surface area was 0.5 m2/g, and the lattice surface spacing d〇2 was 0.3358 nm. Table 2 shows the characteristics of the precursor (1) and the characteristics of the graphite material (10). Further, using the graphite material (10), a working electrode and an evaluation battery were fabricated in the same manner and under the same conditions as in Example 1, and a charge and discharge test was carried out. The evaluation results of the battery characteristics are shown in Table 3. As shown in Table 3, the graphite material (10) on the surface does not have a bulge, 38 326\patent specification (supplement)\94-11 \94127847 1271382, although its initial charge and discharge efficiency is high, but it is not High rapid charge and discharge characteristics or cycle characteristics are obtained. Further, since the graphite compounds have little contact with each other, the original discharge capacity of the graphitized material is not completely exhibited, and the discharge capacity is lowered. Further, as a result of observation by a polarizing microscope, it was found that the surface of the precursor (1) had a film-like optical isotropic phase, and the inside thereof had an optical anisotropic phase. Further, regarding the graphite material (10), the crystal structure of the surface was analyzed.

At the time of analysis, the graphite material (10) was supported by a resin, and was cut by a focused ion beam processing apparatus (FB 2 0 0 0 manufactured by 曰立工所), and the graphite material (10) was processed into a thickness. A film of about 0.1 m. Next, regarding this film, in the field near the surface of the graphite material (10) (1 // m X 1 // m ), 10 parts are optionally used, and a transmission electron microscope (HF manufactured by Hitachi, Ltd.) is used. 2200 and JE Μ 2 0 1 0 F) of Japan Electronics Co., Ltd., irradiating an electron beam (pressing voltage 1 50~2 0 0 kV, electron beam diameter tens of nm) to perform electron diffraction, The crystallinity and crystallite size were measured. As a result, it was found that 8 of the 10 sites had a polycrystalline property, and it was confirmed to have a polycrystalline structure. Furthermore, the crystallite size is 60 n m (the average value is rounded to the value of 10 n m). In addition, the crystallite size is observed from a cross section of the crystallite through a transmission electron microscope to measure the length of a portion exposed on the surface. (Example 2) In Example 1, a method of preparing a graphite material precursor was changed. The mesophase small spheres were previously pulverized to obtain block particles having an average particle diameter of 1 5 // m. This was fired at a temperature of 60 ° C for 3 hours in a nitrogen atmosphere to obtain a bulk precursor (2). Its average aspect ratio is 1.25. Using this precursor (2), a graphite material (2) was prepared in the same manner and under the same conditions as in Example 1 in the specification of 39 326\patent specification (supplement)\94-11\94127847 1271382. The graphite material (2) has a block shape of an average particle diameter of 14 μm and has a structure having a hemispherical to spherical bulge of 7/100//m2 on its surface. The average height h of the ridge is 2. 8 / zm, the average substrate length g is 2.3 / m, and the average h / g is 1.2. The graphite material (2) had an average aspect ratio of 1,500, a specific surface area of 4.5 m2/g, and a lattice spacing d〇2 of 0.3356 nm. In Table 1, the characteristics of the precursor (2), the adhesion treatment of the metal material, the characteristics of the graphite material (2), and the characteristics of the bulging are shown. Further, using the graphite material (2), the working electrode and the evaluation battery were fabricated in the same manner and in the same manner as in Example 1, and a charge and discharge test was performed. The evaluation results of the battery characteristics are shown in Table 3. As shown in Table 3, the graphite material (2) of Example 2 was used as the negative electrode material of the working electrode, and the obtained battery was evaluated to have a surface discharge capacity and a high initial charge and discharge efficiency. It also shows excellent rapid charge and discharge characteristics and cycle characteristics. (Comparative Example 2) In Example 2, the metal material was not used, and only the precursor (2) was heated at a temperature of 300 ° C in a non-gastric oxidizing atmosphere to prepare a graphite material (20). ). The graphite material (20) is a massive particle having an average particle diameter of 1 4 // m and having no bulging. The average aspect ratio of the particles was 1.5, the specific surface area was 0.9 m 2 /g, and the lattice spacing d 〇〇 2 was 0.3358 nm. Table 2 shows the characteristics of the precursor (2) and the characteristics of the graphite material (20). Further, using the graphite material (20), a working electrode and an evaluation battery were fabricated in the same manner and under the same conditions as in Example 2, and a charge and discharge test was carried out. The evaluation results of the battery characteristics are shown in Table 3. 40 326\Patent specification (supplement)\94-11\94127847 1271382 As shown in Table 3, the high-rapid charge-discharge characteristics or cycle characteristics were not obtained in the case where the surface of the graphite material (2 Ο) was not embossed. Furthermore, the discharge capacity is also reduced. (Example 3) In Example 1, a method of preparing a graphite material precursor was changed. The coal tar pitch was fired at 60 ° in a nitrogen atmosphere for 3 hours to obtain a bulk intermediate phase. The material was pulverized to prepare a block and scale-like precursor with an average particle diameter of 25 // m. (3).

Next, the precursor (3) 100 g and the phenol resin belonging to the carbon source material (the residual ratio after graphitization is 40% by mass) 5 g are impregnated with ethylene glycol 100 g and hexamethylenetetramine 0. . 5 g of the mixture. The obtained mixture was stirred while removing ethylene glycol under reduced pressure (1.3 P a ) at a temperature of 150 ° C to obtain a resin-coated precursor. The resin-coated precursor is subjected to heat treatment at a temperature of 270 ° C in air for 5 hours to harden the resin, thereby obtaining a hardened resin precursor (3 1 ) having an aspect ratio of 2 · 8 . Further, as a result of observation by a polarizing microscope, the precursor (31) was found to have a film-like optical isotropic phase on its surface and an optical anisotropic phase inside. Using the precursor (31), the iron hydroxide was dispersed in the same manner and in the same manner as in Example 1, and then graphitized to prepare the graphite material (3 1) of the present invention. In Table 1, the characteristics of the precursor (3), the adhesion treatment of the metal material, the characteristics of the graphite material (31), the characteristics of the bulging, and the like are shown. Further, using the graphite material (3 1 ), the working electrode and the evaluation battery were fabricated in the same manner as in the example 1 41 326\patent specification (supplement)\94-11\94127847 1271382, and a charge and discharge test was performed. . The evaluation results of the battery characteristics are shown in Table 3. As shown in Table 3, the graphite material (3 1 ) of Example 3 was used as the negative electrode material of the working electrode, and the evaluation battery obtained showed high discharge capacity and high initial charge and discharge efficiency. It also shows excellent rapid charge and discharge characteristics and cycle characteristics. (Comparative Example 3) In Example 3, the metal material was not used, and only the phenol resin hard Φ precursor precursor (3 1 ) was applied at a temperature of 300 ° C in a non-oxidizing atmosphere to It is heated to form a graphite material (3 1 0 ). The graphite material (3 1 0 ) is a block-like to scaly particle having an average particle diameter of 2 4 // m and having no bulging. The particles have an average aspect ratio of 2, 4, a specific surface area of 0.7 m2 / g, and a lattice spacing d 〇〇 2 of 0.3357 nm. Table 2 shows the characteristics of the precursor (3) and the characteristics of the graphite material (3 1 0).

Further, using a graphite material (3 1 0 ), a working electrode and an evaluation battery were fabricated in the same manner and under the same conditions as in Example 3, and a charge and discharge test was performed. The evaluation results of the battery characteristics are shown in Table 3. As shown in Table 3, in the case where the surface of the graphite material (3 10 0) was not embossed, high initial charge and discharge efficiency, rapid charge and discharge characteristics, or cycle characteristics were not obtained. Moreover, the discharge capacity is also lowered. With respect to the graphite material (3 1 0), as in Example 1, electron diffraction was performed on 10 sites in the vicinity of the surface, and crystallinity and crystallite size were measured. As a result, it was found that seven sites have polycrystalline properties, and it was confirmed to have a polycrystalline structure. The crystallite size is rounded off to a mean value of 1 Οηπι, which is 30 nm. 42 326\Patent specification (supplement) \94-11\94127847 1271382 (Example 4) The precursor (1) prepared in Example 1 was made up of 0 parts by mass and nickel powder (average particle diameter 0.22 / / m, globular) 3 parts by mass are mixed together using a Henschel mixer (manufactured by Mitsui Mining Co., Ltd.) to obtain a nickel fine powder in which the precursor is dispersed on the surface thereof (hereinafter, referred to as nickel dispersion) Precursor). Here, the stirring speed of the Henschel mixer was set to 70 rpm, and mixing was performed for 30 minutes. The nickel was dispersed in the presence of the precursor in a non-oxidizing atmosphere at a temperature of 300 ° C for 6 hours to obtain a graphite material (4). The graphite material (4) is a spherical shape having an average particle diameter of 2 4 // m, and has a structure in which a hemispherical to spherical bulge of 4/100//m 2 is dispersed on the surface thereof. The average height h of the ridges was 3.2 / / m, the average substrate length g was 3.3 / / m, and the average h / g was 0.97. The graphite material (4) has an average aspect ratio of 1.2, a specific surface area of 1 · 8 m 2 / g, and a lattice spacing d. ο 2 is Ο . 3 3 5 6 n m. In Table 1, the characteristics of the precursor (1), the adhesion treatment of the metal material, the characteristics of the graphite material (4), and the characteristics of the bulge thereof are shown. ® In addition, regarding the obtained graphite material (4), the element was analyzed using an I CP luminescence spectroscopic analyzer, and nickel was not detected. Further, for the case where the nickel-dispersed precursor is subjected to heat treatment at a temperature of 100 ° C for 2 hours in a non-oxidizing atmosphere, X-ray diffraction analysis is performed to identify the result of the contained compound, N i 3 C is detected. From this, it can be inferred that in the temperature rising process during the graphitization treatment, the carbide of nickel is generated. Next, using the graphite material (4), a working electrode and an evaluation battery were fabricated in the same manner and under the same conditions as in Example 1, and a charge and discharge test was performed. Electricity 43 326\Patent Specification (Supplement)\94-11\94127847 1271382 The evaluation results of the pool characteristics are shown in Table 3. As shown in Table 3, the graphite material (4) of Example 4 was used as the negative electrode material of the working electrode, and the evaluation battery obtained showed high discharge capacity and high charge and discharge efficiency. It also shows excellent rapid charge and discharge characteristics and cycle characteristics. (Example 5)

The precursor (1) prepared in the first embodiment is disposed on the platform of the anode side of the DC two-pole sputtering apparatus, and a purity of 99.99% of the single crystal is placed on the cathode side, and The conditions of the pressure of 0.5 P a, the voltage of 6 Ο Ο V and the current of 0.5 A were sputtered for 3 hours. Further, an ultrasonic vibrator is attached to the platform on the anode side to perform sputtering while vibrating the precursor (1). The fact that the precursor (1) in which cobalt was dispersed (hereinafter referred to as a cobalt-dispersed precursor) was subjected to quantitative analysis of cobalt by an I C P luminescence spectroscopic analyzer, and the fact that 7 mass % / 〇 was contained was confirmed. The state of adhesion of cobalt was observed using a scanning electron microscope, and the state in which the particles were dispersed was observed. With respect to the 50 dispersed cobalt particles, the respective maximum lengths were measured to obtain an average value of 0.3 Å. The cobalt was dispersed in the presence of the precursor in a non-oxidizing atmosphere at a temperature of 300 ° C for 6 hours to obtain a graphite material (5). The graphite material (5) has a spherical shape of an average particle diameter of 2 4 // m, and has a structure in which a hemispherical to spherical bulge which is dispersed on the surface thereof is 5 / 1 0 0 / m 2 . The average height h of the ridges was 1.8 / / m, the average substrate length g was 2.8 / / Π 1, and the average h / g was 0.64. The graphite material (5) has an aspect ratio of 1.2, a specific surface area of 2.5 m2 / g, a lattice 44 326\patent specification (supplement)\94-11\94127847

1271382 Surface spacing d〇()2 is 0.3356nm. In Table 1, the characteristics of the precursor (1), the attachment of the metal material, the characteristics of the graphite material (5), and the characteristics of the bulge thereof are shown. Further, regarding the obtained graphite material (5), an element was analyzed by using an I C P luminescence analyzer, and as a result, no abnormality was detected. Further, when the cobalt precursor is dispersed and subjected to heat treatment at a temperature of ° C for 2 hours in a non-oxidizing atmosphere, X-ray diffraction analysis is performed, and the result of the compound is determined, and C 〇 2 C is detected. . From this, it can be inferred that during the temperature rise during the graphitization treatment, the graphite material (5) is used for the carbonization of cobalt, and the working electrode and the evaluation battery are fabricated in the same manner and in the same manner as in the first embodiment, and the charge and discharge test is performed. . The evaluation results of the battery are shown in Table 3. As shown in Table 3, the graphite material (5) was used as the negative electrode material of the working electrode, and the evaluation battery obtained showed high discharge capacity and high charge and discharge efficiency. It also shows excellent rapid charge and discharge characteristics and characteristics. (Comparative Example 4) The graphite material (10) obtained by graphitization in Comparative Example 1 was mixed with KETJEN BLACK (EC 6 0 0 JD, average particle diameter μ m manufactured by Lion King) 3 parts by mass. And the obtained mixture (raw material 2 3 ) is put into a mechanochemical processing apparatus (Nara Machinery Manufacturing Co., Ltd. (shared "high mixing system") shown in the schematic form. The apparatus is composed of a fixed cylinder 2 1 and a rotating rotor raw material. Circulation structure 2 4 and discharge mechanism 2 5, blade 2 6 , stator 2 7 cover 2 8 etc. ' 326 \ patent specification (supplement) \94-11\94127847 45 L light points for 1000 to learn, The article, the characteristic example 5, and the cyclic component 0.03 3) 11 and 1231382 are supplied between the fixed cylinder 21 and the rotor 2 2, whereby the fixed cylinder 21 can be caused. A mechanical force such as a compressive force, a shearing force, and a frictional force which is different from the speed of the rotor 22 is applied to the raw material 23. The treatment was carried out under the conditions of a peripheral speed of 40 m / s e c of the rotating rotor 2 and a treatment time of 6 minutes, whereby mechanical action was repeatedly applied to the graphite material (10) and K E T J E N B L A C K . In this way, a graphite material (100) having K E T J E N B L A C K attached to the surface was obtained. The graphite material (100) has an average particle diameter of 2 4 // m and has a structure in which fine carbon particles derived from K E T J E N B L A C K are buried on the surface. The number of buried objects φ is 100 or more/100//m2, and the average height of the embedded objects and the average substrate length cannot be measured because the height of each embedded object is 0.1 or less. The graphite material (100) has an average aspect ratio of 1.25, a specific surface area of 2 1 · 5 m 2 /g, and a lattice spacing dG 〇 2 of 0.3360 nm. Table 2 shows the characteristics of the graphite material (10) used as the precursor and the characteristics of the graphite material (100) in which KET JEN BLACK is embedded. Further, using a graphite material (100), a working electrode and an evaluation battery were fabricated in the same manner and under the same conditions as in Example 1, and a charge and discharge test was performed. The evaluation results of the battery characteristics are shown in Table 3. As shown in Table 3, there is no integrated ridge on the surface of the graphite material (100), and when the fine carbon particles are buried to form a deposit, high rapid charge and discharge characteristics or cycle characteristics cannot be obtained. Further, since the specific surface area is too large, the initial charge and discharge efficiency is lowered. Further, the surface of the working electrode was observed by a scanning electron microscope, and as a result, a part of the fine carbon particles was observed to be partially scattered and locally aggregated on the surface of the graphite material (100). For this reason, it can be inferred that the system is detached during the electrode manufacturing process. Further, the comparative example 4 is equivalent to the technique described in Japanese Patent Application No. Hei No. Hei No. Hei No. 2, 516, 847, 127, 127, 127, pp. (Comparative Example 5) 100 parts by mass of the precursor (1) prepared in Example 1 was added to 100 parts by mass of an ethanol solution having a concentration of iron nitrate equivalent to 5 mass%, and the mixture was stirred and mixed. Decompression was carried out from a pressure of normal pressure to 50 Tor r (=1.3 P a ) to allow the ferric nitrate solution to permeate the precursor (1). Subsequently, it was desiccated and dried at 80 ° C for 24 hours to completely remove the ethanol. Thus, the precursor to which iron nitrate was attached (hereinafter referred to as an iron nitrate-attached precursor) was obtained.

The appearance of the iron nitrate-attached precursor was observed by a scanning electron microscope, and a film-like iron compound was adhered to the surface of the precursor (1), and the iron nitrate precursor was attached to the non-oxidizing environment. Heating at a temperature of 3 0 0 °C for 6 hours gave a graphite material (50). This graphite material (50) was observed to have a granular shape of an average particle diameter of 2 4 // m and a very fine bulge on the surface. The observed ridges are 2 / 1 0 0 // m2, the average height h is 0.4/zm, the average substrate length g is 0.6//m, and the average 〇 h / g is 0.67. The graphite material (50) has an average aspect ratio of 1.2, a specific surface area of 1.0 m2/g, and a hazel surface spacing d〇2 of 0.3357 nm. In Table 2, the characteristics of the precursor (1), the characteristics of the graphite material (50), and the characteristics of its bulging are shown. Further, using a graphite material (50), a working electrode and an evaluation battery were fabricated in the same manner and under the same conditions as in Example 1, and a charge and discharge test was performed. The evaluation results of the battery characteristics are shown in Table 3. As shown in Table 3, the negative electrode material used as the working electrode used the graphite material 47 326\patent specification (supplement)\94-11\94127847 1271382 material (5 Ο), and the obtained battery was not obtained with high rapid charge. Discharge characteristics or cycle characteristics. Since the graphite material (50) is a graphite material obtained by mixing a metal material as a solution with the precursor (1), the surface bulging does not reach the size specified in the present invention. Further, Comparative Example 5 corresponds to the technique described in Japanese Patent Laid-Open No. Hei 10 - 2 5 5 7 7 0. (Example 6) A phenol resin belonging to a carbon source material (residual ratio after graphitization of 50% by mass) 8 parts by mass was dissolved in 100 parts by mass of ethanol, and an average particle diameter of φ 1 0 // m was added thereto. And an average aspect ratio of 7.6 scaly natural graphite (hereinafter referred to as natural graphite (6)) after 96 parts by mass, adding iron oxide fine powder (F e 2 0 3, average particle diameter 0.3 oz, m Shape) 6 parts by mass. The obtained mixture was degassed while being reduced in pressure from normal pressure to 1 · 3 P a while stirring, so that the ethanol solution of the phenol resin penetrated into the natural graphite (6 ). Next, after distilling off the ethanol, heat treatment was applied for 7 hours at a temperature of 500 ° C in a nitrogen atmosphere to harden the resin and then carbonize. Since the heat treatment caused the mixture to be slightly dissolved, it was pulverized again to carry out particle size adjustment so that the average particle diameter became 1 4 // m. The average aspect ratio of the Φ after the particle size adjustment is 4.0. Natural graphite (6 1 ) coated with a resin which is carbonized in a state containing the iron oxide fine powder, and heated at a temperature of 300 ° C for 6 hours in a non-oxidizing atmosphere to obtain a graphite material (6 1 ) . In Table 1, the characteristics of natural graphite (6), the adhesion treatment of the metal material, the characteristics of the graphite material (61), and the characteristics of the bulging thereof are shown. Further, using the graphite material (6 1 ), a working electrode and an evaluation battery were fabricated in the same manner and under the same conditions as in Example 1, and a charge and discharge test was carried out. 48 326\Patent Specification (Replenishment)\94-11\94127847 1271382 The evaluation of battery characteristics is shown in Table 3. As shown in Table 3, a graphite material (61) was used as the anode material of the working electrode, and the obtained battery was evaluated to have a high discharge capacity and to have high charge and discharge efficiency. It also shows excellent rapid charge and discharge characteristics and cycle characteristics. (Comparative Example 6)

8 parts by mass of the phenol resin (the residual ratio after graphitization) of the carbon source material was dissolved in 100 parts by mass of ethanol, and 96 parts by mass of the natural graphite (6) used in Example 6 was added thereto. The resulting mixture was stirred while being decompressed under reduced pressure from normal pressure to 1.3 Pa to allow the ethanol solution of the phenol resin to permeate into the natural graphite (6). Next, after distilling off the ethanol, heat treatment was applied for 7 hours at a temperature of 500 ° C in a nitrogen atmosphere to harden the resin and then carbonize. Since the heat treatment caused the mixture to be slightly fused, it was pulverized again to carry out particle size adjustment so that the average particle diameter became 1 2 μ Π1. 5。 The average aspect ratio after the particle size adjustment is 4.3. Further, the natural graphite (60) coated with the carbonized resin was observed by a polarizing microscope to have a film-like optical isotropic phase on the surface and an optical anisotropic phase inside. This natural graphite (60) was heated at a temperature of 300 ° C for 6 hours in a non-oxidizing atmosphere to obtain a graphite material (600 °). With respect to the graphite material (600), as in Example 1, electron diffraction was performed on 10 sites near the surface, and crystallinity and crystallite size were measured. As a result, it was found that eight sites have polycrystalline properties, and it was confirmed to have a polycrystalline structure. The crystallite size rounds the average by 10 nm to 40 n. In Table 2, the characteristics of natural graphite (6) and the characteristics of graphite material (600) 49 326\patent specification (supplement) \94-11 \94127847 1271382 are shown. Further, using the graphite material (600), a working electrode and an evaluation battery were fabricated in the same manner and under the same conditions as in Example 1, and a charge and discharge test was performed. The evaluation results of the battery characteristics are shown in Table 3. As shown in Table 3, the graphite material (600) was used as the negative electrode material of the working electrode, and the obtained battery was not subjected to high rapid charge and discharge characteristics or cycle characteristics. Because the graphite material (600) is only coated and graphitized by the resin, it does not have a bulge.

The lithium ion secondary battery using the graphite material of the present invention as a negative electrode material has high rapid charge and discharge characteristics, and also exhibits excellent initial charge and discharge efficiency and cycle characteristics, and also has excellent discharge capacity. Moreover, according to the method of the present invention, the graphite material can be produced at low cost. Therefore, the lithium ion secondary battery using the negative electrode material of the present invention satisfies the requirement of increasing the energy density, and is effective in miniaturization and high performance of the mounted machine.

50 326\Patent specification (supplement)\94-11\94127847 1271382

Example 6 CO Natural graphite crucible r-Η Bu inch · Flaky phenolic resin iron oxide suspension * Dispersed (61) inch Τ.....< ο 卜 CjD 1 0.3355 5 ο CNI oo oo CO LO Q· Example 5 τ-Η 1 mesophase small sphere | LO CNI C<3 r-Η spherical sputtering dispersion exists /""N LO inch CNI CNI τ " H LO c<i 1 0.3356 5 OO τ i Oo <n! inch CD CD Example 4 τ1 i mesophase small sphere LO οα οα τ—Η spherical disk micro-powder dispersed in inch (NI oa τ—H oo r—i 0.3356 4 oa CO CO oo Bu CZ5 implementation Example 3 CO block-like mesophase LO CNI οο οά Block and scale-like resin iron hydroxide suspension dispersed (31) inch οα inch oi LO oi 0.3356 4 oa c>i oo T < 03 T-t Example 2 CNI mesophase small sphere LO rH LO 1 < block 41 iron hydroxide suspension dispersed οα 1 "·Ι LO τ—Η LO inch· ! 0.3356 7 00 01 CO cvi CNJ r—H Example 1 / ^s \w^ Mesophase small sphere LO oa οα rH Spherical 41 Iron hydroxide suspension dispersed in τ-Η inch (N1 03 rH V 11 "'< CO 0. 33 56 6 LO CO ◦ CO CNI r—i Type average particle size (//m) Average aspect ratio Shape Carbon source material Treatment Metal material type Metal material treatment form Metal material adhesion state average particle size (//m) Average aspect ratio U) CM 3 jlJ ancestor 1 icO 丨Ϊ ^ 1 CD 臼· ◦ Cl , an i 11 ® g| i nn Ei base® l V 1 4l 平均1 average height of the ridges h ( // m) bulge Average substrate length g (//m) Average h/g of the ridges Attachment treatment of the metal material _ _Long case r-SAZI inch 6\II46\(#:»)_^^DVKr*\9 (Ne 1271382

Comparative Example 6 CO Natural graphite crucible) T—Η 鳞 Scale-like resin 1 1 (600) <N1 τ·"Η CO Inch·〇〇0. 3356 0 1 1 1 Comparative Example 5 /^N y Ή Middle Phase small sphere LO οα CNJ T—S spherical iron nitrate solution film § CNl C<1 r—Η CD T丨"called 0. 3357 2 inch ◦·CD 〇· Bu CO cz> Comparative Example 4 Graphite material ( 10) Mesophase small sphere CO (XJ 1 Η spherical 1 1 〇 CD τ··· Η inch οα οο r - Η LO r-Η Cd 0.3360 100 or more # Unable to measure ^ Unable to measure Μ 1 Unable to measure w Comparative example 3 CO Bulk mesophase LO οα 〇〇<ΝΪ Block and scale-like resin disc 1 1 (310) Inch CNl inch oi Bu CD 0. 3357 0 1 1 1 Comparative example 2 r^s οα Mesophase small sphere LO r—Η LO τ— i Block disc 1 1 (20) inch LO r—1 3 CD 0. 3358 0 1 1 1 Comparative example 1 ι—Ι mesophase small sphere LO CNl CsJ rH spherical 1 1 ( 10) inch CNl rH LO <zi 0. 3358 0 ! 1 1 1 type average particle size (//m) average aspect ratio shape carbon source material treatment metal material type metal material treatment shape complaint metal material State d Average particle size (//m) Average aspect ratio specific surface area (m2/g) 1 1 S \ 1 〇白1 ◦ C 1 τ—1 W \ 1 *M π Warm 1 on E? Pain® i W 屮*The average height h of the 浚1 隆 h h (//m) The average base length of the ridge g ( //m) The average h/g of the bulge Material-V Attachment treatment θ _ Long trial. ¥冢丧碟-e/y "0«<铡砸衾-ffi:^-3⁄4 •^^w χονΉΝωαΉ ·· # .哳(01)实龙1,^衾铋刼夂衾铋刼夂夺妩}ΙονΉ Ν3Γ53 Case:* V, A inch 8Ζ .Π inch 6\11-inch 6\ipsi)_&^_fjVK-#\9ze 1271382

Co< Cycle characteristics (%) CO CD LO CD LO CD inch 05 CNI CD oo oo CNI Oi 5 CO oo Rapid discharge rate (°/〇) LO CJ5 CO C^5 inch inch CD CO 7 s 05 oo s oo oo OO Charging rate (%) oa 〇〇CO CO CD (NI CO sm CO inch LO inch inch C7D CO oo CNI inch initial charge and discharge efficiency (%) LO 05 CO CD CO CJ5 LO CJ5 inch CO 1 LO s oo oo s inch 05 CO CJ5 Discharge Capacity (mAh/g) 357 356 358 LO LO CO 356 T '< CO CO 348 349 CD LO CO 1 343 353 357 Example 1 Example 2 Example 3 Example 4 Example 5 Example 6 Comparative Example 1 Comparative Example 2 Comparative Example 3 Comparative Example 4 Comparative Example 5 Comparative Example 6 eloASI><NI176\I l46\ff}*)_^^DVK-w\9CNe 1271382 · [Industrial Applicability] The present invention The graphite material can be used as a negative electrode material for a chain ion secondary battery which is effective in miniaturization and high performance of a mounted machine. Further, it can be used for various applications requiring electrical conductivity or heat resistance, for example, a conductive material for resin addition, a conductive material for a fuel cell separator, and graphite for fireworks. BRIEF DESCRIPTION OF THE DRAWINGS Fig. 1 is a photograph of a scanning electron microscope 10 showing an example of a graphite material of the present invention. Fig. 2 is a schematic cross-sectional view showing the construction of a button type evaluation battery for a charge and discharge test. Figure 3 is a schematic view of a mechanochemical treatment apparatus used in the comparative example. Figure 4 is a schematic cross-sectional view of a graphite material having a dispersed ridge. [Main component symbol description] 1 Base material 2 Surface • 3 bulge 4 Enemy 1 1 Outer cup 1 2 Working electrode 1 3 Outer can 1 4 Counter 1 5 Separator 1 6 Insulation pad 326\Patent specification Parts)\94-11\94127847 54 1271382 17a, 17b collector 2 1 fixed cylinder 22 rotor 23 raw material 24 circulation mechanism 25 discharge mechanism 26 blade 27 stator 28 cover g base length h bulge

326\Patent specification (supplement)\94-ll\94127847 55

Claims (1)

1271382 X. Patent application scope: 1. A graphite material with a bulge with a height of more than 1 μm dispersed. 2. The graphite material according to claim 1, wherein the ratio of the height (h) of the ridge to the length (g) of the substrate (h/g) is from 0.1 to 15. 3. The graphite material as claimed in claim 1 wherein the graphite material has an average particle diameter of 3 to 1 0 0 // m. 4. The graphite material according to item 1 of the patent application, wherein the graphite material is a graphite of a mesophase small sphere. 5. A method of producing a graphite material by contacting a metal material having at least one of a property reactive with carbon and a property of dissolving carbon in a non-solution state with a precursor of the graphite material to cause the The metal material is dispersed on the precursor and heated at a temperature above 1 500 °C. 6. The method of producing a graphite material according to claim 5, wherein the powdery metal material is mixed with the precursor such that the metal material is dispersedly present on the precursor. 7. The method of producing a graphite material according to claim 5, wherein the metal material and the precursor are mixed in a dispersion medium, the dispersion medium is removed, and the metal material is dispersed and present on the precursor. 8. The method of producing a graphite material according to claim 5, wherein the metal material is dispersed on the precursor by a PVD method or a CVD method. 9. The method for producing a graphite material according to claim 5, wherein the precursor has optical isotropic properties in at least a part of its surface in 56 326\patent specification (supplement)\94-11\94127847 1271382 Crystal structure. 1 〇. A method for producing a graphite material, which is a metal material having at least one of a property of reacting with carbon and a property of dissolving carbon; and after graphitization, forming at least a portion of the optical material The carbon source material of the isotropic crystal structure is mixed, and the mixture is attached to the graphite material precursor and heated at a temperature of 1 500 ° C or higher. The method for producing a graphite material according to any one of claims 5 to 10, wherein the heating temperature is from 1 500 to 3300 °C. The method of producing a graphite material according to any one of claims 5 to 10, wherein the precursor is a mesophase small sphere. A negative electrode material for a lithium ion secondary battery, which comprises the graphite material according to any one of claims 1 to 4. 1 . A negative electrode for a lithium ion secondary battery, which comprises a negative electrode material for a lithium ion secondary battery according to the thirteenth aspect of the patent application. A lithium ion secondary battery using the negative electrode for an ion secondary battery as set forth in claim 14 of the patent application. 1 6 . A graphite material characterized by a ridge having a height of more than 1 // m on the surface. 326\Patent specification (supplement)\94·11\94127847 57