JP5169248B2 - Carbon microsphere powder for lithium ion secondary battery negative electrode material and method for producing the same - Google Patents

Description

  The present invention relates to a carbon material used as a negative electrode material of a lithium ion secondary battery having high capacity and high input / output, and a method for producing the same.

  Lithium ion secondary batteries using lithium salt organic electrolytes as non-aqueous electrolytic secondary batteries are lightweight and have high energy density, and are used for power sources such as portable cars and electric vehicles in recent years, including power supplies for portable small electronic devices. Expected as a power source.

  With recent high performance of portable small devices such as cellular phones, portable audio devices, portable video cameras, digital cameras, etc., their power consumption is increasing, and lithium ion batteries used as their power sources are increasing. Secondary batteries are required to have higher capacities. On the other hand, power sources such as hybrid cars and electric vehicles are required to have high input / output characteristics, that is, rapid charge / discharge characteristics, and long life, that is, excellent cycle characteristics. Thus, a lithium ion secondary battery is required to have a negative electrode material for lithium ion secondary batteries having various characteristics.

  It is conceivable to use metallic lithium as a negative electrode material as one means for increasing the capacity. However, lithium metal is difficult to handle because lithium ions are deposited in a dendritic state during growth and grow and have safety problems.

  Since the graphite material is excellent in the adsorption and desorption of lithium ions, the charge / discharge efficiency is high, and further, the potential at the time of discharge is almost equal to that of metallic lithium, and a high voltage battery can be obtained. However, the theoretical capacity in the case of using a graphite material is 372 mAh / g, and recent graphite materials are almost close to the value, so there is a limit to increasing the capacity of graphite alone.

  Thus, alloy-based negative electrode materials have been developed, and typical examples of metals include silicon, tin, bismuth, aluminum, and antimony. Among them, silicon has many coordination numbers for taking in lithium, and its theoretical capacity is 4000 mAh / g. However, on the other hand, the volume expansion is large and the pulverization of silicon proceeds, so that it cannot be used repeatedly. Therefore, by combining silicon oxide, graphite, and carbon with silicon, the volume expansion is suppressed and the material far exceeds the capacity of existing graphite.

  In the composite material using silicon as described above, it is preferable that the particle diameter of silicon is small, and when it is present at a level of several nanometers, it can be used repeatedly.

  As a composite material with carbon containing silicon, for example, JP-A-7-315822 (Patent Document 1) discloses a liquid such as benzene and a liquid such as silicon tetrachloride and dimethyldicyclosilane as a carbon source of a raw material. Each of these is inserted into a pyrolysis furnace using a carrier such as high-purity argon gas, pyrolyzed in a temperature range of 200 to 1100 ° C., and kept for 1 to 5 hours to obtain a deposit (chemical vapor deposition method ( A carbonaceous insertion compound obtained by the CVD method) is disclosed.

  Japanese Patent Application Laid-Open No. 2004-47404 (Patent Document 2) discloses a silicon compound obtained by heat-treating silicon oxide in advance under an inert gas atmosphere at 900 to 1400 ° C. to disproportionate, and silicon fine particles obtained from silicon dioxide by a sol-gel method. A composite obtained by sintering a composite obtained by solidifying silicon fine powder through fine powdered silica and water, or silicon and its partial oxide or nitride under an inert gas stream The surface of particles having a structure in which silicon microcrystals are dispersed in a silicon-based compound obtained by chemical vapor deposition treatment with an organic gas and / or vapor at a temperature of 800 to 1400 ° C. is heated at 1400 ° C. A conductive silicon composite is disclosed which is coated with

  In JP-A-7-302588 (Patent Document 3), a Li source-containing gas, a Si source-containing gas, and a C source-containing gas are introduced into a reaction vessel, and Li— A negative electrode for a lithium secondary battery containing Li, Si, and C is disclosed by forming a Si—C based composite film.

JP-A-7-315822 (Claims) JP 2004-47404 A (Claims) JP-A-7-302588 (Claims)

  However, since the carbonaceous insertion compound of Patent Document 1 is produced by the CVD method, it is considered that a bulk body is formed, and its size is estimated to be 1 μm or more. Therefore, there was a problem that the input / output characteristics of Li ions were inferior. Patent Document 1 also has problems such as difficulty in mass-producing the carbonaceous insertion compound efficiently, difficulty in handling, and unstable insertion of raw materials.

  Moreover, in patent document 2, although Si microcrystal particle | grains are disperse | distributed in silicon dioxide and the carbon which has a braphite structure is coated on the silicon dioxide surface, the carbon amount is described as preferably 10-30 wt%. Therefore, the conductivity cannot be ensured as compared with a pure carbon material having a nanostructure. Therefore, a decrease in current collecting performance is inevitable, and movement of Li ions in the electrode is hindered, resulting in poor high input / output characteristics.

  Moreover, in patent document 3, there existed a problem that a film thickness was as thick as 5-20 micrometers and the high input / output characteristic was inferior.

  Accordingly, an object of the present invention is to provide a negative electrode material for a lithium ion secondary battery having high capacity and high input / output while maintaining excellent rapid charge / discharge characteristics, excellent charge / discharge cycle characteristics and high initial efficiency. It is in.

  As a result of intensive studies to solve the above-described problems in the prior art, the present inventors have diluted a compound serving as a silicon source and a compound serving as a carbon source with an inert gas, and thereby applied external heat at a specific temperature. When introduced into a reaction furnace and passed through the external heating reactor at a specific linear velocity, the carbon source compound is decomposed and carbonized into spherical carbon microspheres. Since silicon generated by the decomposition of the compound serving as a silicon source is taken into the carbon microspheres, it was found that carbon microspheres enclosing fine silicon can be obtained, and the present invention has been completed.

  That is, in the present invention (1), the silicon content is 1 to 30% by weight in terms of silicon atom, the arithmetic average primary particle diameter dn measured with an electron microscope is 150 to 1000 nm, the volatile matter Vm is 5.0% or less, The ratio of the half-value width ΔDst to the Stokes mode diameter Dst measured by the disc centrifuging apparatus (DCF) (half-value width ΔDst / Stokes mode diameter Dst) is 0.40 to 1.10, and the crystallite lattice plane measured by the X-ray diffraction method Provided is a carbon microsphere powder for a negative electrode material of a lithium ion secondary battery, characterized in that the distance d (002) is a carbon microsphere having a diameter of 0.370 nm or less.

  Further, the present invention provides a raw material-containing gas in which an organosilicon compound is diluted with an inert gas and the concentration of the organosilicon compound is 10 to 50% by volume, and the temperature inside the reactor is outside 1000 to 1400 ° C. Introduced into a thermal reactor, passed through the externally heated reactor at a linear flow rate of 0.02 to 4.0 m / sec, and then the generated thermal decomposition product was cooled from the externally heated reactor to the cooling zone. The method for producing a carbon microsphere powder for a lithium ion secondary battery negative electrode material, characterized in that the carbon microsphere powder for a lithium ion secondary battery negative electrode material is obtained Is to provide.

  The present invention also provides a raw material-containing gas in which the organosilicon compound and hydrocarbon are diluted with an inert gas and the total concentration of the organosilicon compound and the hydrocarbon is 10 to 50% by volume in the reactor. It was introduced into an externally heated reactor having a temperature of 1000 to 1400 ° C., passed through the externally heated reactor at a linear flow rate of 0.02 to 4.0 m / sec, and then the generated pyrolyzate was For lithium ion secondary battery negative electrode material characterized in that it is transferred from an external heat reactor to a cooling region, cooled, and then collected to obtain carbon microsphere powder for negative electrode material of lithium ion secondary battery A method for producing a carbon microsphere powder is provided.

  In the present invention, the inorganic silicon compound and the hydrocarbon are diluted with an inert gas, the concentration of the hydrocarbon is 10 to 50% by volume, and the concentration of the inorganic silicon compound is 1 to 30% by volume. The raw material-containing gas was introduced into an externally heated reactor having a temperature in the reactor of 1000 to 1400 ° C., and passed through the externally heated reactor at a linear flow rate of 0.02 to 4.0 m / sec. The produced thermal decomposition product is transferred from the external heating reactor to a cooling region, cooled, and then collected to obtain carbon microsphere powder for a lithium ion secondary battery negative electrode material. The manufacturing method of the carbon microsphere powder for lithium ion secondary battery negative electrode materials to be performed is provided.

  In the present invention, the organosilicon compound and the inorganic silicon compound are diluted with an inert gas, the concentration of the organosilicon compound is 10 to 50% by volume, and the concentration of the inorganic silicon compound is 1 to 30% by volume. The raw material-containing gas is introduced into an externally heated reactor whose temperature in the reactor is 1000 to 1400 ° C., and is allowed to pass through the externally heated reactor at a linear flow rate of 0.02 to 4.0 m / sec. Then, the generated pyrolyzate is transferred from the external heating reactor to the cooling region, cooled, and then collected to obtain carbon microsphere powder for a lithium ion secondary battery negative electrode material. A feature of the present invention is to provide a method for producing carbon microsphere powder for a negative electrode material for a lithium ion secondary battery.

  In the present invention, the organosilicon compound, the inorganic silicon compound and the hydrocarbon are diluted with an inert gas, the total concentration of the organosilicon compound and the hydrocarbon is 10 to 50% by volume, and the inorganic silicon compound A raw material-containing gas having a concentration of 1 to 30% by volume is introduced into an externally heated reactor whose temperature in the reactor is 1000 to 1400 ° C., and at a linear flow rate of 0.02 to 4.0 m / sec, The externally heated reactor is passed through, and then the generated thermal decomposition product is transferred from the externally heated reactor to the cooling region to be cooled, and then collected and used for a negative electrode material for a lithium ion secondary battery. The present invention provides a method for producing a carbon microsphere powder for a negative electrode material for a lithium ion secondary battery, characterized in that the carbon microsphere powder is obtained.

  According to the present invention, it is possible to provide a negative electrode material for a lithium ion secondary battery having high capacity and high input / output while maintaining excellent rapid charge / discharge characteristics, excellent charge / discharge cycle characteristics and high initial efficiency. .

  In the method for producing a carbon microsphere powder for a negative electrode material for a lithium ion secondary battery of the present invention, a raw material-containing gas is introduced into an externally heated reactor having a temperature in the reactor of 1000 to 1400 ° C. Pass the externally heated reactor at a linear flow rate of 4.0 m / sec, then transfer the generated pyrolyzate from the externally heated reactor to a cooling zone to cool, and then collect it. This is a method for producing a carbon microsphere powder for a lithium ion secondary battery negative electrode material to obtain a carbon microsphere powder for a lithium ion secondary battery negative electrode material.

  The manufacturing method of the carbon microsphere powder for lithium ion secondary battery negative electrode materials of this invention is demonstrated with reference to FIG. FIG. 1 is an explanatory diagram showing the overall configuration of an apparatus for carrying out the method for producing a carbon microsphere powder for a negative electrode material for a lithium ion secondary battery of the present invention. In addition, this apparatus shown in FIG. 1 is an example of the apparatus for implementing the manufacturing method of the carbon microsphere powder for lithium ion secondary battery negative electrode materials of this invention, It is not limited to this. In FIG. 1, 9 is a liquid silicon compound tank in which a liquid silicon compound is stored, 10 is a gas silicon compound cylinder filled with a gaseous silicon compound, and 11 is a gas filled with a gaseous hydrocarbon. A hydrocarbon cylinder, 12 is an inert gas cylinder, 14 is a liquid hydrocarbon tank in which liquid hydrocarbons are stored, and 17 is an externally heated reactor. Reference numeral 15 denotes a preheating heater for preheating the liquid silicon compound tank 9 or the liquid hydrocarbon tank 14 and a heater for vaporizing the liquid silicon compound or the liquid hydrocarbon. 13 is a flow meter for measuring the introduction amount of each raw material of the raw material-containing gas. The liquid silicon compound tank 9, the gas silicon compound cylinder 10, the gas hydrocarbon cylinder 11, and the liquid hydrocarbon tank 14 are connected to the raw material-containing gas introduction pipe 8. The raw material containing gas mixed with and diluted with an inert gas can be introduced into the external heating reactor 17 from the raw material containing gas introduction pipe 8.

  In FIG. 1, 18 is a heater for heating the externally heated reactor 17, 21 is a cooling pipe for cooling the pyrolyzate and inert gas generated in the externally heated reactor 17, 24 Is a collection chamber for collecting the pyrolyzate, 25 is a neutralization tank for neutralizing acidic gas generated by thermal decomposition of the raw material-containing gas, and 26 is generated by thermal decomposition of the raw material-containing gas An exhaust gas combustion apparatus for completely burning the cracked gas. In the neutralization tank 25, for example, a basic liquid such as sodium hydroxide is placed. 20 is a temperature controller for adjusting the temperature of the external heating reactor, and 23 is a vacuum pump for deoxidizing the inside of the external heating reactor in advance. A valve 22 is attached to the pipe connected to the collection chamber 24 and the vacuum pump 23.

  In FIG. 1, reference numeral 19 denotes a rear-stage raw material-containing gas introduction pipe for introducing the raw-material-containing gas into the rear stage of the external heating reactor 17. The liquid silicon compound tank 9, the gas silicon compound cylinder 10, the gas hydrocarbon cylinder 11, and the liquid hydrocarbon tank 14 are also connected to the downstream side raw material-containing gas introduction pipe 19, The raw material containing gas mixed with this raw material and diluted with an inert gas can be introduced into the rear stage portion of the external heating reactor 17 from the rear stage side raw material containing gas introduction pipe 19.

  The externally heated reactor 17 is a reactor for pyrolyzing and carbonizing the raw material in the raw material-containing gas into carbon microspheres containing silicon. Examples of the external heating reactor 17 include an opaque quartz tube having an inner diameter of 145 mm and a length of 1500 mm. In FIG. 1, the heater 18 is installed outside the external heating reactor 17. In the present invention, the external heating system includes a high frequency induction heating system, an electrothermal heating system, and a combustion gas flow system. Etc. are applicable.

  The external heating reactor 17 can be inserted with heat-resistant tubes having different tube diameters in order to control the linear flow velocity of the raw material-containing gas. The heat-resistant tube is made of, for example, mullite or silicon carbide.

  The temperature in the external heating reactor 17 is controlled to a predetermined temperature by the temperature controller 20 by detecting the temperature in the external heating reactor 17 with a thermocouple or a radiation thermometer.

  First, the raw material from the liquid silicon compound tank 9, the gas silicon compound cylinder 10, the gas hydrocarbon cylinder 11 and the liquid hydrocarbon tank 14, the inert gas from the inert gas cylinder 12, the raw material The raw material containing gas is supplied from the raw material containing gas introduction pipe 8 to the external heating reactor 17 by supplying each raw material in the containing gas so as to have a predetermined concentration. Then, the raw material-containing gas is passed through the external heating reactor 17.

  The raw material in the raw material-containing gas introduced into the external heating reactor 17 is pyrolyzed and carbonized by passing through the external heating reactor 17 to become a thermal decomposition product. At this time, the raw material in the raw material-containing gas is carbonized into spherical carbon microspheres, and silicon generated by thermal decomposition is included inside during carbonization. Therefore, the pyrolyzate discharged through the external heat reactor 17 is carbon microspheres containing silicon.

  Next, the pyrolyzate and the inert gas discharged from the external heating reactor 17 are cooled by the cooling pipe 21, and then the pyrolyzate is collected in the collection chamber 24. Thus, carbon microspheres for a negative electrode material for a lithium ion secondary battery are obtained. Further, the exhaust gas is introduced into the neutralization tank 25 at the rear stage of the collection chamber 24, and after acid decomposition products in the exhaust gas are removed, the exhaust gas is introduced into the exhaust gas combustion device 26. The cracked gas is completely burned and discharged to the outside.

  In the apparatus shown in FIG. 1, the raw material-containing gas is introduced from the raw material-containing gas introduction pipe 8, and the raw material-containing gas is introduced from the rear-stage-side raw material-containing gas introduction pipe 19 to the rear stage of the external heating reactor 17. Gas can also be introduced. Then, by introducing the raw material-containing gas into the rear stage portion of the external heating reactor 17, it becomes easy to obtain carbon microspheres having an arithmetic primary average particle diameter exceeding 450 nm.

  Thus, using the apparatus shown in FIG. 1, the method for producing carbon microsphere powder for a negative electrode material of a lithium ion secondary battery of the present invention is performed to obtain carbon microsphere powder.

  That is, the method for producing a carbon microsphere powder for a negative electrode material of a lithium ion secondary battery according to the present invention (hereinafter also referred to as the method for producing the carbon microsphere powder of the present invention) includes the raw material-containing gas in a reactor. Is introduced into an externally heated reactor having a temperature of 1000 to 1400 ° C., and is passed through the externally heated reactor at a linear flow rate of 0.02 to 4.0 m / sec. Carbon microspheres for lithium ion secondary battery negative electrode material obtained by transferring to the cooling region from the external heating reactor and cooling, and then collecting to obtain carbon microsphere powder for lithium ion secondary battery negative electrode material It is a manufacturing method of powder.

  In the method for producing the carbon microsphere powder of the present invention, first, the raw material-containing gas is introduced into the external heating reactor and allowed to pass through the external heating reactor. In the present invention, the part where the raw material-containing gas is introduced into the external heating reactor is referred to as a front-stage raw material-containing gas introduction part, and is distinguished from a later-stage raw material-containing gas introduction part. Moreover, in FIG. 1, the site | part shown by the code | symbol 30 is this front | former stage raw material containing gas introduction | transduction site | part.

The method for producing carbon microsphere powder of the present invention includes the following five embodiments as combinations of raw materials in the raw material-containing gas:
(1) Raw material-containing gas in which an organosilicon compound is diluted with an inert gas (hereinafter also referred to as raw material-containing gas (1)),
(2) A raw material-containing gas in which an organosilicon compound and a hydrocarbon are diluted with an inert gas (hereinafter also referred to as a raw material-containing gas (2)),
(3) Raw material-containing gas obtained by diluting an inorganic silicon compound and hydrocarbon with an inert gas (hereinafter also referred to as raw material-containing gas (3)),
(4) A raw material-containing gas in which an organosilicon compound and an inorganic silicon compound are diluted with an inert gas (hereinafter also referred to as a raw material-containing gas (4)),
(5) A raw material-containing gas in which an organosilicon compound, an inorganic silicon compound, and a hydrocarbon are diluted with an inert gas (hereinafter also referred to as a raw material-containing gas (5)),
There is.

The organosilicon compound related to the raw material-containing gas is a silicon compound having a carbon atom in the molecule. Examples of the organosilicon compound include a silane compound in which at least one of four substituents of Si atom is a substituent that serves as a carbon source such as an alkyl group, an alkoxy group, an aromatic group, or a cycloalkyl group; A compound in which the chain is a repeating unit of -Si-O- and has a substituent serving as a carbon source in the side chain; a compound in which the main chain is a repeating unit of -Si- and has a substituent serving as a carbon source in the side chain; A compound in which the chain is a repeating unit of —Si—C— and a substituent is present in the side chain, specifically, for example, tert-butyldimethylsilane (t—C ₄ H ₉ (CH ₃ ) ₂ SiH ), An alkylsilane compound having 1 to 4 alkyl groups such as trihexylsilane ((CH ₃ (CH ₂ ) ₅ ) ₃ SiH); an alkoxy having 1 to 4 alkoxy groups such as methoxy group and ethoxy group Examples thereof include xylsilane compounds; silicones having a substituent serving as a carbon source in the side chain; polysilane compounds having a substituent serving as a carbon source in the side chain; and organosilicon polymers such as a polycarbosilane compound. These may be one kind or a combination of two or more kinds. Of these, those that are liquid or solid at room temperature are heated to a boiling point or higher, vaporized, and mixed with the raw material-containing gas.

The inorganic silicon compound related to the raw material-containing gas is a silicon compound having no carbon atom in the molecule. Examples of the inorganic silicon compound include monosilane (SiH ₄ ), disilane (Si ₂ H ₆ ), chlorosilane (SiCl _n H _4-n : n is an integer of 1 to 4), and bromosilane (SiBr _n H _4-n : n is an integer of 1 to 4). These may be one kind or a combination of two or more kinds. Of these, those that are liquid or solid at room temperature are heated to a boiling point or higher, vaporized, and mixed with the raw material-containing gas.

  Examples of the hydrocarbons related to the raw material-containing gas include aliphatic hydrocarbons such as methane, ethane, propane, butane, ethylene, propylene and butadiene; monocyclic aromatic hydrocarbons such as benzene, toluene and xylene; naphthalene and anthracene And polycyclic aromatic hydrocarbons such as natural gas, city gas, and liquefied natural gas. These may be one kind or a combination of two or more kinds. Of these, those that are liquid or solid at room temperature are heated to a boiling point or higher, vaporized, and mixed with the raw material-containing gas.

  The inert gas related to the raw material-containing gas is a gas for diluting an organic silicon compound, an inorganic silicon compound or a hydrocarbon as a raw material, and these raw materials are transported to the external heating reactor, It functions as a carrier gas that passes through the thermal reactor and carries out the pyrolyzate produced in the externally heated reactor out of the furnace. The inert gas is an inert gas that is stable and does not react at the time of thermal decomposition of the raw material, excluding hydrogen gas, and examples thereof include nitrogen, argon, helium, neon, xenon, and krypton.

  When hydrogen gas is used as the carrier gas, the thermal decomposition reaction of the raw material is suppressed, so that the yield is lowered and the production efficiency is deteriorated. Furthermore, when hydrogen gas is used as a carrier gas, the surface of the carbon microspheres is always in a hydrogen atmosphere, so the dehydrogenation reaction is hindered during the carbonization process, resulting in carbon microspheres with many irregularities, It is easy for carbon content to remain.

  The raw material-containing gas is a gas containing the organic silicon compound, the inorganic silicon compound or the hydrocarbon as a raw material, and is a gas obtained by diluting the raw material with an inert gas.

  When the raw material-containing gas is the raw material-containing gas (1), the concentration of the organosilicon compound in the raw material-containing gas (1) is 10 to 50% by volume, preferably 12 to 48% by volume, particularly preferably. 15 to 45% by volume. If the concentration of the organosilicon compound in the raw material-containing gas (1) is less than the above range, it is necessary to reduce the linear velocity of the raw material-containing gas, so that the pyrolyzate adheres significantly to the reaction tube wall. On the other hand, when the above range is exceeded, it is difficult for a uniform reaction to proceed, and it becomes difficult to obtain carbon microspheres having a sharp particle distribution, and the reaction tube may be blocked.

  The ratio of carbon element and silicon element in all raw materials contained in the raw material-containing gas (1) is the weight ratio of silicon atoms to the total of carbon atoms and silicon atoms in terms of atoms "Si / (C + Si)" And preferably from 0.013 to 0.37, particularly preferably from 0.03 to 0.32, and even more preferably from 0.05 to 0.30. When the ratio of carbon element and silicon element in all raw materials contained in the raw material-containing gas (1) is within the above range, the content of silicon atoms in the carbon microsphere powder is 1 to 30% by weight. Therefore, it is possible to increase the capacity and input / output while maintaining excellent rapid charge / discharge characteristics, excellent charge / discharge cycle characteristics, and high initial efficiency.

  When the raw material-containing gas is the raw material-containing gas (2), the total concentration of the organosilicon compound and the hydrocarbon in the raw material-containing gas (2) is 10 to 50 volume%, preferably 12 to 48 volume. %, Particularly preferably 15 to 45% by volume. If the total concentration of the organosilicon compound and the hydrocarbon in the raw material-containing gas (2) is less than the above range, it is necessary to reduce the linear velocity of the raw material-containing gas. On the other hand, when the above range is exceeded, uniform reaction is difficult to proceed, and it is difficult to obtain carbon microspheres having a sharp particle distribution, and the reaction tube may be blocked.

  The ratio of carbon element and silicon element in all raw materials contained in the raw material-containing gas (2) is the weight ratio of silicon atoms to the total of carbon atoms and silicon atoms in terms of atoms "Si / (C + Si)" And preferably from 0.013 to 0.37, particularly preferably from 0.03 to 0.32, and even more preferably from 0.05 to 0.30. When the ratio of carbon element and silicon element in all raw materials contained in the raw material-containing gas (2) is within the above range, the content of silicon atoms in the carbon microsphere powder is 1 to 30% by weight. Therefore, it is possible to increase the capacity and input / output while maintaining excellent rapid charge / discharge characteristics, excellent charge / discharge cycle characteristics, and high initial efficiency.

  When the raw material-containing gas is the raw material-containing gas (3), the concentration of the hydrocarbon in the raw material-containing gas (3) is 10 to 50% by volume, preferably 12 to 48% by volume, particularly preferably 10 ~ 45% by volume. If the concentration of the hydrocarbon in the raw material-containing gas (3) is less than the above range, it is necessary to lower the linear velocity of the raw material-containing gas, so that the pyrolysis product adheres to the reaction tube wall. On the other hand, when the above range is exceeded, it is difficult for a uniform reaction to proceed, and it becomes difficult to obtain carbon microspheres having a sharp particle distribution, and the reaction tube may be blocked.

  The concentration of the inorganic silicon compound in the raw material-containing gas (3) is 1 to 30% by volume, preferably 1.2 to 29.5% by volume, particularly preferably 1.5 to 29% by volume. Since the concentration of the inorganic silicon compound in the raw material-containing gas (3) is within the above range, the content of silicon atoms in the carbon microsphere powder can be 1 to 30% by weight. The capacity and input / output can be increased while maintaining the rapid charge / discharge characteristics, excellent charge / discharge cycle characteristics, and high initial efficiency.

  The ratio of carbon element and silicon element in all raw materials contained in the raw material-containing gas (3) is the weight ratio of silicon atoms to the total of carbon atoms and silicon atoms in terms of atoms "Si / (C + Si)" And preferably from 0.013 to 0.37, particularly preferably from 0.03 to 0.32, and even more preferably from 0.05 to 0.30. When the ratio of carbon element and silicon element in all raw materials contained in the raw material-containing gas (3) is within the above range, the content of Si atoms in the carbon microsphere powder is 0.5-30. Therefore, the capacity and input / output can be increased while maintaining high lithium ion adsorption / desorption rate, excellent charge / discharge cycle characteristics and high initial efficiency.

  When the raw material-containing gas is the raw material-containing gas (4), the concentration of the organosilicon compound in the raw material-containing gas (4) is 10 to 50% by volume, preferably 12 to 48% by volume, particularly preferably. 15 to 45% by volume. If the concentration of the organosilicon compound in the raw material-containing gas (4) is less than the above range, it is necessary to reduce the linear velocity of the raw material-containing gas, so that the pyrolysis product adheres significantly to the reaction tube wall. On the other hand, when the above range is exceeded, it is difficult for a uniform reaction to proceed, and it becomes difficult to obtain carbon microspheres having a sharp particle distribution, and the reaction tube may be blocked.

  The concentration of the inorganic silicon compound in the raw material-containing gas (4) is 1 to 30% by volume, preferably 1.2 to 29.5% by volume, particularly preferably 1.5 to 29% by volume. Since the concentration of the inorganic silicon compound in the raw material-containing gas (4) is within the above range, the content of silicon atoms in the carbon microsphere powder can be 1 to 30% by weight. The capacity and input / output can be increased while maintaining the rapid charge / discharge characteristics, excellent charge / discharge cycle characteristics, and high initial efficiency.

  The ratio of carbon element and silicon element in all the raw materials contained in the raw material-containing gas (4) is the weight ratio of silicon atoms to the total of carbon atoms and silicon atoms in terms of atoms "Si / (C + Si)" And preferably from 0.013 to 0.37, particularly preferably from 0.03 to 0.32, and even more preferably from 0.05 to 0.30. When the ratio of carbon element and silicon element in all raw materials contained in the raw material-containing gas (4) is within the above range, the content of silicon atoms in the carbon microsphere powder is 1 to 30% by weight. Therefore, it is possible to increase the capacity and input / output while maintaining excellent rapid charge / discharge characteristics, excellent charge / discharge cycle characteristics, and high initial efficiency.

  When the raw material-containing gas is the raw material-containing gas (5), the total concentration of the organosilicon compound and the hydrocarbon in the raw material-containing gas (5) is 10 to 50 volume%, preferably 12 to 48 volume. %, Particularly preferably 15 to 45% by volume. If the total concentration of the organosilicon compound and the hydrocarbon in the raw material-containing gas (5) is less than the above range, it is necessary to reduce the linear velocity of the raw material-containing gas. On the other hand, when the above range is exceeded, uniform reaction is difficult to proceed, and it is difficult to obtain carbon microspheres having a sharp particle distribution, and the reaction tube may be blocked.

  The concentration of the inorganic silicon compound in the raw material-containing gas (5) is 1 to 30% by volume, preferably 1.2 to 29.5% by volume, particularly preferably 1.5 to 29% by volume. Since the concentration of the inorganic silicon compound in the raw material-containing gas (5) is within the above range, the content of silicon atoms in the carbon microsphere powder can be 1 to 30% by weight. The capacity and input / output can be increased while maintaining the rapid charge / discharge characteristics, excellent charge / discharge cycle characteristics, and high initial efficiency.

  The ratio of carbon element and silicon element in all raw materials contained in the raw material-containing gas (5) is the weight ratio of silicon atoms to the total of carbon atoms and silicon atoms in terms of atoms "Si / (C + Si)" And preferably from 0.013 to 0.37, particularly preferably from 0.03 to 0.32, and even more preferably from 0.05 to 0.30. When the ratio of carbon element and silicon element in all raw materials contained in the raw material-containing gas (5) is within the above range, the content of silicon atoms in the carbon microsphere powder is 0.5-30. Therefore, the capacity and input / output can be increased while maintaining excellent rapid charge / discharge characteristics, excellent charge / discharge cycle characteristics and high initial efficiency.

  In the method for producing carbon microsphere powder of the present invention, the linear velocity of the raw material-containing gas when the raw material-containing gas is introduced into the externally heated reactor and passed through the externally heated reactor is 0. It is 02 to 4.0 m / sec, preferably 0.04 to 2.0 m / sec. When the linear velocity of the raw material-containing gas is less than the above range, thermal decomposition products on the reaction tube wall are remarkably attached, and the passage is likely to be clogged, resulting in difficulty in production. On the other hand, when the linear velocity of the raw material-containing gas exceeds the above range, the uniformity of the flow of the raw material-containing gas becomes low, the particle size distribution becomes wide, and sufficient residence time of the raw material-containing gas cannot be obtained, The thermal decomposition reaction or carbonization reaction does not proceed sufficiently.

  In the method for producing carbon microsphere powder of the present invention, the temperature in the externally heated reactor is 1000 to 1400 ° C, preferably 1050 to 1350 ° C. When the temperature in the external heating reactor is less than the above range, the raw material is not carbonized and goes out of the furnace, and carbon microspheres cannot be obtained. On the other hand, if the temperature in the externally heated reactor exceeds the above range, the carbonization reaction becomes faster, so it tends to become fine particles, making it difficult to obtain a sharp particle distribution, and the thermal decomposition reaction is promoted too much, so that Since there are too many opportunities for the produced particles to collide with each other, the aggregation of the particles proceeds and the particle size distribution becomes broad. Moreover, 1000-1200 degreeC is preferable at the point which becomes easy to suppress the production | generation of SiC which does not adsorb / desorb lithium ion as the temperature in this external heating type reactor.

  In the method for producing the carbon microsphere powder of the present invention, the raw material-containing gas can be introduced also from the subsequent raw material-containing gas introduction site while the raw material-containing gas is introduced from the preceding raw material-containing gas introduction site. In addition, the site | part shown with the code | symbol 31 in FIG. 1 is this back | latter stage raw material containing gas introduction part. That is, the raw material-containing gas is introduced from the upstream raw material-containing gas introduction site, passed through the external heating reactor, and discharged from the external heating reactor. The raw material-containing gas is further introduced in the middle of the flow. And, in the method for producing the carbon microsphere powder of the present invention, while introducing the raw material-containing gas from the preceding raw material-containing gas introduction site, by introducing the raw material-containing gas also from the subsequent raw material-containing gas introduction site, It becomes easy to obtain carbon microsphere powders exceeding 450 nm. The raw material in the raw material-containing gas introduced from the former raw material-containing gas introduction part is likely to become carbon microsphere powder having an arithmetic average primary particle diameter of 150 to 450 nm due to thermal decomposition and carbonization, and the external heat In the latter part of the reaction furnace, the concentration of the raw material becomes dilute with the generation of carbon microspheres, so that it is difficult for the grains to grow. Therefore, grain growth can be achieved by introducing the raw material-containing gas into the subsequent stage where the concentration of the raw material is dilute. In the present invention, the latter-stage raw material-containing gas introduction site is introduced from the previous-stage raw material-containing gas introduction site, passes through the external heating reactor, and is discharged from the external heating reactor. The raw material containing gas is in the middle of the flow and may be behind the preceding raw material containing gas introduction site, and the position of the latter raw material containing gas introduction site is the linear velocity of the raw material containing gas, the raw material containing It is appropriately selected depending on conditions such as the concentration of each raw material in the gas and the temperature in the external heating reactor. For example, the position of the latter-stage raw material-containing gas introduction site may be in the latter half of the heating zone of the external heating reactor. Further, since the raw material is at a temperature sufficient for thermal decomposition and carbonization in the latter part of the heating zone in the external heating reactor, the position of the latter raw material-containing gas introduction site is The latter part may be sufficient as compared with the heating zone in the thermal reactor.

  The raw material containing gas introduced from the subsequent raw material containing gas introduction site is the raw material containing gas (1), the raw material containing gas (2), the raw material containing gas (3), the raw material containing gas (4) or the raw material. The gas containing gas (5), which may be the same as the raw material containing gas introduced from the preceding raw material containing gas introduction site, or a combination of the raw material containing gas and the raw material introduced from the preceding raw material containing gas introduction site Or the density | concentration of a raw material may differ.

  The introduction amount of the raw material containing gas introduced from the subsequent raw material containing gas introduction site is 50 to 100% by volume of the introduction amount of the raw material containing gas introduced from the previous raw material containing gas introduction site. It is appropriately selected depending on the particle size.

  In the method for producing carbon microsphere powder of the present invention, the raw material-containing gas is pyrolyzed and carbonized by passing the raw material-containing gas through the external heating reactor, and the heat It becomes a decomposition product.

  In the carbon microsphere powder manufacturing method of the present invention, the generated pyrolyzate is then discharged out of the externally heated reactor together with the inert gas and cracked gas and transferred to the cooling region. And cool. The method for cooling the pyrolyzate, the inert gas and the cracked gas transferred to the outside heat reactor is not particularly limited.

  In the method for producing carbon microsphere powder of the present invention, the pyrolyzate is then collected to obtain carbon microsphere powder for a lithium ion secondary battery negative electrode material. The method for collecting the pyrolyzate is not particularly limited.

  Thus, by performing the method for producing the carbon microsphere powder of the present invention, the carbon microsphere powder for the lithium ion secondary battery negative electrode material, that is, the carbon microsphere for the lithium ion secondary battery negative electrode material of the present invention. A powder can be obtained.

  The carbon microsphere powder for a negative electrode material of a lithium ion secondary battery of the present invention (hereinafter also referred to as the carbon microsphere powder of the present invention) has a silicon content of 1 to 30% by weight in terms of silicon atoms, an electron microscope The arithmetic average primary particle diameter dn measured by the above is 150 to 1000 nm, the volatile content Vm is 5.0% or less, and the ratio of the half-value width ΔDst to the Stokes mode diameter Dst measured by the disk centrifuging device (DCF) Carbon for a lithium ion secondary battery negative electrode material, which is a carbon microsphere having a mode diameter Dst) of 0.40 to 1.10 and a crystallite lattice spacing d (002) of 0.370 nm or less measured by X-ray diffraction method. It is a microsphere powder.

  The silicon content in the carbon microsphere powder of the present invention is 1 to 30% by weight, preferably 2 to 28% by weight, particularly preferably 3 to 27% by weight in terms of silicon atoms. When the content of silicon in the carbon microsphere powder is less than the above range, the battery capacity is lowered, while when it exceeds the above range, the cycle characteristics are deteriorated.

  The arithmetic average primary particle diameter dn measured by the electron microscope of the carbon microsphere powder of the present invention is 150 to 1000 nm, preferably 200 to 900 nm. When the arithmetic average primary particle diameter of the carbon microsphere powder measured by an electron microscope is less than the above range, the specific surface area is too large, so that it becomes active against the electrolyte, resulting in low initial efficiency of the battery. As the charging / discharging cycle is repeated, the carbon hexagonal network surface is further destroyed, and the cycle characteristics are deteriorated. That is, the battery capacity retention rate when repeatedly charging / discharging is lowered. On the other hand, when the arithmetic average primary particle diameter measured by an electron microscope of the carbon microsphere powder exceeds the above range, the particle diameter is too large, so that the lithium ion diffusion path becomes longer, and the lithium ion doping and undoping speeds are increased. Slow, that is, rapid charge / discharge characteristics cannot be obtained. The arithmetic average primary particle diameter dn is obtained by the following operation. First, a sample of carbon microspheres is dispersed in chloroform using an ultrasonic disperser at a frequency of 28 kHz for 30 seconds, and then the dispersed sample is fixed to a carbon support film (for example, “Powder Physical Properties” powder) (It is described in the body engineering study group edition, P68 (C), "water surface membrane method"). This was taken directly with an electron microscope at a magnification of 10,000 times and a total magnification of 100,000 times. From the obtained photo, 1000 particle diameters were randomly measured, and the histogram was created by dividing each 14 nm, and the arithmetic average primary Obtain the particle size.

  The volatile matter Vm of the carbon microsphere powder of the present invention is 5.0% or less, preferably 4.5% or less. Since the tar-like substances and surface functional groups present on the surface of the carbon microspheres fill the active sites on the surface, it is necessary that the tar-like substances and the surface functional groups be as few as possible. In particular, the tar-like substance that is an undecomposed product of the raw material needs to be eliminated as much as possible. In other words, if there are too many tar-like substances or surface functional groups, active sites such as lattice defects on the surface of the carbon microspheres are filled, and lithium ion doping and undoping are prevented, so the lithium ion adsorption / desorption rate Becomes lower. Therefore, the volatile matter Vm of the carbon microsphere powder is defined as the above range. In the present invention, the volatile matter Vm of the carbon microsphere powder is measured by JIS K6221-1986 “Testing method of carbon black for rubber”.

  The ratio of the half-value width ΔDst of the Stokes mode diameter Dst to the Stokes mode diameter Dst measured by the disc centrifuging device (DCF) of the carbon microsphere powder of the present invention (half-value width ΔDst of the Stokes mode diameter Dst / Stokes mode diameter Dst) is: 0.40 to 1.10, preferably 0.45 to 1.05. If the size distribution of the primary particle aggregates is too wide, local current concentration occurs when a current flows in the negative electrode. Therefore, it is necessary that the size distribution of the primary particle aggregates is narrow. On the other hand, if the size distribution of the primary particle aggregates is too narrow, the coating property at the time of electrode formation is lowered. Therefore, the ratio of the half width ΔDst to the Stokes mode diameter Dst is defined as the above range.

  Moreover, the Stokes mode diameter Dst measured by the disc centrifuging device (DCF) of the carbon microsphere powder of the present invention is preferably 150 to 1500 nm.

In the present invention, the Stokes mode diameter Dst and the half-value width ΔDst of the Stokes mode diameter Dst are measured by the following operation. First, dry carbon microspheres are mixed with a 20 volume% ethanol aqueous solution containing a small amount of a surfactant to prepare a dispersion of carbon microspheres of 0.1 kg / m ³ , and this is sufficiently dispersed with ultrasound. To obtain a carbon microsphere dispersion. Then, set the disk centrifuge apparatus (manufactured by UK JoyesLobel Co.) to the rotational speed of 100s ^-1, spin solution (2 wt% glycerine aqueous solution, 25 ° C.) after the addition 0.015Dm ³ a, buffer solution of 0.001Dm ³ (20 volume% ethanol aqueous solution, 25 ° C.) is injected. Next, after adding 0.0005 dm ³ of carbon microsphere dispersion at a temperature of 25 ° C. with a syringe, centrifugal sedimentation was started, and at the same time, the recorder was operated to show the distribution curve shown in FIG. 2 (horizontal axis: carbon dispersion sample Elapsed time after addition, vertical axis: absorbance at a specific point changed with centrifugal sedimentation of carbon microsphere dispersion. From this distribution curve, each absorbance at each time T is read, and the following equation (Equation 1):

(In Equation 1, η is the viscosity of the spin liquid (0.935 × 10 ⁻³ Pa · s), N is the disk rotation speed (100 s ⁻¹ ), r ₁ is the radius of the dispersion injection point (0.0456 m), r ₂ is the radius to the absorbance measuring point (0.0482m), ρ _CB is the density of the carbon microspheres ^{(kg / m 3), ρ} 1 is the density of the spin fluid (1.00178kg / ^{m 3).)}
From this, the Stokes equivalent diameter Dst (nm) is obtained. Next, the obtained Stokes equivalent diameter Dst and absorbance distribution curve (horizontal axis: Stokes equivalent diameter Dst, vertical axis: absorbance) are prepared (FIG. 3), and the maximum frequency of the Stokes equivalent diameter in the distribution curve is represented by the Stokes mode. The diameter is Dst (nm).

  The difference between two large and small Stokes equivalent diameters at which a frequency of 50% is obtained with respect to the Stokes equivalent diameter and the absorbance distribution curve (FIG. 3) obtained in this manner is half the Stokes mode diameter Dst. The value width is ΔDst (nm).

  The crystallite lattice spacing d (002) measured by the X-ray diffraction method of the carbon microsphere powder of the present invention is 0.370 nm or less, preferably 0.340 to 0.368 nm. When the crystallite lattice spacing d (002) exceeds 0.370 nm, the degree of amorphousness is high, so the sites where lithium ions are doped become extremely low, and lithium ions are intercalated between the carbon hexagonal network layers. Since a sufficient amount cannot be inserted, the battery capacity is lowered. Although the measurement is based on the X-ray diffraction method, the Gakushin method is performed under the condition that the target is a Cu (Kα ray) graphite monochromator, the slit is a diverging slit = 1 degree, the light receiving slit is 0.1 mm, and the scattering slit is 1 degree. To obtain a crystallite lattice spacing d (002).

  The carbon microsphere powder of the present invention has a substantially single spherical form with very little aggregation between spheres and a sharp particle size distribution. In addition, the carbon microsphere powder of the present invention is excellent in rapid charge / discharge characteristics, and is therefore suitably used as a negative electrode material for power sources of power sources such as hybrid cars and electric vehicles that require high output in a short time such as starting on a slope. Is done. In addition, the carbon microsphere powder of the present invention is a non-graphitizable carbon material having a low degree of graphitization and a not-developed hexagonal network structure of graphite crystals, and therefore has excellent cycle characteristics and a long life.

  By using the carbon microsphere powder of the present invention as a negative electrode material for a lithium ion secondary battery, it has excellent rapid charge / discharge characteristics, excellent charge / discharge cycle characteristics, high initial efficiency, high capacity and high capacity. A lithium ion secondary battery which is an input / output can be provided.

  EXAMPLES Next, although an Example is given and this invention is demonstrated more concretely, this is only an illustration and does not restrict | limit this invention.

(Examples 1-6, Comparative Examples 1-3)
(Manufacture of carbon microspheres)
Introducing and passing the raw material-containing gas of the raw material and concentration shown in Table 1 into an externally heated reactor having an inner diameter of 145 mm and a length of 1500 mm at the linear velocity of the raw material-containing gas shown in Table 1 and the temperature in the external heat reactor. The pyrolyzate discharged from the external heating reactor was cooled and collected to obtain carbon microsphere powder. About the obtained carbon microsphere powder, the atomic equivalent content of silicon element, the arithmetic average primary particle diameter dn measured by an electron microscope, the volatile matter Vm, the Stokes mode diameter Dst measured by a disk centrifuging device (DCF) and its half Table 1 shows the measurement results of the value width ΔDst, the half-value width ΔDst / Stokes mode diameter Dst, and the crystallite lattice spacing d (002) measured by the X-ray diffraction method.
-Content in terms of atoms of silicon element After 5 g of carbon microspheres were held in argon gas at 2600 ° C for 1 hour, the amount was calculated from the weight loss.

(Performance evaluation)
<Tripolar test cell>
Polyvinylidene fluoride (PVDF) dissolved in N-methyl-2-pyrrolidone is added to carbon microsphere powder in a solid content of 10% by weight and kneaded to prepare a carbon paste. The carbon paste is rolled copper having a thickness of 18 μm. After apply | coating to foil and drying, it pressed with the roll press. A three-electrode test cell having a negative electrode obtained by cutting out a sheet having a diameter of about 16 mm from this sheet and using metallic lithium as a positive electrode and a reference electrode was measured, and initial efficiency, reversible capacity, and rate characteristics were measured. The results are shown in Table 1.

-Initial efficiency Charge to a lithium reference electrode at a constant current up to 0.002V (doped with lithium ions), then discharge at a constant current up to 1.2V (undoped lithium ions), and the initial charge amount and discharge electricity Measure the quantity and use the following formula:
Initial efficiency (%) = (initial discharge electricity amount / initial charge electricity amount) × 100
From this, the initial efficiency was determined.

-Reversible capacity Furthermore, discharge was repeated under the same conditions, and the amount of electricity that could be discharged at the 10th cycle was determined as a reversible capacity (mAh / g).

-Rate characteristics Rate characteristics were evaluated with the minimum charge / discharge cycle time (minutes) capable of maintaining the charge / discharge capacity as a secondary battery (with a discharge capacity of 100 mAh / g as a lower limit). The rate characteristic is higher in input / output as the charge / discharge cycle is shorter.

<Cycle characteristics>
・ Production of negative electrode 10% by weight of polyvinylidene fluoride (PVDF) dissolved in N-methyl-2-pyrrolidone was added to carbon microsphere powder in a solid content and kneaded to prepare a carbon paste. It apply | coated to 18 micrometers roll copper foil, and after drying, it pressed with the roll press. This sheet was cut into a circle having a diameter of about 16 mm to form a negative electrode.
-Production of positive electrode Lithium cobalt oxide LiCoO ₂ was used for the positive electrode, 5% by weight of polyvinylidene fluoride powder and 5% by weight of conductive agent Ketjen Black EC were added to the lithium cobalt oxide LiCoO ₂ powder, and N-methylpyrrolidone was used. A slurry was prepared by mixing and applied to an aluminum foil and dried to prepare an electrode sheet. A positive electrode was produced by cutting the sheet into a circle having a diameter of about 16 mm.
-Production of battery Using the above-described negative electrode and positive electrode, a solution obtained by dissolving LiPF ₆ at a concentration of 1 mol / liter in a mixed solvent of ethylene carbonate and dimethyl carbonate (volume ratio 1: 1 mixture) as an electrolytic solution was used. A simple coin-shaped battery was produced using a polypropylene nonwoven fabric for the separator.
・ Measurement of cycle characteristics A charge / discharge test was conducted at a constant current of 0.5 mA / cm ² in a potential range where the terminal voltage was 3.0 V and the charge upper limit voltage was 4.2 V at a constant temperature of 25 ° C. It was. The cycle characteristic is the ratio of the discharge capacity per unit weight of the 500th carbon negative electrode material to the discharge capacity per unit weight of the first carbon negative electrode material:
Cycle characteristics (%) = initial discharge capacity (mAh / g) / 500th cycle discharge capacity (mAh / g) × 100
As sought. The results are shown in Table 1.

Organosilane compound: tert-butyldimethylsilane, trihexylsilane, methyldichlorosilane Hydrocarbon: Propane Inorganic silane compound: Monosilane Inert gas: Nitrogen

  In the example, the reversible capacity of the lithium ion secondary battery was higher than that of Comparative Example 7 not containing silicon. In addition, the cycle characteristics and rate characteristics of the examples were better than those of Comparative Example 7 containing no silicon. The initial efficiency was good at an equivalent value as compared with Comparative Example 7 containing no silicon.

  Since Comparative Examples 1 and 2 have almost no silicon content, the rate characteristics, initial efficiency, and cycle characteristics are good levels, but the reversible capacity of the lithium ion secondary battery does not contain silicon. Compared to 7, there was no significant difference. In Comparative Examples 3 to 6 having a large silicon content, the cycle characteristics were poor and the rate characteristics were also poor.

It is explanatory drawing which shows the whole structure of the apparatus for enforcing the manufacturing method of the carbon microsphere powder for lithium ion secondary battery negative electrode materials of this invention. It is the distribution curve which showed the elapsed time after adding a carbon microsphere dispersion at the time of Dst measurement, and the light absorbency in the specific point which changed with the centrifugal sedimentation of a carbon microsphere dispersion. It is a distribution curve which shows the relationship between the Stokes equivalent diameter obtained by Dst measurement, and a light absorbency.

Explanation of symbols

8 Raw material containing gas introduction tube 9 Liquid silicon compound tank 10 Gas silicon compound cylinder 11 Gas hydrocarbon cylinder 12 Inert gas cylinder 13 Flow meter 14 Liquid hydrocarbon tank 15 Preheating heater 16 Pressure gauge 17 External heating reactor 18 Heater 19 Subsequent raw material-containing gas introduction pipe 20 Temperature controller 21 Cooling pipe 22 Valve 23 Vacuum pump 24 Collection chamber 25 Neutralization tank 26 Exhaust gas combustion device 30 Pre-stage raw material-containing gas introduction part 31 Rear-stage raw material-containing gas introduction part

Claims (7)

  The content of silicon was 1 to 30% by weight in terms of silicon atom, the arithmetic average primary particle diameter dn measured with an electron microscope was 150 to 1000 nm, the volatile content Vm was 5.0% or less, and measured with a disc centrifuging device (DCF). The ratio of the half width ΔDst to the Stokes mode diameter Dst (half width ΔDst / Stokes mode diameter Dst) is 0.40 to 1.10, and the crystallite lattice spacing d (002) measured by the X-ray diffraction method is 0.370 nm. A carbon microsphere powder for a negative electrode material for a lithium ion secondary battery, which is the following carbon microsphere.   A raw material-containing gas in which an organosilicon compound is diluted with an inert gas and the concentration of the organosilicon compound is 10 to 50% by volume is introduced into an externally heated reactor having a temperature in the reactor of 1000 to 1400 ° C. And passed through the external heating reactor at a linear flow rate of 0.02 to 4.0 m / sec, and then the generated pyrolyzate is transferred from the external heating reactor to a cooling region to be cooled. Then, the carbon microsphere powder for a lithium ion secondary battery negative electrode material is obtained by collecting and obtaining a carbon microsphere powder for a lithium ion secondary battery negative electrode material.   The raw material-containing gas in which the organosilicon compound and hydrocarbon are diluted with an inert gas and the total concentration of the organosilicon compound and the hydrocarbon is 10 to 50% by volume is set to a temperature in the reactor of 1000 to 1400 ° C. The external thermal reactor was introduced at a linear flow rate of 0.02 to 4.0 m / sec, and then the generated thermal decomposition product was removed from the external thermal reactor. The carbon microsphere powder for a lithium ion secondary battery negative electrode material is obtained by transferring to a cooling region, cooling, and then collecting to obtain a carbon microsphere powder for a lithium ion secondary battery negative electrode material. Production method.   A raw material-containing gas in which an inorganic silicon compound and a hydrocarbon are diluted with an inert gas, the concentration of the hydrocarbon is 10 to 50% by volume, and the concentration of the inorganic silicon compound is 1 to 30% by volume is reacted. It was introduced into an externally heated reactor having a temperature in the furnace of 1000 to 1400 ° C., passed through the externally heated reactor at a linear flow rate of 0.02 to 4.0 m / sec, and then the pyrolyzate produced Is transferred to the cooling region from the external heating reactor, cooled, and then collected to obtain a carbon microsphere powder for a negative electrode material of a lithium ion secondary battery. Manufacturing method of carbon microsphere powder for negative electrode material.   A raw material-containing gas in which an organic silicon compound and an inorganic silicon compound are diluted with an inert gas, the concentration of the organic silicon compound is 10 to 50% by volume, and the concentration of the inorganic silicon compound is 1 to 30% by volume The reactor was introduced into an externally heated reactor having a temperature of 1000 to 1400 ° C., passed through the externally heated reactor at a linear flow rate of 0.02 to 4.0 m / sec, and then generated heat. The decomposition product is transferred from the external heating reactor to a cooling region, cooled, and then collected to obtain a carbon microsphere powder for a negative electrode material of a lithium ion secondary battery. Manufacturing method of carbon microsphere powder for secondary battery negative electrode material.   The organosilicon compound, the inorganic silicon compound and the hydrocarbon are diluted with an inert gas, the total concentration of the organosilicon compound and the hydrocarbon is 10 to 50% by volume, and the concentration of the inorganic silicon compound is 1 to 30 A raw material-containing gas having a volume% is introduced into an externally heated reactor whose temperature in the reactor is 1000 to 1400 ° C., and the externally heated reactor is placed at a linear flow rate of 0.02 to 4.0 m / sec. Then, the generated pyrolyzate is transferred from the external heating reactor to a cooling region to be cooled, and then collected to obtain a carbon microsphere powder for a negative electrode material for a lithium ion secondary battery. A method for producing carbon microsphere powder for a negative electrode material for a lithium ion secondary battery. The following raw material-containing gases (1) to (5) are also introduced from the latter-stage raw material-containing gas introduction portion of the external heating reactor.
(1) a raw material-containing gas in which an organosilicon compound is diluted with an inert gas;
(2) a raw material-containing gas in which an organosilicon compound and a hydrocarbon are diluted with an inert gas;
(3) a raw material-containing gas in which an inorganic silicon compound and a hydrocarbon are diluted with an inert gas;
(4) Raw material-containing gas in which an organosilicon compound and an inorganic silicon compound are diluted with an inert gas,
(5) a raw material-containing gas obtained by diluting an organosilicon compound, an inorganic silicon compound, and a hydrocarbon with an inert gas;
Either of these is introduce | transduced, The manufacturing method of the carbon microsphere powder for lithium ion secondary battery negative electrode materials of any one of Claims 2-6 characterized by the above-mentioned.