TW200403879A - Methophase spherule graphatized substance, and the negative electrode material, the negative electrode and the Li-ion battery using the same - Google Patents

Abstract

The present invention is a method for the process of applying both compression force and shear force on the methophase spherule graphatized substance, and for producing methophase spherule graphatized substance with the average cell interval d002 under X-ray diffraction below 0.337 nm, and in the Raman spectrum using Ar laser in wavelength of 514.5 nm, and the peak strength ID existing between 1350 to 1370 cm-1, and the ID/IG ratio being above 0.4 and under 2, wherein the peak strength IG existing between 1570 to 1630 cm-1 domain. Moreover, the present invention includes the mesophase ball-type graphite composite itself with such X-ray diffraction and Raman spectrum as the basis, wherein the obtained mesophase ball-type graphite composite can be used as the negative electrode of Li-ion battery and the negative electrode material. Even using the aqueous electrode paste, the method can still produce the Li-ion battery for maintaining large discharging and high starting discharge efficiency, and also with highly fast charging efficiency.

Description

200403879

CD 发明, description of the invention [Technical field of the toilet of the invention] The present invention relates to a lithium ion battery and a constituent material which are excellent in discharge capacity, initial charge and discharge efficiency, and fast charge efficiency. In particular, it is related to a lithium-ion battery that can maintain the discharge capacity and the initial discharge efficiency without reducing the fast-rate charging efficiency even when a negative electrode made from a water-based negative electrode mixture paste (paste) is used. Furthermore, the present invention relates to such a negative electrode and a negative electrode material for a lithium ion storage battery, and a graphitized substance constituting such mesophase (m e s o p h a s e) spheres and a method for producing the same. [Prior Art] In recent years, with the miniaturization or high performance of electronic devices, the demand for higher energy density of batteries has become higher and higher. Lithium-ion batteries are more attractive than other batteries because they can increase the voltage and increase the energy density. Lithium-ion batteries are mainly composed of a negative electrode, a positive electrode, and a non-aqueous electrolyte. The lithium ions generated from the non-aqueous electrolyte move between the negative electrode and the positive electrode during the discharge / charge process, and become a battery. Generally, the negative electrode material for the above-mentioned lithium ion battery is a carbon material. As such a carbon material, graphite having a laminated structure that can easily store / release lithium ions during charging / discharging, and which exhibits high discharge capacity and potential flatness has become the mainstream. As for graphite, graphitized materials such as artificial graphite, pitch-based carbon fibers, and mesophase carbon fibers, such as high-temperature fired materials such as natural graphite and coke, are well known. Furthermore, Japanese Patent Application Laid-Open No. 5-2 0 89 3 discloses that (2) (2) 200403879 is obtained by heat-treating mesophase pitch using tar (ta 0 or pitch) as a raw material. Mesophase graphitization. Among the above graphite materials, natural graphite has the advantage of high discharge capacity, but it is easy to orientate when forming a negative electrode because of its scale shape, so that the contact between non-aqueous electrolyte and graphite becomes ineffective. Full and rapid charge and discharge characteristics (also known as rate characteristics) will be reduced. Also, the expansion and contraction of graphite accompanying charging and discharging will become a direction, and the problem that the contact between graphite can no longer be maintained and the cycle characteristics will decrease. In contrast, the graphitized material obtained by subjecting the mesophase pitch to heat treatment, especially the graphitized mesophase spheres formed in the pitch, has a spherical or nearly spherical shape. Therefore, it is easy to follow a random shape during formation. (Random) lamination, so that the non-aqueous electrolyte can be uniformly contained in the negative electrode. In addition, the direction of the expansion and contraction of graphite with mixing charge and discharge will become a random way As a result, good fast charge and discharge characteristics and cycle characteristics will be exhibited. Japanese Patent Application Laid-Open No. 5-2 9 08 3 discloses that if asphalt is maintained at 3 5 0 to 5 0 (TC The resulting carbonaceous mesophase spheres can be obtained by hot melting temperature. After the mesophase spheres are carbonized and graphitized at 2500 to 2900 ° C, graphite can be obtained. In this bulletin, the graphitization of the above mesophase spheroids has an average particle diameter of 2 5 // m, and the average lattice plane interval d 〇 2 under X-ray diffraction is 0.3. 3 6 5 to 0.3 3 90 nm, and the ratio of the peak 値 intensity of 3 6 0 cm · 1 in the Raman spectrum to the peak 値 intensity of 1 5 8 0 cm · 1 is between In the range of 0.2 to 0.4, it is used as a negative electrode material for lithium ion batteries. -7- (3) (3) 200403879 However, if a graphitization of a mesophase sphere is used to make a negative electrode, and such a negative electrode is used to constitute In the case of lithium-ion batteries, depending on the type of solvent used in the production of the negative electrode, sometimes the battery cannot be fully utilized. Yes. Generally, when producing a negative electrode, a carbon material and a binder (a binder (η) resin) are first mixed with a solvent (hereinafter, including a solvent and / or a dispersant) to make it paste. Next, After applying the obtained paste (referred to as a negative electrode mixture paste) on a current collector such as copper foil, a negative electrode is prepared by pressing. For example, in the pasting process, a non-organic solvent such as an organic solvent is used. In the case of an aqueous solvent, an excellent lithium ion battery with a large discharge capacity and high initial charge and discharge efficiency and fast charge efficiency. On the other hand, in recent years, it has been desired to use a water-based solvent, that is, a water-based negative electrode mixture paste, from the viewpoints of the environmental side and the safety side. However, when an aqueous solvent (a medium containing water) is used as the solvent, battery characteristics such as fast charging efficiency may be reduced. That is, if the graphitization of mesophase spheres is used as a negative electrode material, the performance of the obtained lithium ion battery is affected by the type of solvent of the negative electrode mixture paste. In the present application, this is also referred to as the solvent dependency of a lithium ion battery. The inventors of this case used the well-known graphitized mesophase spheroids disclosed in the above-mentioned Japanese Patent Laid-Open No. 5-2 903 and the like as a negative electrode material, and used an aqueous or non-aqueous medium to produce a negative electrode. And explore the solvent dependence of lithium-ion batteries. As a result, it has been confirmed that, if an aqueous medium is used, the fast charging characteristics are degraded. In view of such a situation, the present invention is to obtain excellent crystallinity even when an aqueous negative electrode material mixture paste is used, and the discharge capacity is large, and the initial charge and discharge (4) (4) 200403879 is excellent in both efficiency and fast charging efficiency. For lithium ion batteries. In addition, the present invention aims to provide one or more such negative electrodes and negative electrode materials for lithium ion storage batteries having excellent properties, and graphitized materials forming mesophase spheres such as negative electrodes, and a method for producing the same. [Summary of the Invention] In other words, in the present invention, in the Raman spectrum of the X-ray diffraction, the average lattice plane interval dOO2 is 0.333 nm or less and the argon laser light with a wavelength of 514.5 nm is used, The ratio 强度 of the intensity 値 of the peak 値 existing in the region of 1 3 5 0 to] 3 7 0 c rrT 1 to the intensity g of the peak 1 existing in the field of 1 5 7 0 to 1 6 3 0 c ηΓ 1 I. / I. Graphite of mesophase spheres from 0.4 to 2. Here, the graphitization of the mesophase spheres is preferably a volume-converted average particle diameter of 3 to 50 // m and a specific surface area of 1 to 20 m2 / g. In addition, the graphitization of any of the above mesophase spheres preferably has a higher hardness than the graphitization of the mesophase spheres embedded in the surface, and the average particle size is higher than the average of the graphitization of the mesophase spheres. The small particles have a small particle diameter, and more preferably, the particles are at least one selected from the group consisting of silicon oxide, aluminum oxide, and titanium oxide. In addition, in this case, a negative electrode material for a lithium ion battery containing any of the above-mentioned graphitized mesophase spheres is also provided. Here, it is preferable that the negative electrode material further contains graphite other than the graphitized material of the mesophase spheres. Among these, (5) (5) 200403879 graphite coated with a carbon material having a lower crystallinity than the graphitization of the mesophase spheres is more preferable. Furthermore, the present invention also provides an invention for a negative electrode for a lithium ion battery, which is made of any of the foregoing negative electrode materials. The present invention also provides an invention of a lithium ion battery having any of the above negative electrodes. Furthermore, in this case, a process of simultaneously applying compressive force and shear force to the graphitization of mesophase spheres is also provided, and the average lattice plane spacing dGG2 under X-ray diffraction is 0.37 nm or less, And in the Raman spectrum using argon laser light with a wavelength of 514.5 nm, the intensity Id of the peak chirps existing in the field of 1350 to 1370 cm · 1, and the peak chirps existing in the field of 1 570 to 16 30 cm · 1 The ratio of the strength IG 値 I. / h is an invention of a method for producing graphitized mesophase spheres of 0.4 or more and 2 or less. Here, in this manufacturing method, it is preferable to carry out under the coexistence of fine particles having a hardness higher than that of the graphitized material of the mesophase small sphere and having an average particle size smaller than that of the mesophase small sphere. The said process WHEREIN: It is more preferable that the said fine particle system is a manufacturing method of at least 1 sort (s) chosen from the group which consists of a silicon oxide, an alumina, and a titanium oxide. BEST MODE FOR CARRYING OUT THE INVENTION The present invention is described more specifically as follows. First, the graphitization of the mesophase spheres of the present invention will be described. < Graphite of mesophase spheres > -10- (6) (6) 200403879 Generally, the mesophase spheres of the present invention are manufactured from a carbon material that is easily graphitized due to high-temperature heat treatment. Examples of such carbon materials include petroleum-based or coal-based tars and pitches. For example, when coal tar is heated to 350 to 500 ° C, polycyclic aromatic molecules will undergo a polycondensation reaction and become huge, and mesophase spheres which are small spheres with optical anisotropy will be produced. Mesophase spheroids can be separated and refined from optically isotropic asphalt substrates using benzene, toluene, quinoline, tar in oil, tar heavy oil, or washing oil organic solvent. The mesophase spheres obtained are not necessarily spherical, but most are spherical or nearly spherical. Therefore, it is commonly referred to as “mesophase spheres” among its peers and is different from other carbon materials. If the separated mesophase spheres are calcined at a temperature above 300 ° C in a non-oxidizing atmosphere, and finally treated at a temperature above 2000 ° C, the mesophase of the raw material of the present invention can be obtained. Graphite of small spheres. Since the mesophase spheroids can substantially maintain their shape before graphitization, they are mostly spherical or nearly spherical. The mesophase spheroids in this case may be those subjected to the final high-temperature treatment above 2000 ° C after the mesophase spheroids are crushed. Because the mesophase spheres are optically anisotropic, even if they are pulverized to graphitize them, there will still be no orientation problems like natural graphite, and they will exhibit excellent battery performance as a negative electrode material. However, if it is crushed excessively, it is not suitable because the irreversible capacity may increase. When pulverizing, a well-known pulverizing method and processing method can be appropriately used. The pulverization is preferably performed after a single firing at 300 ° C or higher, and before the final high temperature treatment. In this case, those who have crushed the mesophase spheroids are also graphitized by -11-(7) (7) 200403879. Here, the final high-temperature treatment in a non-oxidizing atmosphere is preferably performed at 2500 ° C or more, and more preferably at 2800T: or more. However, in order to avoid the sublimation or decomposition of graphitization, usually 5 is at most about 3 3 001. For example, mesophase spheres are subjected to a final high temperature treatment at a temperature exceeding 2000 ° C to graphitize them. The mesophase spheroids of mesophase spheroids with an average lattice interval dQ〇2 below 0.3 3 7 nm under X-ray diffraction can be obtained. However, in the Raman spectrum using argon laser light with a wavelength of 514.5 nm, the intensity of the peaks 存在 in the region of 3 50 to 1 370 cm · 1 Id exists in 1 570 to 1 6 3 The ratio of the intensity 値 of the peak 値 in the field of 0 cm · 1 to 〇I. / I. It is 0.3 5 or less. In the present invention, the above-mentioned graphitized compounds of the mesophase spheres (hereinafter referred to as "raw material graphitization") are subjected to a surface modification treatment to increase the above-mentioned Id / I. Compare In other words, the present invention is a method of manufacturing a graphitization of mesophase spheres by applying a compressive force and a shearing force simultaneously, and the average lattice plane interval d 〇〇2 in X-ray diffraction is 0.3 7 In the Raman spectrum using argon laser light having a wavelength of 514.5 nm or less, the intensity I d of the peak chirp existing in the region of 1 3 50 to 1 370 cm · 1 exists in the range of 1 5 7 0 to 1 6 3 The intensity of the peak 値 in the field of 0 c irT 1 is 10 to 之 I. / 1. Invention of a method of graphitizing mesophase spheroids of 0.4 to 2. In addition, the present invention is an invention of a graphitized body of mesophase spheres having such X-ray diffraction and Raman spectrum requirements. (8) (8) 200403879 The graphitization of the mesophase spheres of the present invention (hereinafter, referred to as "modified graphitization") is the average lattice plane interval in the __ direction under X-ray diffraction "ϋ2 It is 0.37 nm or less, and preferably 0.33 65 nm or less. In this way, the shorter graphitization of the average lattice plane interval dOO2 has better crystallinity, in other words, the degree of graphitization is also high Therefore, when used as the negative electrode material of a lithium-ion battery, a lithium-ion battery with a high discharge capacity can be obtained. Here, the average lattice plane interval d 0 0 2 refers to the use of CuK α-rays as X-rays and the use of X-ray diffraction method using high-purity silicon as a standard substance [by Otani Sugirou, carbon fiber, pp. 7 3 3 to 7 42 (published by Modern Press)]. The modified graphitization exhibits a specific Raman spectrum. Specifically, in the Raman spectrum using argon laser light with a wavelength of 5 1 4.5 nm, it exists in the range of 1 350 to 1 37 cm · 1. The intensity ID of the peak crest in the field is the intensity of the peak crest 1 (the peak tenacity at 3 o'clock) existing in the field of B70 to 1630 cm · 1 The ratio Id / I. Is in the range of 0.4 to 2. The peak chirping intensity referred to in this case refers to the intensity obtained by the height of the peak chirping. For example, if the X-ray diffraction and the stretching can be satisfied, The modified graphitization of the two elements of MAN spectrum to make a negative electrode, and when used as a lithium-ion battery, the solvent dependency of the lithium-ion battery will disappear. That is, even if the water-based negative electrode mixture paste is used, the performance can be maintained. The discharge capacity and initial charge-discharge efficiency of the lithium-ion battery, and the effect of fast charging characteristics will not be reduced. Here, at this time, if the Id / I ratio is less than 0.4, the fast charging characteristics may be reduced. On the other hand, if ID / I. When the ratio is more than 2, -13- (9) (9) 200403879 tends to decrease the valley M. The modified graphitization of the present invention is particularly preferably the above-mentioned Id / I The ratio is in the range of 0.45 to 1. The present inventors believe that the Id / Ie ratio in this way will affect the solvent dependence. The reason 'is due to the appearance of graphitization of mesophase spheres as raw materials. .Mechanism capable of obtaining surface modification effect It is very clear, but it may be due to the compressive and shear forces being applied at the same time, and the surface of the graphitized material is honed. Therefore, 'the majority of hydrophilic groups on the surface of the raw material graphitized can be considered to improve the hydrophilicity of the graphitized material itself. Therefore, the process of applying compressive force and shear force simultaneously (hereinafter referred to as "surface modification treatment") implemented in the present invention can be described as a kind of mechanics that changes or imparts chemical properties due to mechanical or physical treatment. Chemical treatment (mechanochemical treatment). As a means for confirming the hydrophilicity of the surface of the raw material graphitized material, the measurement of the contact angle between the graphitized material and water after the surface modification treatment, or the penetration rate of water, The measurement of the permeation amount is evaluated. The device used in the surface modification treatment of the present invention may be any device that can simultaneously apply compressive force and shear force to the object to be treated, and the device structure is not particularly limited. For such a device, for example, a kneading machine such as a pressure kneading machine, a double roll, a rotary ball mill, a hybrid system (manufactured by Nara Machinery Co., Ltd.), a micromechanical cloth (Nara Machinery Co., Ltd. ( )), Mechanical melting system (ni echa η fufu ο n system) (Hosokawa Micron (share) system) and so on. Among the above, it is preferable to use a device that utilizes a difference in rotational speed to simultaneously impart a shear force and a compressive force. For example: Figure 3 (a) and Figure 3 (b) -14-200403879 (10) show the Hosokawa micron (strand) mechanical fusion system of the model mechanism. This device includes a rotating cylinder (rotor 3), internal components (inner parts 32) different from the rotation speed of the cylinder, and a circulation mechanism (e.g., circulation blades 3 3) of the object to be processed. The reference numeral 3 5 is a discharge baffle, and 36 is a product. The raw material graphitide 3 4 supplied between the rotor and the internal parts is subjected to the compressive force and the shear force caused by the speed difference between the internal parts and the rotor under the telecentric force 5 caused by the rotation of the rotor. In addition, the raw material graphitization is repeatedly subjected to this compressive force and shear force due to the circulation mechanism. As another example, the hybrid system of the Nara Machinery Works (stock) system shown in the pattern shown in Fig. 2 may be mentioned. Reference numerals 2 and 3 designate blades, 25 designates circulation paths, 26 designates jackets for cooling or heating, 27 designates discharge valves, and 28 designates discharge ports. The raw material graphitide supplied from the input port simultaneously and repeatedly accepts the compressive force and the shear force caused by the speed difference between the rotor 22 and the fixed cylinder (stator 2 1) rotating at a high speed. In the method of the present invention, the shearing force and the compressive force applied to the graphitized material at the same time are usually larger than those of ordinary stirring. However, these mechanical stresses are preferably applied to the surface of the raw material graphitized material, and to the extent that the skeleton of the graphite material is not damaged. If the particle skeleton of the graphitized material is destroyed ', there is a tendency to cause an increase in the irreversible capacity of the Zhongli battery. When specifically exemplified, the surface modification treatment is preferably performed in such a manner that the reduction rate of the average particle diameter of the raw material graphitization can be suppressed to 20% or less. For example, when using a device having a rotating cylinder and internal components, it is preferable that the peripheral speed difference between the rotating cylinder and the internal components: 5 to 50 m / s, the distance between the two: 1 to 100 mm, and the processing time. : Conditions of 3 minutes to 90 minutes are performed under -15- (11) (11) 200403879. In the case of a device equipped with a fixed cylinder / high-speed rotating rotor, it is preferable that the peripheral speed difference between the fixed cylinder and the high-speed rotating rotor: 10 to 100 m / s, and the processing time is 3.0 seconds. To 10 minutes. According to the manufacturing method of the present invention as exemplified above, a graphitized mesophase sphere that is a modified graphitized compound that satisfies the two requirements of the aforementioned X-ray diffraction and Raman spectrum can be obtained. The shape of the modified graphitization of the present invention is preferably a spherical shape or an approximately spherical shape. However, since it has been treated with simultaneous application of compressive force and shear force, it can also be irregular particles due to granularity or crushing. The modified graphitized material of the present invention is preferably a volume-averaged average particle diameter of 3 to 50 / m. If the average particle size is more than 3 // m, it will not cause an increase in irreversible capacity or a decrease in battery safety when used as the negative electrode material of lithium ion battery. In addition, if it is 50 m or less, a lithium ion battery with good adhesion of the negative electrode can be obtained. The above average particle diameter is particularly preferably 5 to 3 0 // m. The true specific gravity of the modified graphitization is preferably 2.2 or more. The specific surface area of the modified graphitization of the present invention is preferably 1 to 20 m2 / g when measured by the specific surface area of the nitrogen adsorption B E T (Brunau-Emmett-Taylor) method. If it is less than 20m2 / g, it will not increase the irreversible capacity of the battery, and it is also more suitable in terms of safety. It is more preferably 5 m2 / g or less. If it is lm2 / g or more, it is easy to obtain excellent battery characteristics when a water-based negative electrode mixture paste is used. -16- (12) (12) 200403879 The modified graphitized material of the present invention is preferably embedded on the surface with a hardness higher than the hardness of the modified graphitized material itself, and the average particle size is higher than the average of the modified graphitized material. Those with a small particle size. Such a modified graphitization of the present invention can be obtained when the surface modification treatment of the raw graphitization is performed in the coexistence of the fine particles. As for the microparticles, 3 is not particularly limited as long as it has an average particle diameter smaller than the average particle diameter of the modified graphitization and is hard, and any microparticles may be used. For example, when the fine particles are aggregates, the primary particles may have a smaller particle size than the modified graphite. The shape and average particle size of the particles are not specified, but as long as it is about 1 mm, the surface modification effect of the raw material graphitization can be obtained. Further, in a manner that does not impede the contact between the obtained modified graphitides of the present invention with each other and does not adversely affect the charge and discharge characteristics, the upper limit is preferably about 00 nm. The microparticles can be helpful or unhelpful to conductivity or charge and discharge. Specific examples include metals, metal oxides, metal nitrides, metal borides, and metal carbides. Among these, preferred are hard particles having hydrophilic properties. Among them, fine particles of silicon oxide, aluminum oxide, or various metal oxides are preferable. In particular, at least one selected from the group consisting of silicon oxide, aluminum oxide, and titanium oxide is preferably silicon oxide, aluminum oxide, and titanium oxide, and is preferably produced by a gas phase method. The silicon oxide is preferably anhydrous silicon oxide. If the surface modification of the graphitized raw material is performed in the presence of such hydrophilic hard particles, the hydrophilicity of the obtained graphitized material can be further improved. -17- (13) (13) 200403879 In such a surface modification treatment, generally, the fine particles of the raw material graphitization can be used in an amount of from 0.01 to 0% by mass. In addition, the microparticles may be dry-blended with raw material graphitization (d r y b 1 e n d) in advance for the surface modification treatment, or may be added during the treatment of the raw material graphitization. Here, the used microparticles are embedded or integrated in the graphitization of the product, preferably at a level of about 0.1 to 5% by mass, more preferably at a level of about 0.0 to 0.5% by mass. If the surface modification treatment in which the fine particles coexist is performed as described above, in addition to hydrophilicity, a modified graphitized surface having a finely roughened surface can be obtained. In addition to the honing effect of the graphitized surface, the phenomenon that the particles are buried near the surface of the raw graphitized material may also be the reason for enhancing the effect of the present invention. In the present invention, as long as the effect of the present invention is not impaired, various additives such as a known conductive material, ion conductive material, surfactant, polymer compound, etc. can be added. This addition period can be before, during, or after the surface modification treatment. < Negative electrode material for lithium ion battery > In this case, a negative electrode material for a lithium ion battery containing the modified graphitized compound of the present invention described above will also be provided. Generally, when making a negative electrode of a lithium ion battery, first, a carbon material and a binder are mixed in a solvent (including a solvent and / or a dispersant) to make it paste. Next, the obtained paste (referred to as a negative electrode mixture paste) is applied to a current collector, the solvent is removed, and the press is used to cure and / or -18- (14) 200403879 is shaped or shaped, The negative electrode material of the negative electrode must be invented and modified on the graphite surface of the collector's natural graphite lithium ion energy source, and the graphite graphitization solution still capable of contacting the graphite is immersed in order to obtain at least the modified stone material at the end of the negative electrode process. In addition, in the invention of the agent 5 and the like, in the invention, the performance of any battery can be optimized for the reason. Because of the combination with the compound, water. In the material, and the permeability, etc., this description. ° The negative electrode material of the present invention refers to the meaning of this curing and / or all materials. That is, the above-mentioned modified graphitization in this negative electrode material is an essential element. Therefore, this material) itself is also a negative electrode mixture paste obtained by adding the modified graphite compound and the binder of the present invention to the lithium ion battery of the present invention, and then applying the paste, which is also the present invention. Range of negative electrode materials. As long as the modification of the present invention is used as a negative electrode material, even if a water-based negative electrode mixture paste is used, the fast charging efficiency is not reduced. The reason for the different fast charging characteristics may be due to the hydrophilization of the original surface and further roughening. After the expression, the “modified graphitization may become a solid and tight seal in the water system” and it can be recharged and discharged repeatedly. The binding agent and the current collector can be firmly connected to each other. The binding agent can uniformly form a thin film, and the modification may inhibit conductivity, ion conductivity, and electrical factors. In addition to the negative electrode material for the lithium ion battery of the invention, in addition to the negative electrode material of Weiming, graphite other than the modified graphitization (graphite to surface-modified mesophase spheres) of the present invention (hereinafter '' (Referred to as "other graphite"). When other graphites are used, such as other graphites whose combined shape and / or average particle size are different from the modified graphitized materials of the invention of this -19- (15) (15) 200403879, it is more suitable because the fast charging efficiency will be improved. . Specific examples can be exemplified: a combination of the spherical modified graphite compound 5 of the present invention and scaly and / or fibrous other graphite; the scaly modified graphite compound of the present invention, and the spherical and / or fibrous other Graphite combinations. In the case of spherical shapes, for example, for the modified graphitizing material of the present invention having an average particle size of about 30 V m, other methods such as an average particle size of about 10 # m are combined with other graphites. Such other graphites are not particularly limited, but may be specifically exemplified: graphitized (raw material graphitized) mesophase spheres that have not been treated with simultaneous application of compressive force and shear force, etc. ; Burning coal-based tar and pitch to heat the mesophase into carbon (volume mesophase (b 111 k mesophase), coke (green coke, wet coke, pitch coke, needle coke) , Petroleum coke, etc.) and finally heat treated to make it graphitize above 2500 ° C. Or, for example: those who heat-treated petroleum tar and bitumen to graphitize it. Also, as such other Graphite may also be exemplified: artificial graphite, natural graphite, etc. Other graphites may be a combination with the above-exemplified graphite materials. Among the above-mentioned other graphites, it is preferable to use modified graphite that is more crystalline than the present invention. (The surface modification of the mesophase spheroid graphitization) has a low crystallinity of graphite covered with carbon material. The term "coated graphite with low crystallinity" referred to herein means that the core material is less than the coating material. for Relatively high crystalline graphite. It is a carbon material of the coating material (hereinafter, also referred to as the coating material), which is lower in crystallinity than the graphite of the core material (hereinafter also referred to as the core material-20- (16) (16) 200403879). And the more modified graphitization (the surface-modified mesophase spheroid graphitization) is a low-crystalline carbonaceous or graphite carbonaceous material. As long as the coating material is present inside the particles of the core material And / or the surface, but it is preferred that more than one and a half of the coating material exist on the surface of the core material. With the X-ray diffraction of this graphite after coating, it is difficult to judge the crystallinity of the core material and the crystal of the coating material separately. Therefore, the crystallinity of the covering material is defined by the average lattice plane interval d 002 in the x-ray diffraction obtained when the covering material is separately heat-treated. That is, a preferable average of the covering material The lattice plane interval “μ is 0.37 nm, and more preferably 0.34 nm or more. This intensity ratio (ID / I.) in Raman spectroscopy generally represents 0.1 or more. Manufacturing method for attaching and / or impregnating organic compounds in core material It can be obtained by performing the final high temperature treatment at a temperature of 900 ° C or higher and 2800 ° C or lower. Particularly preferred is 1] 50. (: Above, Z temperature below 2300 C) It is made by the final local temperature treatment. If the final high temperature treatment is performed below 900 ° c or 280 (TC or higher), good fast charging efficiency cannot be obtained. The core material can be selected from various natural graphites, Among artificial graphites, scaly graphite, block graphite, spherical graphite, etc. are preferred. The core material is preferably one with moderate voids. The particle size of the core material is preferably between 1 and 3 0 // m The range is. The specific surface area of the core material is not particularly limited, but it is preferably 0.5 m 2 / g or more. The crystallinity of the core material is represented by the average lattice plane interval d〇02 under X-ray diffraction. 〇.337nm or less. As the raw material of the coating material, -21-(17) (17) 200403879 organic compounds which have carbon residues due to heat treatment were selected. It is preferred that rhenium does not contain heavy metals or light metals that hinder charge-discharge reactions or promote decomposition of the electrolyte. Particularly preferred are thermosetting resins, thermoplastic resins, coal-based or petroleum-based heavy oils, tars, and asphalt. Particularly preferred are those containing carbonaceous particles (fine powder of coal carbon, primary QI (< 31-series quinololine insoluble matter), carbon black, graphite or graphite particles, etc.). These composite materials can be directly or after being dissolved or dispersed in a solvent, mixed with the graphite of the core material, and then heat-treated. The mixing ratio of the coating material to the core material is the total amount after the final high temperature treatment, and the coating material is 0.5 to 30% by mass, particularly 3 to 20% by mass. If the coating material is excessive, the discharge capacity will decrease. If there are too few coating materials, the initial charge and discharge efficiency will decrease. The addition amount of such other graphites depends on the shape or average particle size of other graphites and the modified graphitization of the present invention, but the total amount of other graphites and the modified graphitization of the present invention is preferably in the range of 0.5 to 90% by mass. For example, if the upper limit of the amount of addition is made to a better quality of 70. / ° degree 'can obtain more excellent fast charging efficiency. For example, when the modified graphitized material of the present invention has an average particle diameter of 20 to 30 / m, 5 to 40 mass% of flaky shape is used as such other graphite (size of the flat portion: 3 to 15 / / m) of natural graphite and / or artificial graphite. Alternatively, if the modified graphitized material of the present invention has an average particle diameter of 5 to 15 // m, then as such other graphite, 20 to 70% by mass of coated graphite (having an average particle diameter of 15 to 30 M m of graphite with low crystalline coating material). The mixing method of this modified graphitization compound and this other graphite is not particularly limited, but in general, various mixers are used in a dry manner directly according to the state of the powder. In addition, as long as the object of the present invention is not impaired, it may be a mixture with other carbon materials (including amorphous hard carbon, etc.), organic matter, metal compounds, granules, coatings, and laminates. It may also be a liquid, gas, or solid-phase chemical treatment, heat treatment, or oxidation treatment. In addition, in the present invention, it is preferable to use an organic binder that is chemically stable and electrochemically stable to the electrolyte, as a binder that is a negative electrode mixture paste. For example, fluorine-based resins such as polydifluoroethylene and polytetrafluoroethylene, polyvinyl alcohol, carboxymethyl cellulose, and styrene butadiene rubber can be used. These organic binders can also be used. Among the above, in order to achieve the purpose of the present invention and maximize the effect, it is particularly preferable to use carboxymethyl cellulose (water-soluble), polyvinyl alcohol (water-soluble), and styrene butadiene rubber (water Dispersibility) and so on. The binder is preferably used in an amount of about 0.5 to 20% by mass based on the entire amount of the negative electrode mixture. Next, the manufacturing method of the negative electrode is described, and then the negative electrode material will be described. For example, the modified graphitized material of the present invention is adjusted to an appropriate particle size by a method such as classification, and mixed with a binding agent to prepare a negative electrode mixture. This negative electrode mixture is dispersed in a solvent to form a paste, and is usually applied to one side or both sides of a current collector. Then, by drying this, the negative electrode mixture layer can be uniformly and firmly adhered to the current collector to form the negative electrode mixture layer. -23- (19) (19) 200403879 More specifically, any of the modified graphitization compounds of the present invention can be used as a binding agent with, for example, carboxymethyl cellulose, styrene butadiene rubber, and the like, and Solvents such as water and alcohol are mixed to form a slurry, and then coated. Alternatively, a fluororesin powder such as polytetrafluoroethylene or polydifluoroethylene may be mixed with a solvent such as isopropanol, N-methylpyrrolidone, dimethylformamide, or the like, and then coated. Among them, in consideration of the influence on the safety surface and the environmental surface during the removal and drying of the solvent, it is preferable to use water or a water-containing alcohol as a solvent, and use a binding agent such as carboxymethyl cellulose, styrene butadiene rubber, and / Or dispersed water-based negative electrode mixture paste. The paste can be prepared by mixing with a well-known mixer, mixer, kneader, and kneader. In the present invention, if the negative electrode mixture paste is applied to the current collector, the thickness is preferably 10 to 200 // m. In addition, the modified graphitized material of the present invention can also be dry-mixed with resin powders such as polyethylene and polyvinyl alcohol, and formed into a negative electrode by hot-press molding in a metal mold. At this time, of course, the lithium-ion battery does not have a solvent dependency. If there is too much binding agent, the discharge capacity of lithium-ion batteries or the rapid charge and discharge efficiency may be reduced. Since a large amount of binder is required in order to obtain sufficient negative electrode strength in dry mixing, the aforementioned wet mixing (a method of dispersing the binder in a solvent) is preferably used. If the negative electrode mixture layer is formed and then press-bonded with a press or the like, the adhesion strength between the negative electrode mixture layer and the current collector can be further increased. The shape of the current collector used for the negative electrode is not particularly limited. -24- (20) 200403879 can be used in foil or mesh. # In the case of foil,

For electrical materials, such as copper, stainless steel, and nickel, it is better to use a thickness of 5 to 20 // m. < Negative electrode for lithium ion battery> In the present case, also + Usagawa "" invention of a negative electrode for a lithium ion battery made of the negative electrode material of the present invention. The present invention; ># ρ — ′ means that the above-mentioned negative electrode material of the present invention can be E-shaped and / or shaped without & The formation of the negative electrode can be implemented according to the usual method of force, but if the ancestor can fully exert the properties of graphitization, and the formability is very high, it can be chemically stable and stable in electrical chemistry. The negative electrode method is not particularly limited. _This month's modified graphitides are especially suitable for the above-mentioned lithium ion storage anode A-negative anode materials and negative electrodes, but they can also be used for applications other than negative electrode materials. According to the present invention, a lithium ion battery using the negative electrode is further provided. < Lithium-ion battery > The bell-ion battery generally uses a negative electrode, a positive electrode, and a non-aqueous electrolyte as a main battery component. The positive and negative electrodes will become lithium ion beta carriers, respectively. It is a battery mechanism in which lithium ions will be doped (dope) into the negative electrode during charging, and dedoped (de dope) from the negative electrode when discharged. The lithium ion secondary battery of the present invention is not limited to the negative electrode except that the negative electrode is prepared from the negative electrode material containing the modified graphitized material of the present invention. The rest is not limited to -25- (21) (21) 200403879. For other components, the general lithium-ion battery elements are used. As the material of the positive electrode (positive electrode active material), it is preferable to select a material capable of doping / dedoping a sufficient amount of lithium. Examples of such a positive electrode active material include a complex chalcogenide of lithium and a transition metal, particularly a complex oxide of lithium and a transition metal. The composite oxide of lithium and transition metal (also known as lithium-containing transition metal oxide) can be a solution solution of lithium and two or more transition metals. Specifically, LiM (1) 2-XM (2) x02 (where X is OS Xg), and M (1) and M (2) are made of at least one transition metal element. ) Or LiM (1) 2_YM (2) γ04 (where Υ is a number in the range of 0 SYS 1, and M (]) and M (2) are at least one transition metal element.) Means. Among the above, the transition metal element represented by M may be: Co (cobalt), Ni (nickel), Mn (manganese), Ci • (chromium), Ti (titanium), V (vanadium), Fe (iron ), Zιι (zinc), A1 (aluminum), In (indium), Sn (钖), etc. More specifically, LiCo02 or LixNixM γ02 (M is the above transition metal element other than Ni, preferably at least one selected from Co, Fe, Mn, Ti, Cr, V, A1, and 0.05SXS1.10 , 0.5 $ Υ $ 1.0.) And the composite oxide with lithium. Lithium-containing transition metal oxides as described above are based on, for example, Li (lithium), oxides or salts of transition metals as starting materials, and the starting materials are mixed according to the composition, and in the presence of oxygen, It can be prepared by firing at a temperature range of 600 ° C to -26- 200403879 C22) 0 0 0 ° c. The starting material is not limited to a gaseous substance or a salt, but may be synthesized from a hydroxide or the like. In the present invention, as the positive electrode active material, the above-mentioned compound 5 can be used alone or two or more kinds can be used. For example, a carbonate such as lithium carbonate may be added to the positive electrode. Such a positive electrode material is used to form a positive electrode. For example, a positive electrode mixture layer is formed by applying a positive electrode mixture made of a positive electrode material, a binder, and a conductive agent for conductivity to both sides of a current collector. As the binder, any of those exemplified for the negative electrode can be used. As the conductive agent, for example, graphitization can be used. The shape of the current collector is not particularly limited, and a foil shape, an eye shape, a mesh shape such as a mesh, a mesh iron, or the like can be used. For example, the material of the current collector may be aluminum, stainless steel, nickel, or the like. In terms of thickness, 10 to 40 // m is more suitable. In the case of the positive electrode, the positive electrode mixture may be dispersed in a solvent to form a paste, and the paste-like positive electrode mixture may be coated on a current collector and dried to form a positive electrode mixture layer. After the positive electrode mixture layer is formed, compression bonding such as pressurization by a press may be performed. Thereby, the positive electrode mixture layer can be uniformly and firmly adhered to the current collector. When forming a positive electrode as described above, various additives such as a known conductive agent or a binder can be appropriately used. As the electrolyte of the present invention, an organic electrolyte composed of a solvent and an electrolyte H, or a polymer electrolyte composed of a polymer and an electrolyte salt can be used. As the electrolyte salt, for example, L i P F 6, L i B F 4, -27-(23) (23) 200403879 can be used.

LiAsF6, LiC104, LiB (C6H6), LiCl, LiBr, LiCF3S〇3, LiCH3S03 'LiN (CF3SO2) 2, LiC (CF3S〇2) 3,

LiN (CF3CH20S02) 2, LiN (CF3CF20S02) 2,

LiN (HCF2CF2CH2〇S〇2) 2, LiN ((CF3) 2 CH 0 S 0 2) 2, L i B [C e H 3 (CF 3) 2] 4 'L i A 1 C 1 4, L i S i F 6 and so on. In particular, L i P F 6 and L i B F 4 are preferably used because of good oxidation stability. The concentration of the electrolyte salt in the organic electrolyte is preferably 0 to 1 mol / liter, more preferably 0.5 to 3.0 mol / liter. For organic electrolyte solvents, vinyl carbonate, methylenyl carbonate, dimethyl carbonate, diethyl carbonate, I, ^ or I, 2-dimethoxyethane, and 1,2-diethyl can be used. Ethoxyethane, tetrahydrofuran, methyltetrahydrofuran v-butyrolactone, 1 '3-dioxolane, 4-methyl_I, 3_dioxolane, hydrazine, diethyl ether, cyclobutane , Methylcyclobutane, acetonitrile, chloronitrile, propionitrile, trimethyl borate, tetramethyl silicate, nitromethane, dimethylmethanamine, N-methylpyrrolidone, ethyl acetate, orthoformate Proton-inert organic solvents such as methyl ester, nitrobenzene, phenylarsin chloride, phenylarsin bromide, tetrahydrothiophene, dimethyl asus, 3-methyl-oxazolidinone, ethylene glycol, dimethyl sulfur, etc. For example, when a non-aqueous electrolyte is used as the polymer electrolyte, a matrix polymer 1 containing a plastic base (non-aqueous electrolyte) is used as the matrix polymer. An ether system such as polyethylene oxide or a crosslinked body thereof can be used. Polymers, polymethyl propylene ', polyacrylic acid vinegar-based polyvinylidene fluoride or polyvinylidene fluoride water: · Fluoropolymers such as hexafluoropropylene, Greek copolymers, etc. Mixing method -28- (24) (24) 200403879 Among them, since redox stability is better, it is preferable to use a fluorine-based polymer such as polyvinylidene fluoride or a polyvinylidene fluoride-hexafluoropropylene copolymer. 〇 As for the electrolyte salt or the solvent constituting the plasticizer contained in the polymer electrolyte, any of the foregoing can be used. The concentration of the electrolytic salt in the electrolytic solution, which is itself a plasticizer, is preferably 0.1 to 5 mol / liter, and more preferably 0.5 to 2.0 mol / liter. The method for producing such a polymer electrolyte is not particularly limited, and examples thereof include a method in which a matrix-forming polymer compound, a lithium salt, and a solvent are mixed and heated to melt. Furthermore, after dissolving a polymer compound, a lithium salt, and a solvent in an appropriate organic solvent for mixing, a method of evaporating the organic solvent for mixing, and mixing a monomer, a lithium salt, and a solvent, and irradiating ultraviolet rays and electrons thereto A method of forming a polymer by a wire or a molecular wire or the like. The addition ratio of the solvent in the polymer electrolyte is preferably 0 to 90% by mass, and more preferably 30 to 80% by mass. When it is 10 to 90% by mass, the electrical conductivity is high, the mechanical strength is high, and the film is easily formed. In the lithium ion battery of the present invention, a separator (Separator) ° separator can also be used, which is not particularly limited. Examples include woven fabrics, non-woven fabrics, and microporous membranes made of synthetic resin. In particular, a microporous membrane made of synthetic resin is preferred. Among them, polyolefin-based microporous membranes are preferred because they have better membrane strength and membrane resistance. Specifically, it is a microporous film made of polyethylene or polypropylene, or a microporous film that is a composite of these. -29- (25) (25) 200403879 In the lithium ion battery of the present invention, a polymer electrolyte can also be used because of the high initial charge and discharge efficiency. Lithium-ion batteries using polymer electrolytes are generally referred to as polymer batteries. It can be composed of a negative electrode containing the modified graphitization of the present invention, a positive electrode, and a polymer electrolyte. For example, they are laminated in the order of a negative electrode, a polymer electrolyte, and a positive electrode, and are housed in a battery exterior material. Here, a method in which a polymer electrolyte is arranged outside the negative electrode and the positive electrode can also be made. In a polymer battery using the modified graphitizer of the present invention as a negative electrode material, propylene carbonate may be contained in the polymer electrolyte. In general, 'propylene carbonate's electrical decomposition reaction of graphite is fierce', but the reactivity of the modified graphitization of the present invention is relatively low, and 'the structure of the lithium ion battery of the present invention can be determined arbitrarily, The shape and form are not particularly limited. You can choose from cylindrical, square, coin, and button types. In order to obtain a sealed non-aqueous electrolyte battery with higher safety, it is preferable to have a means capable of detecting an increase in the internal pressure of the battery and shutting off the current when an abnormality such as overcharging occurs. In the case of a polymer battery using a polymer electrolyte, it is also possible to have a structure enclosed in a laminated film. [Embodiments] Examples Hereinafter, the present invention will be specifically described by way of examples, but the present invention is not limited by these examples. Further, in the following Examples and Comparative Examples -30- (26) (26) 200403879, the 'series M graphitization was produced as a button-type battery for evaluation with a structure shown in Fig. 1 for evaluation. However, in the real battery, it can be made according to the well-known method according to the concept of the present invention. In this evaluation battery, the active electrode is represented by a negative electrode, and the opposite electrode is represented by a positive electrode. Here, in the following examples and comparative examples, the physical properties of the particles were measured in the following manner. The average particle diameter is measured using a laser diffraction particle size distribution meter. The average lattice plane interval is measured using X-ray diffraction. The specific surface area is a BET specific surface area by nitrogen adsorption. The hardness' is measured by the following method. 5 g of graphene was filled in a cylindrical container (internal diameter: 2.1 μm), and tapped at 2,000 times. Then, a steel rod with an inner diameter of a cylindrical container is pushed in from the top of the concrete filling surface, and a compression test is performed at a rapid speed. The load under) is expressed as relative 値. That is, 'the inflection point load of the graphitization used in the embodiment 丨 described later is taken as! , To represent the relative inflection point load of each graphitized material and hard particles. The Raman analysis of graphitization was performed by using NR-1 800 0 'manufactured by JASCO Corporation using argon laser light having a wavelength of 514.5 nm2. Example 1 (1) Preparation of negative electrode material Mesophase spheroids (made by Kawasaki Steel Co., Ltd., average particle size: 2 5 # m) obtained by heat-treating coal tar pitch at 300 ° C Its graphitization 'makes mesophase spheroid graphitization (raw graphitization). This stone -31-(27) 200403879 The ink system is spherical, and the true specific gravity between the average lattice planes is 2. 2 2 8 (density 2.2 2 8 g / cm 3). The relative hardness of 0.45m2 / g値 is 1. Next, for this graphitization, a processing device (made by Nara Machinery Co., Ltd.) was used as the second |, and simultaneous compressive force and shear were applied under the following conditions, that is, under the condition that the peripheral speed of the rotating rotor was 40 m / sec. The treatment is performed while dispersing the inside of the device while applying compressive force and shear force repeatedly. The places where the above compressive force and shear force are simultaneously applied appear spherical, and the average particle diameter is 24 // m This intensity ratio ( I d / I. ratio) is 0.4 7. The average crystallinity is maintained at 0.3 3 6 2 nm. (2) Modulation of negative electrode mixture paste The graphitized (modified graphitized) obtained by applying a compressive force at the same time as described above, The negative electrode mixture paste of the solvent was prepared separately. ≪ Preparation of the negative electrode mixture paste of the water system > 97% by mass of the modified graphitization, 1% by mass of cellulose, and 2 styrene butadiene rubber were mixed and used. Homogeneous mixer (homomixer minutes, preparing the negative electrode mixture paste of the water system. The interval d 〇 () 2 is 0.3 3 6 2 nm. In addition, the specific surface area is the schematic structure shown in the figure: the hybrid action system) While The processing time is 6 minutes, and the graphitization after the graphitization physics is added. The result obtained by Raman analysis: the grid interval is "02" and the amount of carboxymethyl groups in the aqueous solvent and organic binder after the shear force treatment is% Use water as solvent •) Stir 5 -32- at 28 rpm (28) (28) 200403879 < Preparation of Organic Negative Electrode Mixture Paste > 90% by mass of modified graphitization and polymer as binder Difluoroethylene] 0% by mass, mixed with N-methylpyrrolidone as a solvent, and stirred at 500 rpm for 5 minutes using a homomixer to prepare an organic negative electrode mixture paste. (3) Preparation of negative electrode The negative electrode mixture paste is coated on a copper foil (current collector) with a uniform thickness, and the solvent is evaporated to dryness under a vacuum of 90. Then, the copper foil is coated with a roller press to apply the coating. The negative electrode mixture. Then, it was punched into a circular shape with a diameter of 5.5 mm to produce a negative electrode 2 made of a negative electrode mixture layer which is closely adhered to the current collector 7b. (4) Production of a positive electrode A lithium metal foil was laminated Nickel net (nickel net) and integrated punch-through to a diameter of 15.5 mm It has a circular shape to produce a positive electrode 4 made of a lithium metal foil that is tightly attached to a current collector 7 a of a nickel mesh. (5) The electrolyte is charged with 33% by mole of ethylene carbonate and 67% by ethyl methyl carbonate. LiPF6 is dissolved in a solution mixed at a ratio of 1% to 1 mol / dm 3 to prepare a non-aqueous electrolyte solution, and a separator in which the non-aqueous electrolyte solution is impregnated in the porous polypropylene body is produced. 5. -33- (29) (29) 200403879 (6) Production of evaluation battery As an evaluation battery, a button-type storage battery having the structure shown in the figure is produced. First, a separator 5 impregnated with an electrolyte solution is laminated between the negative electrode 2 in close contact with the current collector 7b and the positive electrode 4 in close contact with the current collector 7a. Then, in a manner that the negative electrode current collector 7b side can be accommodated in the outer casing 1 and the positive electrode current collector 7a side can be accommodated in the outer casing 3, the outer casing 1 and the outer casing 3 are mated. At this time, the peripheral edge portion between the exterior cover 1 and the exterior tank 3 is interposed between the insulation sealing coating 6 and the two peripheral edge portions are tightly closed to be sealed. The evaluation battery produced as described above was subjected to a charge-discharge test of the following formula at a temperature of 2 5 t. (7) Charge and discharge test < Initial discharge efficiency > The circuit voltage can reach 0mV, and a constant current charge of 0.9mA is performed. Then, switch to constant current charging and continue charging until the current 値 reaches 20 μA. Then, rest for 120 minutes. Secondly, discharge at constant current until the circuit voltage reaches 1.5 V with a current of 0.9m A. At this time, the charge capacity and the discharge capacity are obtained from the energization amount in the 1 st cycle, and the initial charge and discharge efficiency is calculated from the following formula. Initial charge and discharge efficiency (%) = (charging capacity / discharging capacity) x 100-34- (30) 200403879 In addition, in this test, the process of doping lithium ions into graphitization was used as charging. The process of graphitization de-doping acts as a discharge. < Fast charging efficiency > Continuing the above, high-speed charging is performed in the second cycle. Make the current 値 4.5 times 5 times, and implement constant current charging until the circuit voltage reaches OmV. From the obtained charging capacity, the fast charging efficiency is calculated according to the following formula. Fast charging efficiency (%) (constant current charging capacity in the second cycle) ^ 100 ′ (discharge capacity in the first cycle) x (8) Evaluation of the hydrophilicity of the negative electrode material It is evaluated as follows. 15 g of the modified graphitization of the present invention was filled in a cylindrical container made of barbed wire and filter paper at the bottom, and tapped 160 times. Then, the bottom of the container was brought into contact with the water surface to measure the change in the permeation amount of water over time. The table below shows the discharge capacity (mAh / g), the initial charge / discharge efficiency (%), and the fast charge efficiency (%) of the modified graphitization per 1 g measured in the above. The evaluation result of hydrophilicity is shown in Fig. 4. Example 2 The procedure (()) of Example 1 was performed in the coexistence of anhydrous silica as described below to prepare a negative electrode material. The rest of the conditions are the same as in the embodiment] -35- (31) (31) 200403879. That is, in the process of (]) in the example], the raw material graphitization compound] 00 parts by mass, and anhydrous silicon oxide (AEROS1L 3 0 0 manufactured by Elosir Japan), average particle size 7ηηι, hardness is relatively high 4J) After 0.2 parts by mass was put into the processing device, except that the processing time was set to 2 minutes, the rest of the processing was performed in the same manner as in Example 1 by applying a compressive force and a shearing force. The graphitized material after the surface modification treatment was spherical, and the average particle diameter was 2 3 m. The intensity ratio (丨 D / 丨. Ratio) in the Raman analysis is 0.57. The average lattice plane interval doQ2 in X-ray diffraction was 0.3 3 62 nm. This negative electrode material was evaluated in the same manner as in Example 1. Table 1 shows the battery characteristics, and Figure 4 shows the hydrophilicity of the negative electrode material. Example 3 In Example 1, when ()) the negative electrode material was prepared, a device for simultaneously applying a compressive force and a shearing force was changed to a simplified structure as shown in Figs. 3 (a) to (b). The treatment device (mechanical melting system manufactured by Hosokawa Micron Co., Ltd.) was implemented in the same manner as in Example 1 except that the surface modification treatment was performed under the following conditions. That is, 'for graphitization, according to the distance between the rotating cylinder and the internal structure 5 m m', the rotation of the rotating cylinder is 200 m / sec and the processing time is 60 minutes, and the processing of applying compressive force and shear force repeatedly is performed simultaneously. The graphitized material after the surface modification treatment was spherical, and the average particle diameter was 2 5 μ 5. The intensity ratio (ID / I. Ratio) in the Raman analysis was 0.45. X-ray diffraction -36- (32) 200403879 The average lattice plane spacing d. . 2 is 0.3 3 6 2 n m. Next, a negative electrode mixture paste, a negative electrode, and a lithium ion storage negative electrode material were prepared, and evaluated in the same manner as in Example 1. 4 shows the battery characteristics, and FIG. 4 shows that the negative electrode material lacks hydrophilicity. Example 4 100 parts by weight of raw material graphitized titanium (P2 5 manufactured by Elosir Japan), average particle size 2] relative to 4.6) in a total of 0.5 parts by mass, with the same surface modification as in Example 3 for a processing time of 10 minutes Sexual treatment. The surface-modified compound has a spherical shape and an average particle diameter of 24 // m. The intensity ratio (I d / I. ratio) in the Raman analysis was 0.6 3. The lower average lattice plane interval do 〇2 is 0.3 3 62 nm. Next, a negative electrode mixture paste, a negative electrode, and a lithium ion storage negative electrode material were prepared, and evaluated in the same manner as in Example 1. The battery characteristics are shown in FIG. 4, and the hydrophilicity of the negative electrode material is shown in Table 1 as shown in Examples 1 to 4 of Table 1. It is shown that the lithium ion battery used as the negative electrode material in the negative electrode not only uses the organic type agent paste, but also maintains high discharge capacity and high initial charge and discharge efficiency even when using the water-based negative electrode mixture paste. The fact of high fast charging efficiency. As shown in Fig. 4 (Examples 1 to 4), the material of the present invention is treated by applying a compressive force and a shear force at the same time, so that the water infiltration increases. Furthermore, the battery is operated in the coexistence of hard particles. ί. In the table below, the battery is made of oxygen n m, hardness, and graphite X-ray diffraction. Take up. In Table 1, when the negative electrode combination of the present invention is used, the negative electrode material also has a large permeation capacity for processing reasons -37- (33) (33) 200403879, and the permeation amount of water is further increased. In addition, for comparison, the raw graphite was pulverized to produce the same specific surface area as that of the modified graphitization of the present invention. The same water absorption test was also performed, but no increase in water permeability was confirmed. It is known from the fact that the negative electrode material 3 of the present invention has been highly hydrophilized. Comparative Example] Instead of the modified graphitization of Example], the raw graphitization of Example 1 without surface modification treatment was used (Raman analysis 値 Id / Ic ratio = 0.20). The rest are prepared in the same manner as in the example to produce a negative electrode and a lithium ion battery. Figure 4 shows the hydrophilicity of this raw material graphitization. Table 1 shows the results of the battery characteristics. As shown in FIG. 4, the negative electrode material 殆 does not exhibit hydrophilicity. As shown in the table], it can be seen that in a lithium ion battery in which a graphitization (raw material graphitization) of mesophase spheres that have not been subjected to a simultaneous application of compressive force and shear force is used as a negative electrode material, an organic negative electrode is used. In the case of the mixture paste, although the same discharge capacity as in Example 1 was shown, 'high initial charge and discharge efficiency and high fast charging efficiency, but in the case of using the aqueous negative electrode mixture paste, the fact that the fast charge efficiency was reduced. . Comparative Example 2 Using a Henschel kneading machine (manufactured by Mitsui Mining Co., Ltd.), the raw material graphitization and anhydrous oxidized sand in Example 2 were mixed with a stirring rotation number of 700 r p m for 30 minutes. Using the resulting mixture, the negative electrode material was prepared in the same manner as in Example 2. (34) (34) 200403879 In this mixing process, compressive force and shear force cannot be applied simultaneously. After stirring and mixing, the intensity ratio (jD / I. Ratio) in the Raman analysis of the mixture was 0.21. The average lattice plane spacing under X-ray diffraction is 0.3 3 62 nm. In addition, the silicon oxide and the graphitized material were separated using a wind classifier, and the intensity ratio (丨 D / ratio) in the Raman analysis of the graphitized elemental substance and the average lattice plane interval d 0q under X-ray diffraction were measured. The result of 2 is the same as that of the mixture containing anhydrous silica. A negative electrode mixture paste was prepared in the same manner as in Example 1 except that the above-obtained graphitized compound and anhydrous silicon oxide were used, and a negative electrode and a lithium ion battery were prepared. Table 1 shows the battery characteristics. As shown in Table 1, it can be seen that even when mixed in the presence of anhydrous silicon oxide, a lithium ion battery using a graphitized material that has not been subjected to simultaneous compressive force and shear force as a negative electrode material is used in a water-based negative electrode mixture paste The situation is the fact that the fast charging efficiency is low. Example 5 Instead of the raw material graphitization of Example 4, the mesophase spheroids obtained by pulverizing the mesophase spheroids in advance and then graphitizing at 300 ° C (average particle size 1 7 // m). The remaining conditions' are the same as those in Example 4, and a process of applying a compressive force and a shear force simultaneously is also performed. The graphitized material of the mesophase smashed matter before the surface modification treatment is mixed in a spherical shape and an irregular shape. The average lattice plane interval d () () 2 is -39- (35) (35) 200403879 0.3362, the true specific gravity is 2.228, and the specific surface area is 0.95m2 / g. The relative hardness of the hardness was 0.9. The graphitized material after the surface modification treatment is still in a shape where the spherical shape and the uncertainty are mixed, and the average particle diameter is 17 V m, but there is no change. However, the specific surface area is 3.45 m2 / g, and the intensity ratio (Id / Iσ) in the Raman analysis is 0-75. The average lattice plane spacing "() 2 under X-ray diffraction is 0.33 62nm. The negative electrode mixture paste was prepared in the same manner as in Example 4, and a negative electrode and a lithium ion battery were produced. Table 1 shows and implements Battery characteristics evaluated in the same manner as in Example 4. Comparative Example 3 A negative electrode material was prepared in the same manner as in Example 5 except that the process of simultaneously applying a compressive force and a shear force was not performed in Example 5 to produce a negative electrode and lithium. Ion battery. Table 1 shows the battery characteristics evaluated in the same manner as in Example 5. As shown in Table 1, the graphene compound of Comparative Example 3 having a low intensity ratio (ID / I c) in Raman analysis was used. In a lithium ion battery that is a negative electrode, if an aqueous negative electrode material mixture paste is used, the fast charging efficiency is low. In contrast, the strength in Raman analysis is improved by applying a compressive force and a shearing force simultaneously. In Example 5 of the ratio (Id / I.), Even in the case of using the water-based negative electrode mixture paste, the fast charging efficiency is still greatly improved. Moreover, the initial charge-discharge efficiency is also improved. In addition, when the organic-based negative electrode mixture is used Quality green, can still obtain the fast charging efficiency and the initial charge and discharge efficiency to further improve the effect.-40- (36) (36) 200403879 Examples 6 to 1 1 will be in-stock examples] to 4 to z The negative electrode of the lithium-ion battery used in any method for the production of the raw materials of the raw materials-the raw rock II compounds and the other graphitized compounds shown in Table 2. In the same manner as in Example 1, a negative electrode paste was prepared, and a negative electrode and a lithium ion battery were fabricated. The results are the same as those of Example 1. Table 2 shows the results.

Comparative Example 4 A mixture of the raw material graphitization of Example 1 and natural stone ballast 32 (SN 0-10 manufactured by ESSIS) was used as a lithium ion battery anode material. The negative electrode mixture was prepared in the same manner as in Example 1. One ^ one was used as the negative electrode and the lithium ion battery. The same results as those of the lithium ion example were evaluated. Table 2 shows the results. Hereinafter, a negative electrode material containing both graphite covered with a carbon material having a lower crystallinity than the modified graphitized material of the present invention and the modified graphitized material will be specifically exemplified. Example 1 2 (1) Preparation of graphite coated with carbon material having lower crystallinity than that of the modified graphitization material of the present invention, the preparation of graphite covered with carbon material was carried out in a pressure cooker, and natural graphite (China-Vietnam graphite (strand)) Yi BF1〇A 'average particle size 10 # m, the average lattice plane interval doQ2 is 0 · J j56nm, the intensity ratio (ID / IG) in Raman analysis is 0.09) 100 -41-(37) ( 37) 200403879 parts by mass, and then as a raw material of the carbon material covering the core material, a solution in which coal tar pitch is dissolved in tar in an amount of 20 parts by mass, and the solution is heated with stirring to 4 ° C . After the heating is continued, the tar is removed by distillation under reduced pressure, so that the asphalt is adhered and / or impregnated on the surface and / or inside. This was put into a stainless steel crucible, and firing was performed at 500 ° C while circulating an inert gas in the firing furnace. Then, it grind | pulverized using the atomizer (atmUer). Furthermore, this was calcined at 1,300 ° C to obtain graphite (hereinafter, simply referred to as "coated graphite") coated with a carbon material having a lower crystallinity than that of the modified petrochemical of the present invention. The graphite-coated carbon material is one in which the asphalt is heat-treated at a final temperature of 1 300 ° C, and the crystallinity is lower than that of the modified graphitization of the present invention. In order to confirm the crystallinity, only coal tar pitch was separately placed in a stainless steel > gantry pot, and the firing was performed at 500 ° C under the flow of an inert gas in the firing furnace. Then, it was pulverized using a sprayer. Furthermore, this was burned at I 3 00 t to produce a carbon material. The crystalline structure of the carbon material was analyzed. The average lattice plane interval dQ () 2 in the X-ray diffraction was 0.3 4 3 nm. From this, it can be seen that the crystallinity of the graphite-coated carbon material element is lower than that of the modified graphitization of the present invention. The coverage of this carbon material is equivalent to 8% by mass of the whole. The intensity ratio (ID / I. Ratio) in the Raman analysis of the coated graphite is 0 · 2 8 and the average particle size is 1 3 // m. (2) Preparation of the negative electrode material and the negative electrode mixture paste The coated graphite obtained above and the modified graphitization produced in the method of Example 1 are based on the modified graphitization: the coated graphite = 60: -42- (38) 200403879 4 〇 The mass ratio is mixed, and the negative electrode mixture paste of the aqueous solvent and the organic solvent is prepared in the same manner as in the example]. Using this negative electrode material, a negative electrode and a lithium ion battery were produced in the same manner as in Example 1. The characteristics of the obtained lithium ion battery were also evaluated in the same manner as in Example 1. Here, the rapid discharge efficiency described below was also measured. The results are shown in Table 3 below. < Rapid discharge efficiency > Continue to initiate charge and discharge, and perform high-speed discharge in the second cycle. After charging in the same manner as the first time, the current was 20 times 18 mA, and the circuit was discharged at a constant current up to 1.5 V. From the obtained discharge capacity ′, the fast discharge efficiency was calculated according to the following formula. Fast discharge efficiency _ (discharge capacity in the second cycle), _ -------- v I Π () (discharge capacity in the first cycle) Example 1 3 The average particle diameter used in Example 1 was 2 5 // m mesophase spheroids (made by Kawasaki Steel Co., Ltd.) were pulverized with an atomizer to an average particle size of 14 m, and then graphitized at 3 000 ° C to obtain raw graphitized materials. In this regard, the same conditions as in Example 1 were used to simultaneously perform a compressive force and a shear force treatment to obtain a modified graphitization. The average particle diameter of the obtained modified graphitization was j 3 "m 'Raman analysis, and the intensity ratio (ID / I. Ratio) was 0.83. This modified graphitization was used in place of The modified graphitization used for the negative electrode material. The remaining conditions were made in the same manner as in Example 12 to make -43- (39) (39) 200403879 as the negative electrode material, negative electrode mixture paste, negative electrode, and lithium ion battery. The characteristics of the obtained lithium-ion battery were evaluated in the same manner as in Example 2. The results are shown in Table 3. Comparative Example 5 The raw material graphitization 5 used in Example 1 was used instead of the anode material used in Example 2 The modified graphitization used. The remaining conditions were the same as in Example 12 to produce a negative electrode material, a negative electrode mixture paste, a negative electrode, and a lithium ion battery. The characteristics of the obtained lithium ion battery were performed in the same manner as in Example I2. The results are shown in Table 3. As shown in Comparative Example 5 in Table 3, the negative electrode material (modified graphitization) of the present invention is not used, and lithium ion storage using unmodified raw material graphite and coated graphite is used. Ponds have excellent characteristics when using organic negative electrode mixture pastes. However, when using aqueous negative electrode mixture pastes, the discharge capacity and fast discharge efficiency will decrease. Comparative Examples 6 In Example 12, the modified graphite was not used, but the coated graphite was used alone. The remaining conditions were the same as in Example 12 to produce a negative electrode material, a negative electrode mixture paste, a negative electrode, and a lithium ion battery. The characteristics of the obtained lithium ion battery were evaluated in the same manner as in Example 12. The results are shown in Table 3. As shown in Comparative Example 6 in Table 3, the negative electrode material (modified graphitization) of the present invention was not used, and The lithium-ion battery using graphite alone is -44-(40) (40) 200403879. When using water-based negative electrode mixture paste, although it has high discharge capacity and high initial charge and discharge efficiency, it has fast charge efficiency and fast discharge. The efficiency is lower. This reason may be because the coated graphite is used as a core material and scale-like natural graphite is used. The coated graphite in the negative electrode is oriented to The contact between the non-aqueous electrolyte and the coated graphite becomes incomplete. As shown in Examples 12 to 3 in Table 3, it was confirmed that lithium was used as the negative electrode material (mixture of modified graphitization and coated graphite) of the present invention. Ion batteries, not only in the case of using organic negative electrode mixture paste, but also in the case of using aqueous negative electrode mixture paste, can maintain large discharge capacity and high initial charge and discharge efficiency, and also have high rapidity. The fact of charging efficiency. As a result of using the mixture of the modified graphitization and coated graphite of the present invention as a negative electrode material, when the coated graphite alone (Comparative Example 6) is used, the fast charging efficiency is low and the fast discharging efficiency is low. 200403879 cq 'rtirr Za unmodified 0.3362 iy-', CTn c5 r- cn CS1 o CN) CO m CNl m C < 1 Comparative Example 2 υη 1—Η CN o oo m Γ < 1 CO cn inch comparative example 1 csi 〇0 CO cn cn mm cn Example 5 Modified cn r- o un 艺 艺 cn Example 4 UO CO 荠 m vo o cn C Guang 1 cn cn C ^) υη On Example 3, one un CNl $ c3 CO m CO cn cn CO Example 2 un τ 4 cn CNi c5 CNl CO cn m CN CO mm Example 1 y- (c5 CN) m C ^) cn CJ OQ CO CO m σ > \ 1ΐηΐ1 X-ray diffraction dcm (nm) Specific surface area (m2 / g) Average particle size (μιτ〇t 〇 ^ Q Discharge capacity (mAh / g) Initial charge and discharge efficiency (%) Fast charge efficiency (%) Discharge capacity (mAh / g) Start Charge-discharge efficiency (%) Fast charge efficiency (%) Graphite of mesophase spheric negative electrode mixture paste miscellaneous 丨 < jtn 艺 擗 腾腾 1moss-46-(42) 200403879 Table 2 Example 6 Example 7 Example 8 Example 9 Example] 〇 Example I] Comparative Example 4 Mesophase spheroid average particle size (μιη) 24 23 25 24 25 Id / Ig 0.47 0.57 0.45 0.63 0.2 Specific surface area (m 2 / g ) 1.45 1.95 1.1 2.35 0.45 Sunite πψι Scale-like natural graphite SNO-10 SNO-5 BF10A SNO-10 Id / Ig 0.04 0.05 0.09 0.04 Specific surface area (m 2 / g) 8.16 13.5 6.31 8.16 Other graphite content ratio (%) 10 20 20 25 25 25 25 Water-based negative electrode L 丨 Paste discharge capacity (mAli / g) 337 339 340 341 342 340勹 〇 ”7 Initial charge and discharge efficiency (%) 93 93 93 93 94 94 92 Fast charge efficiency (%) 47 48 52 52 50 53 32 Organic negative electrode mixture paste discharge capacity (mAh / g) 勹 ο Ί 340 340 341 342 340 337 Initial charge and discharge efficiency (%) 92 92 92 92 93 93 92 Fast charge efficiency (%) 41 40 42 44 47 47 40 -47-(43) 200403879

Examples] 2 Examples] 3 Comparative Example 5 Comparative Example 6 Mesophase small average particle size (μηι) 24 13 25-Id / Ig 0.47 0.83 0.2-Ink specific surface area (m2 / g) 1.45 3.68 0.45- Primary graphite BF-10A BF-10A BF-10A BF-10A Id / Ig of coated graphite graphite 0.09 0.09 0.09 0.09 ID / Ig of stone coated graphite 0.28 0.28 0.28 0.28 Content rate of ink coating material (%) 8 8 8 8 Content of coated graphite (%) 40 40 40 100 Aqueous negative electrode discharge capacity (mAh / g) 348 o ro JJJ 345 360 Initial charge and discharge efficiency (%) 94 94 93 94 Mixture fast charge efficiency (%) 52 50 40 42 Paste fast discharge efficiency (%) 90 90 70 60 Paste discharge capacity (mAh / g) of organic negative electrode mixture 347 351 350-Initial charge and discharge efficiency (%) 93 92 93-Fast charge efficiency (%) 50 50 48 One

-48- (44) (44) 200403879 Industrial Applicability The novel modified graphitized material produced by the surface modification treatment of the present invention has high crystallinity, but the surface surface belongs to the disordered lattice. , And those who have improved surface characteristics such as wettability. This modified graphitization is good for negative electrode and negative electrode material of lithium ion battery. In particular, even when an organic-based mixture paste is used instead of an organic-based mixture paste to produce a negative electrode, it can still be produced while maintaining a large discharge capacity and high initial charge-discharge efficiency, and at the same time has a high Fast-charging efficient lithium-ion battery. Therefore, it can not only meet the requirements of environmental and safety aspects, but also meet the requirements for high energy density of batteries in recent years. It can also contribute to the miniaturization and high performance of the equipment. [Schematic description] Figure 1: A cross-sectional view of an evaluation cell for evaluating the properties of graphitization. Fig. 2 is a schematic explanatory diagram of a device for performing a process of applying a compressive force and a shear force simultaneously. Fig. 3: A schematic explanatory diagram of another device for performing a process of applying a compressive force and a shear force simultaneously. Fig. 4 is a diagram showing the amount of water permeation (hydrophilicity) of the graphitized mesophase spheres obtained in the examples and comparative examples. DESCRIPTION OF SYMBOLS 1 Outer cover -49- (45) (45) 200403879 2 Negative electrode 3 Outer can 4 Positive electrode 5 Separator 6 Insulating sealing coating 7 a Negative electrode collector 7b Positive electrode collector 21 Stator 2 2 Rotor 23 Blade 2 4 Input port 2 5 Circulation path 2 6 Outer jacket for cooling or heating 2 7 Discharge valve 2 8 Discharge port 3 1 Rotor 3 2 Internal parts 3 3 Circulation blade 3 4 Raw material graphitization 3 5 Discharge baffle 36 Product-50 -

Claims (1)

200403879 拾 Pickup, patent application scope 1 · A graphitized mesophase spheroid, which is diffracted in X-rays A-homogeneous lattice plane interval d 0 Q 2 is less than 0.3 3 7 nm, using a wavelength of 5 1 In the Raman spectrum of argon laser light of z, the intensity I d of the peak ridge existing at 1 35 0 to 1 3 70 cm · 1, and the intensity of the region existing at 15 7 0 to 16 3 0 cm The ratio of G] / 1D / is more than 0.4 and less than 2. 2. The mesophase spheroid compound as described in the item of the scope of the patent application, wherein the average particle diameter in volume conversion is 3 to 50 V m, and the area is 1 to 20 m2 / g. 3. The compound of the mesophase sphere described in item i of the scope of the patent application, wherein the hardness of the stone object embedded in the surface is higher than that of the mesophase sphere, and the average particle size is higher than that of the mesophase sphere. The average particle diameter of graphite is small particles. 4. The compound of the mesophase spheres according to item 3 of the scope of the patent application, wherein the particles are at least one selected from the group consisting of silica, alumina, and an oxidized group. 5 · —A kind of anode material for lithium ion livestock batteries, which contains graphitized mesophase spheres as described in item 1 of the scope of application. 6. The anode material according to item 5 of the scope of patent application, among which there are graphites other than graphitized mesophase spheres described in item 1 of the scope of patent application. 7. The negative electrode material according to item 5 of the scope of patent application, wherein there is a graphite coated with a carbon material having a lower crystallinity than that of the graphitization of the mesophase spheres. In the .5 nm field, the peak-to-graphite ratio is greater than that of graphite, graphite, and ink. Graphite titanium has a recontainability of -51. (2) 200403879 8. A kind of negative electrode for lithium-ion batteries is subject to patent application. The negative electrode material according to any one of the items in the range of items 5 to 7. 9 · A lithium-ion battery is the negative electrode described in item 8 of the scope of patent application. 1 0. — A method for manufacturing graphitization of mesophase spheres, which is a process in which the graphitization of mesophase spheres is subjected to simultaneous compressive and shear forces, and the average lattice plane spacing d under X-ray diffraction 〇〇2 is less than 0.33 7 nm, and in the Raman spectrum using argon laser light with a wavelength of 514.5 nm, the intensity of the peak 値 existing in the field of 135 to 137 cnr]] D, the existence of The ratio 値 Id / Ic of the intensity 値 of the peak 値 in the field of 1570 to 1630 cnV] is more than 0.4 and less than 2. 1 1 · The manufacturing method as described in item i 0 of the scope of patent application, wherein the hardness of the graphitized material is higher than that of the mesophase sphere and the average particle diameter is smaller than the average particle diameter of the mesophase sphere With the coexistence of fine particles, the aforementioned treatment is performed. 1 2. The manufacturing method as described in item No. 0 of the patent application scope, wherein the manufactured particles are at least one selected from the group consisting of silicon oxide, aluminum oxide, and titanium oxide. -52-