TW442995B - Carbon material for use in cell and cell using the carbon material - Google Patents

Abstract

A graphite powder as a carbon material has a specific surface area of lower than 3 m<SP>2</SP>/g, an aspect ratio of lower than 6 and a tabbing bulk density of higher than 0.8 g/cm<SP>3</SP>. And a graphite powder as a carbon material has a tabbing bulk density of higher than 0.8 g/cm<SP>3</SP> and an initial oxidation temperature of higher than 600 DEG C. Or a graphite powder as a carbon material has a bulk density of higher than 0.8 g/cm<SP>3</SP> and a specific surface area of lower than 3 m<SP>2</SP>/g, and a powdery electric resistance coefficient thereof under some specific conditions of lower than 0.06 Ωcm. And a cell using said graphite powders as negative electrode materials. The obtained cell possesses high capacity of discharge, recycling property and charge-discharge efficiency.

Description

Λ 49 9 5 A7 B7 Printed by the Consumers ’Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs. 5. Description of the invention (/) Technical section. The present invention relates to carbon materials for lithium batteries: in particular, to discharge capacity and charge and discharge efficiency.碳 A carbon material for lithium batteries with excellent cycle characteristics. This specification is based on a Japanese patent application &lt; Patent Hei 10-287397), and the content of this Japanese application is an excerpt from this specification. In recent years, there have been significant developments in portable devices such as mobile phones, small video recorders, portable notebook computers, etc., so that nickel-metal hydride secondary batteries or lithium secondary batteries such as lithium-ion secondary batteries are used as power sources. The demand for secondary batteries has increased. In particular, the non-aqueous solvent-based lithium batteries using the lightest gold alloy lithium have the high feasibility of achieving small and lightweight batteries with high energy density, and are currently being developed in large scale. . However, a lithium secondary battery using metallic lithium as a negative electrode with the charge and discharge cycle operation, k is apt to generate dendritic needle-like lithium crystals: the crystals may pierce the electrode separator and cause a short circuit. An effective method to solve this problem is to use a carbonized or graphitized carbon material on the negative electrode, and a lithium ion secondary battery using a non-aqueous solvent containing lithium ions as an electrolyte is also being put into practical use, that is, lithium. Ions are doped in carbon: charge in the case of intercalation, discharge in the case of deionization, and discharge in the case of de-intercalation. I charge and discharge reactions in this form, as long as the control metal is fully used The precipitation of lithium is feasible, but about the reaction mechanism head 3 (read the precautions on the back before filling in this page)

In the application of this paper, «national rubbing standards (CpS &gt; 8 4 gauge (2 丨 0X297 mm) 442995 A7 B7 V. Description of the invention (2) The key points that are not completely clear in the front are still being investigated in a grand way. : The negative electrode of this lithium secondary battery is formed by natural graphite, artificial graphite, cyanine carbon particles *, pitch carbon fiber, and carbon fiber by gas phase method: What's more difficult is the low temperature treatment of graphite products. The active material is used in carbon materials. In order to increase the discharge capacity in lithium batteries, as much lithium as possible must be retrieved in the carbon. The lithium that is retrieved must be easily released during discharge. The discharge can be carried out smoothly. * It is hoped that the balance between the two will not change much when repeated. In this way, the current efficiency can be improved and the cycle life will be longer. The amount of lithium recovered from the carbon (graphite) material It is considered to be related to the increase in the degree of high crystallinity of graphite. Generally, the crystallinity of graphite is improved due to the higher graphitization temperature. Therefore, the graphitization temperature is usually limited to about 3200 ° C, and only the temperature conditions are Crystallization in graphite Certain restrictions at the time * * To solve this problem, Indun, the Shellfish Consumer Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs, added boron (B) to carbon powder by the method described in Japanese Patent Application Laid-Open No. 8-3 1422. The use of graphite The chemical treatment improves the crystallization. The method described in Japanese Patent Application Laid-Open No. 9-259886 uses special carbon treatment to improve the crystallinity of graphite powder. At the same time, it also reduces the specific surface area. 9 For lithium batteries, The graphite powder is made into a paste form using a binder «coated on gold foil and metal mesh to form an electrode (negative electrode). It is desirable that the specific surface area of the powder be as small as possible. The reason is that the graphite The surface of the powder is a non-dynamic film formed by the electrolyte and so on. Therefore, as the specific surface area of the powder becomes larger, the film also increases: 4 paper sizes of the fixed film are applicable to the country's national rate (CNS &gt; A4 Specifications (210X297 mm) -442995 α7 B7 V. Description of the invention M) Production has become the main reason for the decline in lithium utilization efficiency .. The high activity of carbon materials and the decomposition of the electrolyte will shorten the cycle life *.The lower the activity, the better. Therefore, it is better to use a carbon material with low chemical activity (reactivity) and a small specific surface area. • The specific surface area of the powder becomes larger and the binder used when the electrode plate is formed The amount of use will increase. The ratio of so many graphite particles covered with a binder will increase. As a result, the charge and discharge capacity will also decrease because the contact ratio between graphite particles and the electrolyte becomes lower. The higher the capacity of the battery: The larger the charge and discharge current: Moreover, in the past, the 髙 conductivity of the electrodes required was due to the poor conductivity of the material: and poor coating properties. Therefore, a large amount of binder material is needed: the resistance of the electrode plate itself will also increase. *. Not only cause low discharge capacity or low Coulomb efficiency, but also cause rise in heat generation or partial heating, and there is a danger of generating tree-like crystals: safety is not ideal. 碳 Carbon itself is conductive A material that is excellent and has excellent coating properties. Therefore, it is necessary to develop and jointly improve the charge and discharge capacity of the carbon material. The method for obtaining graphite powder is to pulverize coke. A method of performing graphitization after waiting, or a method of pulverizing after graphite. The latter method is adopted in Japanese Patent Application Laid-Open No. Hei 6.295725. The crystallization after graphitization is very developed: pulverization is not easy due to hard strength: and not only must a large force be used when pulverizing graphite materials. And when the force is applied to a certain limit, the shape of the fine powder particles often becomes scaly when crushing: the aspect ratio also becomes larger, and then the larger aspect ratio is the relationship of more plate-shaped crystal powder. The specific surface area becomes larger but the performance of the battery is lowered. The paper size is applicable to the Chinese National Standards (cys &gt; Α4 size &lt; 210X297 mm) (Please read the precautions on the back before filling this page)

Printed by the Consumer Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs 1 442995 A7 B7 V. Description of the invention (d) Please read the following item and fill in this page to improve the crystallinity of graphite and the specific surface area of graphite powder becomes smaller. The discharge capacity is It will improve but not completely. The shape of graphite powder is related to the battery characteristics such as the permeability of the original electrolyte or the charging rate when the electrode is formed. As for the above-mentioned patents, there is no special contact with such problems. Other factors that must be considered, such as the active (reactive) conductivity of graphite powder, etc. The invention shows that the present invention utilizes the characteristics of the carbon powder before the graphitization is controlled in advance to achieve a large discharge capacity, excellent charge and discharge efficiency and cycle characteristics, and good coating performance, and an increase in the carbon density in the electrode. The purpose of a carbon material for a lithium battery is to provide a carbon material with low activity and a carbon material with low specific resistance. The present invention is composed of the following inventions. (1) Carbon material for lithium batteries composed of graphite powder having a specific surface area of 3 mVg or less, an aspect ratio of 6 or less, and an overall density of 0.8 g / cm3 or more .. Printed by the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs (2) Carbon materials for lithium batteries as described in (1) above: Graphite powder has an oxidation starting temperature of 600eC or higher. (3) As described in the above (1) or (2>) carbon material for lithium battery, when pressure is applied to the graphite powder until the overall density of the powder becomes 1.5 g / ctt ^, the The specific resistance of the powder in the orthogonal direction is below 0.06Qcm. (4) The overall density of the powder is above 0. S g / cm3, and the oxidation oxidation temperature is 6. This paper is applicable to the kneaded rate (CNS) A4 specification (210X297) of this paper. (Mm) 5 442995 A7 B7 V. Description of the invention (female) Carbon for lithium batteries composed of graphite powder with a temperature above 600 ° C

material. I (5) The carbon material for a lithium battery according to the above (4) has a specific surface area of 3 m2 / g or less. (6) The aspect ratio of the carbon material for a lithium battery as described in (4) or (5) above is 6 or less. (7) The specific surface area is 3 m2 / g or less. • The graphite powder with a total density of 0.8 g / cm3 or more is added. When pressure is applied to the powder, the total density of the powder becomes 1-5 g / cm3. A carbon material for a lithium battery having a specific resistance of powder in a right-angle direction of the pressing direction of not more than 0.06 cm. (8) As described in the above (1 &gt; ~ (7), the carbon material for lithium battery is graphite powder with an average particle diameter of 8 ~ (9) As described in (1) ~ (S), the lithium battery The carbon material used as the graphite powder does not substantially include particles having a particle size of 3 / zm or less and / or 53 / zm or more. (10) The carbon material for a lithium battery as described in (1) to (9) above is The graphite powder has a Co 値 of 6.745 A or less. (11) As described in (1) to (10) above, the carbon material for lithium batteries is a graphite powder containing boron f (12) As described in (1) to (11) above. ) The graphite powder is used as the main raw material and polyvinylidene fluoride powder is added and kneaded to form a paste for battery negative electrodes. * (13) As described in (1) to (U) above, the graphite powder is 7 copies. Paper + 818 | 3 ^^ (CNS) A4 * w * · (21GX297mm) (Please read the notes on the back before filling out this page)-D. Printed by K! II 9 9 ο Α7 Β7 V. Description of the invention (Hand) A battery made of the main raw material of the negative electrode: (14) As described in U) to (11) above, graphite powder is used as a negative electrode. The main raw material of the lithium batteries "since the graphite powder an aspect of the present invention is smaller than that, so fewer particles are scaly. If the particles are scaly, particles on the electrode surface will be arranged along the surface, which will cause poor permeability of the electrolyte: the graphite powder particles of the present invention have a nearly spherical shape, so the electrolyte has good permeability. . Less scale-like particles: and removing such fine particles with a particle size of 5 // ΠΙ or less, the overall density of the powder will be high. If the overall density is increased, the average graphite particles per unit volume will increase., Therefore, the insertion rate of lithium will increase. The graphite powder of the present invention is pulverized by coke, etc., and graphitized. Moreover, it is smaller than the surface 稹, which is obtained by removing fine particles, etc., so that the surface of the particles is not affected by the electrolyte. Forms a non-dynamic film, and * because the specific surface area is small, when the electrode is formed: the use of the binder can be reduced. Therefore, the interference between the binder and the graphite particles and the electrolyte will be reduced. In addition, the addition of boron to powders such as coke can improve the degree of graphitization (crystallinity) obtained by graphitization, and therefore increase the lithium insertion rate into the graphite crystal lattice. This important invention is the use of boron to improve the oxidation resistance. It can reduce the resistance of the powder. It significantly improves the mold resistance. So the improvement of the oxidation resistance is to reduce the surface activity of the particles. It is related to the improvement of insertion ability ... 8 This paper size is used by the Chinese Minjia Mou (&gt; A4 «t 格 ί 210X297 mm &gt; (Please read the precautions on the back before filling out this page) -i. Order · Consumption of Industrial Workers, Intellectual Property Bureau, Ministry of Economic Affairs Cooperative Du printed · ： 9 9 5 A7 __B7 V. Description of the invention (7) Simple explanation of formula (1) Figure 1 shows the relationship between the calorific value and weight reduction of graphite powder when tested by TG / DTA. Figure 2 shows the graphite powder. Sectional view of a resistance test device / Shi Jiajuan Shi Li, the method of application of the invention The first item of the present invention is a lithium battery composed of graphite powder having the specific surface area, the aspect ratio, and the overall density of the above. Carbon material This carbon material is particularly suitable for the negative surface area of the negative electrode of the lithium battery. The specific surface area of the graphite powder of the lithium battery electrode is preferably small. The specific surface area (BET method) of the graphite powder of the present invention is 3 tn2 / g or less. * Specific surface area such as The surface activity of graphite powder exceeding 3m2 / g will become higher. Due to the decomposition of the electrolyte, etc., the Coulomb efficiency is reduced. Even a large amount of binder must be used when the electrode is formed. As a result, the coating ratio of the graphite particles on the graphite becomes higher. battery The amount is reduced. As mentioned above, the higher the activity and the non-dynamic change of the electrolyte on the graphite particle surface can easily cause the performance to decrease. The smaller the specific surface area is related to the particle diameter, particle shape, and particle size distribution. 、 .Surface properties and other important factors. * Among them, it is better to make the particles as close to a spherical shape as possible. To increase the battery capacity, it is very important to increase the charge density of graphite particles. Therefore, graphite powder None of the particles should be scaly. It is better to make them as close to a spherical shape as possible. The shape of the particles is expressed by the aspect ratio. The aspect ratio of the graphite powder particles of the present invention is 6 or less. It is better to be less than 5. • The aspect ratio is expressed by the ratio of (major axis length) / (minor axis length) of ordinary particles: these numbers are calculated by particles 9 in the paper standard (C) ^ iS &gt; A4 specification (2I0XW7mm) (谙 Please read the note on the back before filling this page)

Printed by 1T, Intellectual Property Bureau, Ministry of Economic Affairs, Consumer Goods Cooperative, 442995 A7 ______B7 V. Obtained from the micrograph of the description of the invention (), and the aspect ratio in the present invention is calculated by the following method. (Please read the notes on the back before filling in this page) First calculate the average particle diameter A by laser refraction scattering method and the average particle diameter B by electronic test method (Coulter-Counter method). Here are various measurement theories The obtained A is the diameter of the longest sphere of the particle, and B is regarded as the diameter of a sphere with the same volume as the particle: Then assume that the particle is in the shape of an original plate. The diameter of the bottom surface of the original plate is A, and the volume is 4 / 3X (B / 2) When 3 / T = C, calculate the thickness of the original plate T = C / (A / 2) 2? Γ, then you can get the aspect ratio of A / T ^-In general, graphite will often become scaly when crushed. In particular, if it is subjected to a high temperature treatment, it is more likely to have a scaly tendency when pulverized after graphitization, and the finer the particle size of the powder, the easier it is to form scaly by a strong method during pulverization. The electrode plate of the battery is a metal mesh such as aluminum or a gold plate. The surface of the graphite powder is larger than 6 when the graphite powder is coated with a paste containing graphite powder. The scaly graphite particles on the surface will form a mirror surface. The same tendency, this result will make the permeability of the electrolyte entering the electrode plate worse, the discharge capacity of the battery will decrease, and the graphite particles printed by the consumer cooperative of the scale-like Intellectual Property Bureau of the Ministry of Economic Affairs will be poorly charged. It will cause the graphite density in the electrode to be lower. The graphite powder constituting the lithium battery electrode should be as chargeable as possible, that is, the higher the overall density, the higher the discharge capacity of the battery. The overall density of the graphite powder of the present invention Above 0.8 g / cm3, preferably above 0.9 g / cm3. In the present invention, the overall density is measured by the following method. 10 Winter &amp; Zhang scales are applicable to China's National Sample Rate (CNS) A4 Washing (210X297 mm) Printed by the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs * 442995 A7 B7 V. Description of the invention (y) First weigh a certain amount of graphite powder (6.0g) is filled with a small container for 15mm Shanghai measurement, equipped with a charging device, dropping at a height of 45mm, the charging speed is 2 seconds / time, and the volume is measured after 400 free-fall operations Then, from the relationship between weight and volume, calculate the overall density of graphite powder. The overall density is related to the particle size and shape of the powder, and even the surface properties. The particles with the same average particle size have different particle size distributions. Therefore If there are many flaky particles and more fine powders, the overall density of the filler will not increase. For example, the graphite material will be crushed to an average particle size of 10-3 0: a large amount of fine powder will be required to reach the filler. Density of 0.8 g / cm3 or more is quite difficult. The graphite powder of the present invention can reduce the fine powder as much as possible, and the overall density of the filler is increased, and the aspect ratio is as small as the graphite powder described above *, that is, no scale The degree of flakes or scales is low. It can reduce the interference of electrolyte penetration and increase the charge density. The graphite powder used in lithium batteries has the same low activity as mentioned above, and it has conductivity. High is better. The oxidation start temperature of graphite powder is used as an index of activity. • The oxidation start temperature of high activity is generally lower. 〇The graphite powder of the present invention has the specific surface area, aspect ratio, and overall density. Its oxidation starting temperature (described later under test conditions) is preferably 600 ° C or higher, and its specific resistance (described later under test conditions) indicates that its conductivity is preferably 0.06 Qcm or less. The second item of the present invention has the foregoing Carbon materials for lithium batteries with specific oxidation initiation temperature and overall density: graphite powder oxidation initiation 11 BH family standard rate (CNS) A4 specification U10X297 mm for paper size application '~ 1 (Please read first (Notes on the back then fill out this page)

442 ^ 9 5 A7 B7 V. Description of the invention (K) Temperature is an indicator of graphite activity. It is expected that the oxidation starting temperature is high, that is, the activity is low. In the present invention, the oxidation starting temperature is measured under the following test methods and conditions, that is, when the temperature is raised in the air stream using a normal TG / DTA test device (thermogravimetric test / differential thermal analysis). Test of the calorific value and weight reduction of oxidation: the first qualitative state is shown in Fig. 1, and the horizontal axis in Fig. 1 is the temperature of the predetermined heating rate. The curve A is

The calorific value curve (corresponding to the left vertical axis) obtained by differential thermal analysis. * Curve B is the weight reduction curve (corresponding to the right vertical axis) tested by thermal weight.

The sample heats up and heats up due to oxidation. The starting temperature appears at point T in Figure 1, and the reduction in oxidation weight of the test sample begins to occur. For example, the weight reduction of curve B is slightly later than the point T: and the weight reduction The starting point is not as sharp as the starting point of the calorific value. Here, in the present invention, the starting point T of the calorific value is used as the oxidation starting temperature. The test conditions are 5 mg of the test sample and the air flow rate is 100 ml / min. .The heating rate is 10eC / min, and the test samples are graphite powders of various particle sizes used in lithium batteries. Then we can know that graphite powders of the same material, for example, have a smaller particle size * oxidized by employees of the Intellectual Property Bureau of the Ministry of Economic Affairs Consumer cooperatives' printing starting temperature tends to decrease slightly * According to the above measurement method ** The oxidation starting temperature of the graphite powder of the second item of the present invention is above 600 ° C *, and the oxidation starting temperature may not necessarily be completely graphite The chemical activity of the powder is also related to the shape of the powder and the specific surface area. To reduce the chemical activity, it is better to use easily graphitizable carbon materials such as coke as graphite raw materials: about the shape of the powder As stated in the aforementioned regulations, it is better to have an aspect ratio of less than 6 and a specific surface area of 3m2 / g at 12 paper scales. National Standard (CNS) A4 specification (210X297 mm) — ~~ ' 442995 A7 _B7____ 5. The description of the invention (//) is better; · The overall density of the graphite powder is to achieve the purpose of increasing the battery capacity, which is 0.8 g / cm3 or more as in the first invention, and 0.9 g / cm3 or more is The specific resistance of the graphite powder to be described later is set to 0.06 Ωcm or less. The third aspect of the present invention is a carbon material for lithium batteries having the aforementioned specific specific resistance, specific surface area, and overall density of the graphite powder. High specific resistance and low electrical conductivity will not only cause a decrease in battery discharge capacity or Coulomb efficiency, but also increase heat generation. The specific resistance of the third invention is 0.06f) cm or less. The test is as follows. The test method is illustrated in Figure 2. In Figure 2, .1 is an electrode composed of a copper plate, .2 is a compression rod made of resin, and .3 is a bearing platform. 4 is a side frame. , Are made of resin, 5 is the graphite powder of the test sample, 6 is mounted at the lower end of the test sample is provided at the center portion in the direction perpendicular to the paper of the test voltage terminal .. Use the four-terminal method shown in Figure 2 to test the specific resistance of the following test samples. The test sample is compressed with a compression rod 2 and a current is passed from electrode 1 (I). The voltage between the terminals is tested at terminal 6. (V): The voltage at this time is obtained by using a compression rod to obtain the overall density 値 as measured at 1.5 g / cm3

The resistance of the sample (between the terminals) is set to R. Then R = V / I, and the specific resistance is obtained by p = R * S / L (p: specific resistance, .S = direction and face of the test sample). The cross-sectional area (c m2) in the right-angle direction of the pressing direction: L is the distance between the terminals 6 (cm)). The cross-section in the right-angle direction of the test sample in the international test is about lcm wide and about 0.5 ~ high lcm *, length 4cm in the direction of current: 13 This paper size is applicable to the Chinese National Standard (CNS) A4 size (210X297) Ϊ i &quot; / (Please read the notes on the back before filling this page) Order &quot; 'Ministry of Economy Printed by the Intellectual Property Bureau employee consumer cooperative 442995 Printed by the Intellectual Property Bureau employee consumer cooperative of the Ministry of Economic Affairs A7 B7___ V. Description of the invention (/ 2) The distance between the terminals (L) is lcm .. In order to improve the conductivity of graphite powder, it must be To improve the conductivity of graphite itself, for this purpose, it is necessary to improve the crystallinity. Therefore, for example, graphite made from raw materials with easy graphitization properties is used, or the temperature of graphitization is even increased using boron (B &gt; etc.) Graphitization catalyst can also achieve the effect of improving the crystallinity of graphite • The number of contact points between the same graphite is reduced: that is, the content of fine powder is effectively reduced. From the point of conductivity, the graphite particles are better. However, the thickness of the graphite powder layer coated by the electrode of the battery is limited. It seems that you cannot use too large graphite particles * * • So the average particle size of the graphite powder must be as large as possible within the obstacle range of the electrode ^ The specific surface area in the third invention, the overall density and the One invention is individually less than 3 m2 / g, 0.8 g / m3 or more, preferably 0.9 g / m3 or more, and the aspect ratio is preferably 6 or less, 5 or less is better, and graphite is more. The oxidation starting temperature of the powder is the same as above 600 ° C ^ It is desirable that the graphite powder of the present invention (the first to third inventions described above) have as good crystallinity as possible. The lattice interval (Co) of the stacked graphite structure is preferably 6.745 A or less. It is more preferably 6.730 A or less. It is more preferably 6.720 A or less. Therefore, the crystallinity of the graphite powder is improved. To increase the charge and discharge capacity of the battery and reduce the specific resistance. · Graphite powder contains boron (B), beryllium, aluminum, silicon, and other graphitizing catalysts, especially boron. • Effective addition of boron to carbon powder can enhance the stone 14 Paper size is applicable Chinese National Standard (CNS &gt; A4 Specification (210X: 297 mm) Printed by the Industrial and Commercial Cooperatives of the Ministry of Economic Affairs and Industrial Cooperatives A7 B7_ V. Description of the invention (d) Degree of inking and graphitization (crystallinity), .Co 値It becomes smaller. When boron is added to graphite with the same crystallinity. The processing temperature is lower when it is not added. The content of boron is preferably in the range of solid solution in the graphite crystal. Too much does not enhance the effect of the catalyst. The upper limit is in the range of 10% by weight. That is, the boron in the graphite powder of the present invention is in the range of 10% by weight or less. It is preferable to contain 5% by weight. The particle size of the medium graphite powder is preferably an average particle size of 8 to 30, and more preferably 10 to 25 # m. The average particle size is determined by a laser diffraction scattering method. 1 Specifically, it is manufactured by Nikkiso Co., Ltd. Tested by the MICROTRAC HRA device. The test conditions are 50mg sample: add 50ml of distilled water After adding 2¾ Triton (surfactant) aqueous solution, test with this device after ultrasonic dispersion for 3 minutes: If the average particle diameter of graphite powder is smaller than 8 / m, not only the aspect ratio will change easily Large and the specific surface area will also increase. It is difficult to achieve the range below 3 m2 / g of the present invention, and the overall density of the powder filling cannot be improved. The result is poor voltage flatness: it is difficult to form a battery. The so-called voltage flatness is the flatness of the charge-discharge curve: that is, using lithium gold as the reference electrode. In the case of lithium in the carbon electrode, lithium is inserted / discharged back and forth for a fixed current charge and discharge. • The charge-discharge force curve There is an extended plateau range near 100mV: the voltage change in this part is small and the condition is better. It can be used as an indicator of flatness. The capacity of the battery is the plateau range plus whatever the lithium absorption in the particle surface Suppression / desorption with a continuous and intense voltage rise suppression (trapping) Fan 圔 Sum. The suppression range is increased as the particle surface area becomes larger. As a result, the flatness is reduced. Original 15 This paper size is applicable to Chinese national standards (CNS) A4 specification (2Ϊ0 × 297297) 1 (Please read the precautions on the back before filling this page)

44299S A7 _B7_ V. Explanation of the invention (/ 幺) Because then, due to the decrease in flatness, the voltage change will occur in the case of the battery combination. In the case of a device that must have a stable voltage, the use range will be It is shortened and the capacity is reduced, which is a bad phenomenon. When forming electrodes made of graphite powder: apply paste, which is generally used as a binder for graphite powder, * to be applied on metal plates, etc., if the particle size of the powder is less than 8, the content is smaller than 8 The viscosity of the fine powder paste increases, and the coatability also deteriorates: so from this point of view, the average particle diameter of the powder is preferably more than the average particle diameter. It is smaller than 8 or contains less than 3; / m The activity of the powder of the particles will increase, and the specific resistance of the powder will also increase. In this case, it is better if the particles can be divided and removed. The upper limit of the particle size of the graphite powder is as described above. The thickness of the graphite powder layer formed by the paste is usually in the range of 50 ~ 200 // Π ». From this viewpoint, the average particle size of the graphite powder is limited in order to coat the graphite particles as much as possible. The diameter is preferably 30jt / m or less. * When graphite particles are mixed with particles as large as 53 // m or more, it will cause more unevenness on the electrode surface. It will cause injury when using the battery. The reason for the separator% From these viewpoints, the graphite powder of the present invention preferably has a particle diameter of 8 to 30 # π, and it is best to remove particles below 3 jttm and / or 53 / zm or more. Graphite powder that does not contain such particles (5% by weight or less). The average particle diameter of the graphite powder when particles below 3 / zm and / or 53 or more are removed is 10 to 25 // m. The graphite powder of the present invention is Of the graphite powders obtained by the following methods, coke is usually produced first. Coke raw materials 16 The paper size is applicable to the Chinese National Standard (CpS) 8 4 specifications (210X297 mm) '~~' (Please (Please read the notes on the back before filling in 1 page.) Printed by the Consumer Cooperative of the Property Bureau -If ί Printed by the Consumer Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs A7 ______B7_V. Description of the invention (/ Γ) is the use of petroleum-based asphalt X coal-based asphalt, etc. The coke is transformed into graphite powder in coke. Generally, it is a method of pulverizing coke and then graphitizing. The method of coke itself is graphitized and pulverized, or a binder is added to the coke to form a fired product (ie, Coke and coke of the fired product, etc.) Regraphing method and pulverization method. * Here, if coke is graphitized and then pulverized. Due to the developed crystallinity, it is easy to cause scaly powder during pulverization, and in order to achieve a small aspect ratio in the present invention, that is, the particles are as close to the spherical shape as possible. The purpose is to pulverize the ungraphitized coke, etc .: It is desirable to grade it to adjust the predetermined particle size and specific surface area, and then perform graphitization. The raw material coke is preferably as crystallized as possible. Therefore, the heat treatment at 2000 ° C or lower and 1200 ° C or lower is more suitable for I. The aspect ratio after pulverization depends on the type of raw coke. Known so-called acicular coke with easy graphitization characteristics and non-acicular coke with poor graphitization characteristics are known from the field observations of the inventors in the case of pulverized coke as powder. The size ratio is small, that is, it is known to be suitable to obtain powder particles close to the shape of a sphere. Then the raw coke is preferably heated below 2000 ° C, and preferably non-needle coke under 1200 ° C. -Graphite-treated coke powder not only promotes crystallization, but also reduces the specific surface area of the particles'. The reason for this can be easily found, for example, by pulverizing coke to obtain coke powder having an average particle size of about 10 // m. Approx. 17 paper standards applicable to the a® furniture ratio (CPS) compliance & (2ΐ〇χ297ϋ) (Please read the precautions on the back before filling this page)

Printed by the Ministry of Economic Affairs ’s Smart Financial Cooperative Consumer Cooperative Γ 442995 Α7 ____ Β7 V. Description of the Invention (/ Z) is 14 m2 / g, and its graphitization ratio surface at 2800 eC becomes 2 ~ 3 m2 / g • However The change in particle size varies from graphitization to pulverization. At least 5 m2 / g or more. Sometimes it changes to 10 m2 / g. * In comparison, the method of graphitization after pulverization and carbon during graphitization are compared. Atoms are rearranged and the surface is cleaned or smoothed due to the evaporation of a part of the high-temperature surface. It is believed that the specific surface area can be reduced. High-speed pulverizers (hammer pulverizers, pin-types, etc.) can be used in the pulverization of coke and the like. Mills, cage mills) or various ball mills (rotating ball mills, vibrating ball mills, and star-type ball mills) stirring mills (melt ball mills: Atreida (transliteration, a kind of pulverizer)), circulation tubular mills , • Ring mill &gt; etc. *, sieve mills for pulverizers, turbo mills: ultra-micron mills, jet mills, etc. ♦ It is also possible to use under specific conditions: Use these mills Machine to crush coke, etc., at this time crush the bar For the selection of parts and the need for powder classification, the average particle diameter should preferably be within the range of 8 ~ 30 ^ m: 3 // m or less particles and 5: μm or more particles are removed In the method of grading from 10-25 to mi coke powder, etc., any form can be used as long as it can be separated. For example, using a sieving method or a forced vortex centrifugal classifier (micron separator., Turbo type Purex) Process: Turbine classifiers, super-separators, inertial separators (improved high-efficiency impactors, air-bag classifiers) and other air classifiers also use wet sedimentation separation methods or centrifugal classification methods. The graphitization temperature of coke and other powders is preferably high. The equipment used is preferably controlled in the range of 2500 ~ 3200eC. The graphitization method is 18 I paper scale, using China National Standards (CNS) A4 Specifications (210X297 mm &gt; 442995 A7 B7 V. Description of the Invention (/;) Method for charging powders such as coke into a graphite crucible · 'Method for manufacturing a graphite furnace using direct current (Acheson). The graphite powder contains The case of boron Add boron-derived boron monomers H3B〇3, B2O3BC4, BN, etc. to the coke and graphitize them. If the boron compound is not uniformly mixed, the product itself will not only be uneven and sintered during graphitization It is more likely that the amount of boron added is also small: the boron source is below 50 ^ m •, it is better to mix the powder with the range below 20 // tn with powder such as coke: the content of boron is because The graphite powder may actually contain less than wt%. Therefore, it is desirable that the amount of boron added to the coke is less than 10 wt% in the graphitized graphite powder. The graphite powder particles are not well developed by crushing and crystallization. Coke before graphitization: reducing the aspect ratio by reducing flaky particles ... and also removing fine particles such as 3μη »or less will become larger. The vertical and horizontal dimensions of graphite powder obtained by these methods The ratio is below 6 and preferably below 5. The overall density of graphite powder becomes higher as the aspect ratio becomes smaller. In terms of particle size, there are more fine particles: the overall density becomes smaller: even if the powder has the same average particle size, its particle size distribution will be different and The graphitization method after pulverization will smoothen the surface as the crystallization progresses. The overall density will increase due to fewer uneven surfaces. F Adjusting the particle size distribution such as the above aspect ratio and average particle size control classification To increase the overall density of the filling to 0.8 g / cm3 or more, and preferably 0.9 g / cm3 or more. 19 This paper is applicable in the national grade (cys) Α4 size (210X297 mm) Please read the ί item on the back before filling in this page. Page printed by the Intellectual Property Office of the Intellectual Property Office of the Ministry of Economic Affairs and Consumer Cooperatives 442995 A7 B7 V. Invention Note (β) The battery of the present invention is a battery made of the graphite powder as the main material of the negative electrode. In the battery of the present invention, the positive electrode material is a metal oxide, a metal sulfide, a conductive polymer, or Electrode active materials (positive electrode active materials) with high redox potential, such as carbon materials 1. It is better to obtain high-voltage, high-capacity batteries. 'In such electrode active materials, in order to increase the charge density and increase the volume capacity From the viewpoint of density, cobalt oxide, manganese oxide, * vanadium oxide, * nickel oxide: metal oxides such as molybdenum oxide, molybdenum sulfide, titanium sulfide, and metal sulfides such as vanadium sulfide are particularly preferred. From the viewpoint of high capacity and high voltage, molybdenum oxide, nickel oxide, and cobalt oxide are preferred. In this case, the method for producing the metal oxide or metal sulfide is not particularly limited. * For example, as described in "Electrical Chemistry, Vol. 22, .5 74 pages, .1954 years": Manufactured by general electrolytic method or heating method, and these active materials are used in lithium batteries. In the case of use in a battery. When manufacturing a battery, for example, lithium is inserted (composite) in the form of gold oxide or metal sulfide such as LLCoC ^ or LLMn02. There is no such method for inserting lithium. A particular limitation is that, for example, in electrochemical electrochemical lithium ion insertion methods, salts such as Li2C03 and metal oxides are described in US Patent No. 4,357,215, and heat treatment is performed. From the viewpoint of flexibility and ease of forming a thin film, the positive electrode material is preferably a conductive polymer. Examples of the conductive polymer include polyaniline, polyacetylene and a conductor, and polyparaphenylene and a conductor. 'Polypyrrole and conductive hip, polythiophene and conductive body; polythiopyridine and conductive body: polyisothioxo 20 ^ Paper size applies to a country ’s National Mou (CNS) person 4 specifications (YlOX297 public 嫠) &quot; (Please read the notes on the back before filling in this page)-Order printed by the R Industrial Consumer Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs ^ 44 ^ ^ 95 Α7 _Β7 ___ V. Description of the invention (丨 7) Please read the notes on the back first Fill in this page again with Yanai and conductors, polyweights and conductors, polyselenium and conductors, polyparastyrene, polysethene, polyethylenes, polyethylenes. Polyaniline ethylene such as polyethylene, polyselenium ethylene, polythiopiperidine ethylene, etc., and the conductors and the like exemplified, especially the polymer in which the aniline conductor is soluble in an organic solvent is preferable, The conductive polymer used in the electrode active material of this type of battery or electrode is As a chemical or electrochemical method or other well-known manufacturing methods. . Still other organic substances such as disulfide compounds such as 2,5-dithio-1,3,4- azole, and the mixture of conductive polymers of this type are better to achieve the purpose of capacity ^ Ministry of Economic Affairs wisdom The electrolyte used in the present invention printed by the Consumer Cooperative of the Property Bureau includes, for example, low-carbon ethers such as triethylglycol methyl ether, tetraethylglycol methyl ether, ethyl carbonate, propyl carbonate, Carbonates such as dimethyl carbonate, diethyl carbonate, ethylene carbonate (m) propylene carbonate, etc. / lactones such as r-butyrolactone *, aromatic eyes such as phenylcyanide, tolylxylene, etc. Sulfur-containing and nitrogen-containing compounds such as dimethyldiamine, dimethylthioamine, N-methylpyrrolidone, .N-vinylpyrrolidone, vanadium Alcohols such as phosphate ethers, ethanol: propanol, butanol. Among them, low-carbon ethers, carbonates and lactones are preferred. The separator is made of polyethylene porous membrane (PE), polypropylene porous membrane (PP), PP / PE / PP porous membrane, and fluorene molecular solid electrolyte membrane containing epoxy vinyl. The electrolytic salts used are alkali metal salts, for example, LiCF3 S03, LiPF3, LiPF6, LiCJ04, Lil 'UBF4' · USCN, LiAsF6, LiN (CF3SOj) 2 and the like. 21 This paper is once again applicable to China ’s poverty rate (CNS &gt; A4 size (210X297mm) A7 * 442995 B7______ V. Description of the invention (&gt; 〇) The following examples are used to illustrate the present invention in detail. In the following The coke used in the examples and comparative examples is non-needle coke (pre-calcined product). LPC-S coke (hereinafter referred to as coke A) and needle-shaped coke (pre-calcined product) manufactured by Nippon Steel Chemical Co., Ltd. LPC-UL coke (hereinafter referred to as Coke B) made by the same company (In the individual experiments, 30 kg of the above coke are provided for testing purposes: (Test of battery characteristics) Examples and comparisons of the following battery characteristics tests In the examples, 3% by weight of polyethylene fluoride powder was added to graphite powder under the same conditions on the batteries prepared as follows. After kneading with a small amount of N-methylpropyl ketone (NMP), The electrode was pressed and dried on a copper wire to form an electrode, and a reference electrode for evaluating the characteristics of the electrode and a three-electrode battery using lithium metal as a reference electrode were printed on the electrolyte by the Ministry of Economic Affairs, Intellectual Property Bureau, and the Consumers ’Cooperative. Carbonic acid A mixed solution of ethylene ester and dimethyl carbonate (volume ratio of 1: 1) dissolves Imole / liter LiPFe. The battery is assembled in a glove box that is adjusted in a dry argon ambient gas with a dew point below -60 ° c The battery is charged and discharged within the range of potential 0 to 1.5V. The charge and discharge are implemented at a current density of 0.2 mA / cm2. The charge and discharge efficiency shown in the table is the electrical capacity ratio of the discharge to the charged electrical capacity. Example 1 Coke A was coarsely pulverized into large particles of 2 to 3 mm in size by a pulverizer (manufactured by Hosokawa Micro Co., Ltd.). • This coarsely pulverized sample was pulverized by a jet mill (IDS2UR, manufactured by Nippon Gas Co., Ltd.). Finely smashed. At this time, 96 _22_ can be continuously calibrated in the β countries of this paper standard () A4 size (210X297 Gong &quot; 7 Ιί 442995 Α7 __Β7 ___) 5. Description of the invention (&gt; /) Please read the following notes Please fill in the following items: %% (¾ is weight%: the same below) coarse powder of 35μm or more is removed. 'Next, classify by turbine type (TC15N Nikkei Engineering Co., Ltd.) by airflow. The following can be classified For particle removal, The aspect ratio is 4.0: a 15 kg portion of the finely pulverized sample is sealed in a graphite crucible with a lid of 40 cm in diameter and a volume of 40 liters, and placed in a graphite furnace using a graphite heater at 2800 ° Graphitization at a temperature of C: After cooling, the powder was taken out to obtain 14 kg of powder. The particles of 53 // m or more formed by agglutination during graphitization were removed with an ASTM standard 270 screen (53 # πι). The obtained graphite The powder characteristics are shown in Table 1. This powder is the result of re-graphitization after controlling the pulverized particles: specific surface area, aspect ratio: good overall density and excellent coatability. Powders with a carbon density standard can be obtained, but because boron is not used as much as possible, discharge The capacity is about 281 mAh / g. However, the discharge capacity is still comparative example 1. High c. Example 2 The coke A is coarsely pulverized by a pulverizer (manufactured by Hosokawa Micro Co., Ltd.) into large particles of 2 to 3 mm. Crushing machine (IDS2UR, Japanese version * Employees of the Intellectual Property Bureau of the Ministry of Economy ’s Consumer Cooperative Printed Gas Co., Ltd.) finely pulverizes the coarsely pulverized sample. At this time, 95% (¾ is the weight%) Removal of coarse powder above 50 # m: Next, classify by air flow using a turbo classifier (manufactured by TC15N Nikkei Engineering Co., Ltd.). Particles below 5 tfin can be removed. At this time, the average vertical and horizontal size of the particles is removed. The ratio is 3.9. A 15 kg portion of this finely pulverized sample was sealed in a 40 crt inner diameter graphite crucible with a capacity of 40 liters and placed in graphite (Aches〇ii) «graphite at 2900eC. ,. 23 paper rulers after cooling Quick-use armor «National Kneading Standard (€ yang) into 4 specifications (210 father 297 mm) 442995 A7 B7 V. Description of the invention (&gt; v) Take out the powder to get the Subaru Dan willow machine (transliteration &gt; 14kg) The powder was removed by using an ASTM standard 270 mesh (53 // m) to remove particles with a size of 53 μ * η or more. The characteristics of the obtained graphite powder are shown in Table 1. The results of graphitization after pulverization were the same as in Example 1. • Powders with good specific surface area, aspect ratio, and overall density. Example 3 Coke A was coarsely pulverized into large particles of 2 to 3 mm or less by a pulverizer (manufactured by Hosokawa Micro Co., Ltd.): a jet mill (IDS 2UR, manufactured by Japan Gas Co., Ltd.) This coarsely pulverized sample is finely pulverized. At this time, the coarse powder of more than 50 μm can be continuously removed by 95% (% is the weight of the child%, the same below). Down with a turbo classifier (TC15N Nikkei Engineering Co., Ltd.) to classify by airflow, .. 5 μπ »can be removed as particles. At this time, the average aspect ratio of the particles is 4.0. A portion of 14.4 kg was added with boron carbide (B4C) and 0.6 kg. Mix at 0 rpm for 5 minutes. Put into a sealed graphite crucible with an inner diameter of 40 cm and a volume of 40 liters. Put it into a graphitization furnace using a graphite heater to perform graphitization at a temperature of 2900 ° C. ** After cooling, remove the powder. 14 kg of powder was obtained: the particles above 53 Mm were removed with an ASTM standard 270 screen (53 / zm), and the characteristics of the obtained graphite powder are shown in Table 1 ^ This example is after crushing and particle size adjustment, adding B4c to graphite As a result, a negative electrode material with excellent coating properties and a discharge capacity of 335 mAh / g, an initial efficiency of 91.¾, and excellent battery performance was obtained, and the resistance of powders that were not available with ordinary coke-based graphitization was as small as 〇.〇〇30Qcm, and the oxidation start temperature is as high as 63 It: excellent electrical conductivity and excellent stability 24 This paper size is applicable to the National Standards (CNS) Α4 specifications (2 丨 0X297 mm) Please read the notes on the back Matters reprinted by the Consumers ’Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs, printed 442995 A7 B7___ Five 'inventory description (&gt; $) materials' Example 4' Coarsely crushed coke A with a pulverizer (manufactured by Hosokawa Micro Co., Ltd.) to 2 ~ 3mm or less Particles. This coarsely pulverized sample is finely pulverized by a jet mill (IDS2UR, manufactured by Nihon Gas Co., Ltd.), and at this time, coarse powders of more than 50 ^ m in diameter of 95¾ can be continuously removed, and the average aspect of the particles at this time The size ratio is 3.9. 4% by weight of B4C is mixed in the finely pulverized sample. A 15 kg portion of the sample is sealed in a 40-liter inner diameter graphite crucible with a capacity of 40 liters. Put into graphite to heat The graphitization furnace is used to perform graphitization at a temperature of 2800 ° C. After cooling, the powder is taken out to obtain 14 kg of powder, and the particles above 53 μιη are removed by an ASTM standard 270 screen (53 μιη). The characteristics of the obtained graphite powder are as follows As shown in Table 1, an electrode material having excellent electrical conductivity and excellent stability was obtained as in Example 3. 寊 Example 5 Coke A was coarsely pulverized by a pulverizer (manufactured by Hosokawa Micro Co., Ltd.) to a size of 2 to 3 mm or less. Granulate the coarsely pulverized sample to a size of 50 / zm or less using a jet mill (IDS2URi, Japan Intellectual Property Bureau, Intellectual Property Bureau, Employees' Cooperative Printing Co., Ltd.): a part of the obtained coarsely pulverized sample 14.4 0.6 kg of boron carbide (B4C) · Mix with sample 3, put the finely pulverized sample into a covered graphite crucible with an inner diameter of 40cm and a volume of 40 liters, perform graphitization in the same graphitization furnace at a temperature of 2900aC, and cool Then, the powder was taken out and finely pulverized by a jet mill. The fine powder of 5 # ιη or less was removed by using a Trepex (manufactured by Hosokawa Micro Co., Ltd.) in accordance with ASTM standard 270 25 paper size Applicable to China National Kneading Rate (CNS) Α4 specification (210X297 mm) ~ Printed by the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs 442995 A7 _____B7_ V. Description of the invention (&gt; f) Screen (53; / m) the powder Removal of particles above 53; / m, the characteristics of the obtained graphite powder are as shown in Table 1. This powder is slightly the same as that of Comparative Example 1/2, and is pulverized after graphitization. The aspect ratio is 6.1. The specific surface area is 4'1 m2 / g but not complete. Due to the graphitization of b4C, the discharge capacity is 345 mAh / g '. The initial efficiency is 85) ¾ • and the powder resistance is 〇.〇 〇33Qcm, the oxidation start temperature of 633 ° C, has the same good performance as Examples 3., 4. . Example 6 · Coke A was coarsely pulverized into large particles having a size of 2 to 3 mm by a pulverizer (manufactured by Hosokawa Micro Co., Ltd.), and the coarsely pulverized sample was pulverized by a jet mill (IDS2UR, manufactured by Nihon Gas Co., Ltd.). Fine pulverization. At this time, coarse powder with a diameter of 50 #m or more can be removed continuously. Next, classify by turbine type (TC15N Nikkei Engineering Co., Ltd.) by air flow, and remove particles below km. At this time, the average aspect ratio of the particles was 4.5. 0.64 kg of boron carbide (B4C) was added to 14.4 kg of the finely pulverized sample, and 80 in a Hansel (transliteration) mixer. Mix for 5 minutes at rpm. The sample was sealed in a covered graphite crucible with an inner diameter of 40 cm and a volume of 40 liters. Graphitization was performed in the same graphitization furnace at a temperature of 28 to 50 ° C. After cooling, the powder was taken out to ASTM The characteristics of the graphite powder obtained by removing the% or more of the particles of 5 3 or more by a 27 ° sieve (53 // m) are as shown in Table 1. The same results as in Example 34 were obtained. Example 7 Crush A (coarsely manufactured by Hosokawa Micro Co., Ltd.) was used to coarsely pulverize coke A into large particles with a diameter of 2 to 3 mm, and a jet mill (IDS2UR, Japan ’s 26-scale scale was used in China ’s country ( CNS) A ^ grid (210X297 ft) Printed by the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs 442995 A7 __B7_ V. Description of the invention (/) made by Gas Co., Ltd. This coarsely pulverized sample is finely pulverized to 15 μΐη or less, and The following fine powder was removed using Temprex (Hosokawa: manufactured by MICRO Co., Ltd.). At this time, the average aspect ratio of the particles was 6.2. A 14.4 kg portion of the finely pulverized sample was added and mixed. After 0.6 kg of ENC, the 15 kg sample was sealed in a graphite crucible with a lid of 40 cm in diameter and a volume of 40 liters, and graphitized in a graphite manufacturing (Acheson) furnace at a temperature of 28 00 ° C. Cooling After the powder was taken out, it was pulverized by a Subaru willow (transliteration), and the particles above 53iim were removed with an ASTM standard 270 screen (53 // m). The characteristics of the obtained graphite powder are as shown in Table 1. The powder is graphitized by adding boron after crushing. . Resulting fine powder having an aspect ratio of at least 6.0: volumetric efficiency, powder resistance • oxidation initiation temperature were good. Example 8 The coke A was coarsely pulverized into large particles having a size of 2 to 3 mm by a pulverizer (manufactured by Hosokawa Micro Co., Ltd.). The coarsely pulverized sample was pulverized by a jet mill (IDS2UR, manufactured by Nippon Gas Co., Ltd.). Finely pulverize to finely pulverize particles to an average particle size of 50 μm or less. · Next, classify by turbine type classifier (manufactured by TC15N Nikkei Engineering Co., Ltd.) with air flow: 98% of particles below 3 μΐη can be removed With an average aspect ratio of 4.1 ·, 0,6 kg of B4C was added to 14-4 kg of a part of the finely pulverized sample and mixed in a Hansel mixer at SOO rpm for 5 minutes. The sample was sealed in an inner diameter. Covered graphite crucible with a capacity of 40 cm and a volume of 40 liters. • Graphitization in a graphitization furnace at a temperature of 290 eC "After cooling, take out the powder and disintegrate it with a Subaru willow machine (transliteration) to obtain 14 kg of powder. . Use the national standard car of ASTM paper 27〇27 paper size (CpS &gt; A4 specification (210X291 mmΪ) (Please read the precautions on the back before filling this page)

44 ^^ 95 A7 B7 V. Description of the invention (: 4) The sieve (53 / ζιη) removes more than 53μιη of this powder.

Read the precautions on the back before filling in the characteristics of this X ink powder as shown in Table 1. This powder is a method with a large particle size containing 4.1¾ micron powder. It has a good specific surface area, aspect ratio, etc., and has a capacity efficiency. .. Powder resistance. Oxidation onset temperature is also good. Comparative Example 1 Graphitization of coke A in the same graphitization furnace as before at a temperature of 2800 ° C: After cooling, the powder is taken out and the sample is taken out. A part of 15 kg of powder is coarsely pulverized with a pulverizer (manufactured by Hosokawa Micro Co., Ltd.) into large particles having a size of 2 to 3 mm, and the powder is pulverized by a jet mill (IDS2UR, manufactured by Yoshimoto Gas Co., Ltd.). The coarsely pulverized sample is finely pulverized. At this time, coarse powders above 955¾-35 can be continuously removed. Next, a turbo-type classifier (TC15N Nisshin Engineering Co., Ltd.) is used to classify by airflow. Particles below 5μΐη can be removed At this time, the average aspect ratio of the particles is 5.1. The particles of the powder 53 # m or more are removed with an AS TM standard 27Ό screen (53 # m). The characteristics of the obtained graphite powder are as shown in Table 1. The powder is crushed after graphitization *. Large surface area: small overall density, small discharge capacity, and high powder resistance to 0.1lOlQcm. »Printed by Consumer Consumption Cooperative of Intellectual Property Bureau, Ministry of Economic Affairs, Comparative Example 2 Place coke A in the same graphitization furnace at 2900 ° C Graphitize at a temperature of 50 ° C. Remove the powder after cooling. • A 15 kg portion of this sample is coarsely pulverized into large particles of 2 to 3 mm in size by a pulverizer (manufactured by Hosokawa Micro Co., Ltd.), and spray-milled. Crusher (IDS2UR, manufactured by Nihon Gas Co., Ltd.) This coarsely pulverized sample is finely pulverized to about the following time. At this time, coarse powders of 95¾ 50 // m or more can be continuously removed. Next, a turbine type classifier 28 papers are used. Standard Quick-Speed China® Home Standard (CNS &gt; A4 for "Grid (210X297 mm) 442995 Printed by A7 B7___ Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs V. Invention Description (&gt; /) (TC15N Sundial Project ( Co., Ltd.) by air flow classification, can remove particles below 8 / im of 98¾. At this time, the average aspect ratio of the particles is 5.4, and this powder is 53 / m with an ASTM standard 27 sieve (53 # m). The particles above zin are removed, and the characteristics of the obtained graphite powder are as shown in Table 1. In the same way as in Example 1, pulverizing after graphitization yields a method with a large specific surface area and a small overall density. * However, the discharge capacity has not been improved. Comparative Example 3 Coke B was coarsely ground with a pulverizer (manufactured by Hosokawa Micro Co., Ltd.). Crush into large particles with a size of 2 ~ 3mm. Using a jet mill (IDS2UR., Manufactured by Nihon Gas Co., Ltd.), the coarsely pulverized sample is finely pulverized to less than lhm. Powder removal: Next, classify by turbine classifier (manufactured by TCISN Nikkei Engineering Co., Ltd.) by airflow. Particles below 98% l // m can be removed. At this time, the average aspect ratio of the particles is-this A 15 kg portion of the finely pulverized sample was packed into a covered graphite crucible with an inner diameter of 40 cm and a volume of 40 liters. Graphitization was performed in a graphitization furnace at a temperature of 2800 ° C. After cooling, the powder was removed to obtain 14k Powder, using ASTM standard 270 mesh (53um &gt; particles of 53 # ιη or more of this powder are removed.) The properties of the graphite powder obtained are shown in Table 1. Compared with Examples 1 and 2, the method has a larger specific surface area. The discharge capacity is very poor. Comparative Example 4 Pulverizer (manufactured by Hosokawa Micro Co., Ltd.) is coarsely pulverized into large particles having a diameter of 2 to 3 mm. The coarsely pulverized sample is finely pulverized by a jet mill (IDS2ur 'Nippon Gas Co., Ltd.): at this time, continuous Reprinted 95 29 ^ paper «Chinese BB Family Standards (CNS) A4 Regulations ΓΓ (2IOX297 mm) &quot; 442995 A7 B7 Printed by the Intellectual Property Bureau of the Ministry of Economic Affairs and Industrial Cooperatives, Poverty Alleviation Cooperative, F50, 50% of the invention The above coarse powder is removed. Next, using a turbo classifier (manufactured by TC15N Nikkei Engineering Co., Ltd.) to classify particles below 9986 by airflow. At this time, the average aspect ratio of the particles is 6.4. A 15 kg portion of the crushed sample was sealed in a covered graphite crucible with an inner diameter of 40 cm and a volume of 40 liters: graphitized in a graphite furnace at 2800 ° C, and the powder was removed to obtain Hk. The powder obtained by removing particles of 53 pm or more from the powder with an ASTM standard 270 mesh (53 ^ m) is shown in Table 1. The aspect ratio of this powder is as large as 6.4. Its overall density is as small as 0.71 g / cm3. · Comparative Example 5 * Coke B was coarsely pulverized by a pulverizer (manufactured by Hosokawa Micro Co., Ltd.) into large particles having a size of 2 to 3 mm, and this was pulverized by a jet mill (IDS2UR, manufactured by Nippon Gas Co., Ltd.) The coarsely pulverized sample is finely pulverized to an average particle diameter of less than 40 # m. At this time, the average aspect ratio of the particles is 6.0. A portion of the finely pulverized sample is packed in an inner diameter of 40cm and a volume of 40 liters. Cover the graphite crucible '· Graphitize in a graphitization furnace at a temperature of 2800 ° C'. After cooling, remove the powder to obtain a 14k powder. Remove the particles with a particle size of 53pm or more using an ASTM standard 270 screen (Shin). The characteristics of the obtained graphite powder are as shown in Table 1. Although this powder has a large particle size, there are many fine powders, and the overall density is small. 30 This paper size is applicable to the Chinese national standard (C%) A4 size (210X297 cm) ) (Please read the notes on the back before filling this page)

A7 B7 V. Description of the invention (top?) Table 1 Example 1 Average particle size // m) 11 Specific surface area (mVg) 縦 4 Dimensional overall density (g / cm3) 5; / m or less (wt%) 53 μ m or less (wt%) Lattice interval (Co 値) _CA), boron content (wt%) Specific resistance Σαη Oxidation onset Cc) Discharge capacity mAh / g Initial efficiency (% &gt; 2.54 4.0 0.98 0.2 0 6.733 0 0.091 572 281 1 ^ 〆 · ^ Example 2 21.4 1.74 3.9 1.1 6.740 0.088 573 Example 3 Example 4 Example 5 20.6 1.34 4.0 1.0 0.2 6.717 0.98 0.0030 631 20.5 1.99 3.9 0.97 0.3 6.716 1.3 0.0031 633 22.5 4.10 6.1 0.89 6.716 2.10 0.0033 633 335 335 one 345 (please reward '% &quot; Jiangyi ^^ save and fill in winter K) Example 6 21.4 2.03 4.5 1.02 0 6.717 2.12 0.0034 632 Example 7 8.5 2.92 6.2 0.80 0 6.720 1.09 0.0031 628 321 Example 8 Comparison I Example 1 29.0 10.6 2.82 9.26 4.1 5.1 0,81 0.67 4.1 0.4 6.715 0.97 0.0030 631 34ί 6.735 0.101 569 278

SI Comparative Example 2 20.5 6.14 5.4 0.77 0 6.737 0.096 571 279 85 Printed by S Industrial Consumer Cooperative, Intellectual Property Bureau, Ministry of Economic Affairs 7.8 13.1 7.8 0.65 6.6 6.734 0 0.089 570 267 77 20.5 2.3] 6.4 0.71 6.743 0.051 575 252 85 31.1 2.92 6.0 0.78 2.5 0.1 6.733 0.078 572 240 This paper size is applicable to China ’s household solids ratio (CNS &gt; A4 size (210x297 mm) &31; 431 995 995 A7 B7. Industrial availability. The graphite powder of the present invention is used in negative lithium batteries To increase the discharge capacity, the cycle characteristics (battery life) are good, and at the same time, the initial charge and discharge efficiency is high (compared with the discharge capacity ratio of the first 1 to 3 times of charge storage): Please read the back, winter idea _ matters Refill% r

Printed by the Intellectual Property Bureau of the Ministry of Economic Affairs' Consumer Cooperatives 32 This paper size applies to the Chinese national standard (CNS &gt; A4 size (2 丨 0X297 mm &gt;)

Claims (1)

OQOQOOq? ABCS 442995 and March 7th Amendment / Correction / Supplement 6 、 Patent Application No. 88 1 1 7520 "Patent for Carbon Materials for Batteries and Batteries Using the Carbon Material" (Amended on February 9, 1990) Scope of patent application: 1. A carbon material for lithium batteries, which uses graphite powder as the carbon material for the negative electrode of lithium batteries. It is characterized by a specific surface area of 3 mz / g or less, an aspect ratio of 6 or less, and an overall density of It is composed of graphite powder of 0.8g / cm3 or more. 2. For the carbon material for lithium battery in the first scope of the patent application, the oxidation temperature of graphite powder is 600 ° C or more. 3. For example, the carbon material for lithium battery in the first or second scope of the patent application, wherein the powder ratio in the right-angle direction of the pressure direction when the graphite powder is pressed until the overall density of the powder becomes 1-5 g / cm3. The resistance is below 0.06Ω cm》 4. ~ A kind of carbon material for lithium battery, which uses graphite powder as the carbon material for the negative electrode of lithium battery. It is characterized by the overall density of the charge is 0.8 g / cra3 or more, and the oxidation starting temperature is 600. Made of graphite powder above ° C. 5. If the carbon material for lithium battery in item 4 of the patent application, the specific surface area is less than 3 mVg "6_If the carbon material for lithium battery in item 4 or 5 of the patent application, the aspect ratio is 6 or less" 7. A kind of carbon material for lithium battery, which uses graphite powder as the carbon material for the negative electrode of lithium battery. It is characterized by graphite powder with a specific surface area of 3 m2 / g or less and a charge density of 0.8 g / cm3 or more. The size of the pink paper is applicable to China National Standard (CNS) A4 (210 X 297 mm) ----- J — ^ ------------ Order --------- Line y (Please read the notes on the back before filling this page) Printed by the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs · 'A8 B8 C8 D8 / 、, Apply pressure at the end of the patent application range until the overall density of the powder becomes 1.5 g / At cm3, the specific resistance of the powder in the right-angle direction of the pressing direction is 0.06 Ω cm or less. 8. The carbon material for a lithium battery according to any one of claims 1, 2, 4, and 5'7, wherein the average particle diameter of the graphite powder is 8 to 30 β m. 9. For example, the carbon material for lithium battery in item 3 of the patent application scope, wherein the average particle size of graphite powder is 8 ~ 30 &quot; m. 10. The carbon material for a lithium battery according to any one of claims 1, 2, 4, 5, and 7, wherein the graphite powder does not substantially include particles having a particle diameter of 3 / zm or less and / or 53βηm or more. 11. For example, the carbon material for lithium battery in item 3 of the scope of patent application, wherein the graphite powder does not substantially include particles having a particle size of the following and / or 53 # m or more "12. For the lithium battery in item 8 of the scope of patent application A carbon material in which the graphite powder does not substantially include particles having a particle diameter of 3 μm or less and / or 53 / ζιη or more. η The carbon material for a lithium battery according to item 9 of the patent application scope, wherein the graphite powder does not substantially include particles having a particle diameter of less than and / or 53em. 14. For the lithium battery carbon material according to any one of the claims 1, 2, 4, 5, and 7, in which the Co of the graphite powder is below 6.745, "-2- this paper is applicable to national painters 楳Standard (CNS) A4 Regulations &lt; 210x297 mm) 1111 11 111 ----- I ί I ^ --------- line ^ --- V (Please read the notes on the back before filling (This page) Printed by the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs-4 years AU charge i-8δδΰ ABCS Printed by the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs * 1 ^ VI. Scope of patent application 15 Carbon materials for lithium batteries, in which the Co 値 of graphite powder is 6.745A or less. 16. For example, the carbon material for lithium battery in item 8 of the patent application scope, in which the Co 値 of the graphite powder is 6.745A or less. 17. For example, the carbon material for lithium battery in item 9 of the patent application scope, in which the Co 値 of the graphite powder is 6.745A or less. 18. For example, the carbon material for lithium batteries in item 10 of the patent application scope, in which the Co 値 of the graphite powder is 6.745A or less. 19. For example, the carbon material for lithium battery in item 11 of the patent application scope, in which the Co 値 of the graphite powder is 6.745A or less. 20. For example, the carbon material for lithium battery in item 12 of the patent application scope, in which the Co 値 of the graphite powder is 6.745A or less. 21. For example, the carbon material for lithium battery of item 13 of the scope of patent application, wherein the Co 値 of the graphite powder is 6.745A or less. 22. The carbon material for a lithium battery according to any one of claims 1, 2, 4, S, and 7, wherein boron is contained in the graphite powder. 23. The carbon material for lithium batteries according to item 3 of the scope of patent application, wherein graphite powder is contained in graphite powder. 24. The carbon material for a lithium battery such as the item No. 8 of the patent application scope, wherein the graphite powder contains boron. 25. The carbon material for thorium batteries, such as in the scope of the patent application No. 9, wherein the graphite powder contains boron. 26 The carbon material for the lithium batteries, in the scope of the patent application, contains boron. -3- This paper size uses China National Standard (CNS) A4 specifications (210 X 297 public love) ----- ^ --- ^-11 in ---- Order -------- -Line W--1 / (Please read the precautions on the back before filling this page) Λ8 m C8 D8 4 4 2 9 9 5. Amendment / Correction / Supplement on March 7th, Patent Application Z /. For example, the carbon material for lithium battery in the scope of application for patent No. 11 includes boron in graphite powder. 28. A paste for battery negative electrode, which is made of graphite powder as described in any one of claims 1, 2, 4, 5, and 7 as the main raw material, and added with polyvinylidene fluoride powder. A blender. 29. —A battery negative paste, which is prepared by mixing graphite powder as the main raw material as described in item 3 of the patent application scope and adding polyvinylidene fluoride powder. 30. —A battery, which It is made by using the graphite powder as described in any one of the claims 1, 2, 4, 5, and 7 as the main raw material of the negative electrode. 31. A type of battery 'is produced by using graphite powder as described in item 3 of the patent application as the main raw material of the negative electrode. 32—A kind of lithium battery, which is produced by using graphite powder as the main raw material of the negative electrode as described in any one of the items 1'2, 4, 5, 7 of the scope of the applied patent》 33—A kind of lithium battery ' It is made by using graphite powder as described in item 3 of the scope of patent application as the main raw material of the negative electrode. (Please read the precautions on the back before filling this page). When the Ministry of Economic Affairs is wise and evil, printed by the t-Bureau's Gongxiao Bone Cooperative -4--/ 1. This paper size is applicable to the Chinese national standard (CNS &gt; A4 size (2 丨 OX297 male *)