WO2024095539A1 - 酸化ケイ素およびその製造方法 - Google Patents

酸化ケイ素およびその製造方法 Download PDF

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Publication number
WO2024095539A1
WO2024095539A1 PCT/JP2023/026221 JP2023026221W WO2024095539A1 WO 2024095539 A1 WO2024095539 A1 WO 2024095539A1 JP 2023026221 W JP2023026221 W JP 2023026221W WO 2024095539 A1 WO2024095539 A1 WO 2024095539A1
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silicon oxide
oxide powder
containing silicon
lithium
ppm
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French (fr)
Japanese (ja)
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浩樹 竹下
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Osaka Titanium Technologies Co Ltd
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Osaka Titanium Technologies Co Ltd
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Priority to EP23885312.1A priority Critical patent/EP4613707A4/en
Priority to JP2024554260A priority patent/JPWO2024095539A1/ja
Priority to CN202380074707.4A priority patent/CN120112484A/zh
Priority to KR1020257010874A priority patent/KR20250065851A/ko
Publication of WO2024095539A1 publication Critical patent/WO2024095539A1/ja
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    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B33/00—Silicon; Compounds thereof
    • C01B33/113—Silicon oxides; Hydrates thereof
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B33/00—Silicon; Compounds thereof
    • C01B33/113—Silicon oxides; Hydrates thereof
    • C01B33/12—Silica; Hydrates thereof, e.g. lepidoic silicic acid
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B33/00—Silicon; Compounds thereof
    • C01B33/113—Silicon oxides; Hydrates thereof
    • C01B33/12—Silica; Hydrates thereof, e.g. lepidoic silicic acid
    • C01B33/18—Preparation of finely divided silica neither in sol nor in gel form; After-treatment thereof
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/05—Accumulators with non-aqueous electrolyte
    • H01M10/052—Li-accumulators
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/362—Composites
    • H01M4/366—Composites as layered products
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
    • H01M4/483—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides for non-aqueous cells
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
    • H01M4/485—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of mixed oxides or hydroxides for inserting or intercalating light metals, e.g. LiTi2O4 or LiTi2OxFy
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
    • H01M4/624—Electric conductive fillers
    • H01M4/625—Carbon or graphite
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2002/00—Crystal-structural characteristics
    • C01P2002/70—Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2006/00—Physical properties of inorganic compounds
    • C01P2006/12—Surface area
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M2004/026—Electrodes composed of, or comprising, active material characterised by the polarity
    • H01M2004/027—Negative electrodes
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/10—Energy storage using batteries

Definitions

  • the present invention relates to silicon oxide (including metal element-containing silicon oxide).
  • the present invention also relates to a method for producing silicon oxide.
  • silicon monoxide SiO
  • silicon monoxide has been expected to be a high-capacity negative electrode active material.
  • silicon monoxide has the disadvantage of having a large irreversible capacity.
  • the gas-phase lithium pre-doping method is proposed in JP 2021-52014 A.
  • the gas-phase lithium pre-doping method disclosed in this publication is a method for obtaining lithium-containing silicon oxide (lithium-doped silicon oxide) by doping SiO with lithium in the gas phase.
  • elements such as aluminum, which have a low vapor pressure and are contained in the raw materials, vaporize together with the silicon monoxide, which causes the problem that a certain amount of impurities remain in the target silicon oxide.
  • Elemental impurities such as aluminum diffuse within the active material particles during the charge and discharge process of the battery and precipitate at the grain boundaries, promoting pulverization, which may ultimately deteriorate the cycle characteristics of the battery.
  • the objective of the present invention is to provide a method for reducing elemental impurities such as aluminum in silicon oxide.
  • the method for producing silicon oxide (including metal element-containing silicon oxide) comprises a water treatment step, a reduced pressure heating step, and a sublimation step.
  • silicon is brought into contact with water and then dried to obtain water-treated silicon.
  • the reduced pressure heating step (a) the water-treated silicon is heated under reduced pressure together with at least one compound selected from the group consisting of (b1) silicon dioxide, (b2) metal silicate, and (b3) metal oxide to generate gas.
  • the gas is sublimated to obtain a solid.
  • this silicon oxide manufacturing method includes a water treatment process. This makes it possible to change the aluminum and iron elements contained in the silicon powder into a form that is less likely to vaporize in the reduced pressure heating process. Therefore, this silicon oxide manufacturing method makes it possible to reduce the aluminum and iron element concentrations in the silicon oxide (solid material).
  • the method for producing silicon oxide according to the second aspect of the present invention comprises a granulation step, a reduced pressure heating step, and a sublimation step.
  • a mixture containing (A) silicon and (B) at least one compound selected from the group consisting of (b1) silicon dioxide, (b2) metal silicate, and (b3) metal oxide is granulated using water to obtain a granulated material.
  • the reduced pressure heating step the granulated material is heated under reduced pressure to generate gas from the granulated material.
  • the gas is sublimated to obtain a solid material.
  • this silicon oxide manufacturing method includes a granulation process.
  • the aluminum and iron elements contained in the granulated silicon can be changed by the water used for granulation into a form that is less likely to vaporize in the reduced pressure heating process. Therefore, this silicon oxide manufacturing method can reduce the aluminum and iron element concentrations in the silicon oxide (solid material).
  • granulation improves flowability and reduces spoutability, making it easier to handle during the process.
  • the method for producing silicon oxide according to the third aspect of the present invention includes a charging step, a reduced pressure heating step, and a sublimation step.
  • the charging step (A) silicon and (B) a mixture containing (A) silicon and at least one compound selected from the group consisting of (b1) silicon dioxide, (b2) metal silicate, and (b3) metal oxide are charged into a heat-resistant container so that the aluminum element concentration in the mixture is less than 50 ppm by mass, the iron element concentration is less than 1000 ppm by mass, and the copper element concentration is less than 200 ppm by mass.
  • the reduced pressure heating step the mixture is heated under reduced pressure to generate gas from the mixture.
  • the sublimation step the gas is sublimated to obtain a solid.
  • this silicon oxide manufacturing method includes an introduction step.
  • silicon and the mixture are introduced into a heat-resistant container so that the aluminum element concentration in the mixture is less than 50 ppm by mass, the iron element concentration is less than 1000 ppm by mass, and the copper element concentration is less than 200 ppm by mass. Therefore, this silicon oxide manufacturing method can sufficiently reduce the aluminum element concentration, iron element concentration, and copper element concentration in the lithium-containing silicon oxide (solid material).
  • the method for producing silicon oxide according to the fourth aspect of the present invention includes a charging step, a reduced pressure heating step, and a sublimation step.
  • the charging step (A) silicon and (B) one or more compounds selected from (b1) silicon dioxide, (b2) metal silicate, and (b3) metal oxide are charged into a heat-resistant container so that the elemental ratio O/Si during the reaction is in the range of more than 1 and less than 1.5. From the viewpoint of maintaining a good reaction rate, the elemental ratio O/Si during the reaction is preferably less than 1.3, and more preferably less than 1.1.
  • the reduced pressure heating step the compound charged into the heat-resistant container is heated under reduced pressure to generate gas from the compound.
  • the gas is sublimated to obtain a solid.
  • the elemental ratio O/Si during the reaction refers to the value obtained by dividing the amount of O element contained in the raw material charged into the heat-resistant container by the amount of Si element contained in the raw material charged into the heat-resistant container.
  • the method for producing silicon oxide includes a charging step.
  • (A) silicon and (B) one or more compounds selected from (b1) silicon dioxide, (b2) metal silicate, and (b3) metal oxide are charged into a heat-resistant container so that the elemental ratio O/Si during the reaction is in the range of more than 1 and less than 1.5.
  • the aluminum element in the raw material reacts with the excess silicon oxide or metal silicate in the heat-resistant container and remains in the crucible, which leads to the inhibition of vaporization of the aluminum element and the iron element, and the concentrations of the aluminum element and the iron element in the silicon oxide obtained as the target product can be sufficiently reduced.
  • a step that does not affect the elemental ratio may be carried out along the way.
  • Specific methods for setting the element ratio during the reaction to a desired value include mixing the raw materials in advance so that the element ratio O/Si is in the range of more than 1 and less than 1.5, and then charging the raw materials into the heat-resistant container; setting the amount of each raw material charged per hour so that the element ratio O/Si is always in the range of more than 1 and less than 1.5, and then charging the raw materials into the heat-resistant container from separate routes.
  • a method for producing silicon oxide according to a fifth aspect of the present invention is a method for producing silicon oxide according to any one of the first to fourth aspects, wherein, when the heating temperature in the reduced pressure heating step is TR , the melting point of (A) silicon is TA , the lowest melting point among the melting points of (b1) silicon dioxide, (b2) metal silicate, and (b3) metal oxide is TBH , if TA ⁇ TBL holds, TR is set so as to satisfy TA ⁇ TR ⁇ TBL , if TBL ⁇ TA ⁇ TBH holds, TR is set so as to satisfy TBL ⁇ TR ⁇ TA , and if TBH ⁇ TA holds, TR is set so as to satisfy TBH ⁇ TR ⁇ TA .
  • the heating temperature in the reduced pressure heating step is set as described above. Therefore, the heating temperature in the reduced pressure heating step can be set to a temperature suitable for generating gas.
  • a silicon oxide according to a sixth aspect of the present invention has a composition represented by MxSiOy (wherein, in the composition formula, M is at least one metal element selected from Li, Na, K, Mg, and Ca, y is in the range of more than 0.5 and less than 1.5, x/y is in the range of 0 or more and less than 1, and x is more than 0).
  • MxSiOy wherein, in the composition formula, M is at least one metal element selected from Li, Na, K, Mg, and Ca, y is in the range of more than 0.5 and less than 1.5, x/y is in the range of 0 or more and less than 1, and x is more than 0).
  • the aluminum element concentration as impurities is 150 ppm or less by mass
  • the iron element concentration is less than 100 ppm
  • the copper element concentration is less than 100 ppm.
  • the aluminum element concentration as an impurity is 150 ppm or less by mass, the iron element concentration is less than 100 ppm, and the copper element concentration is less than 100 ppm. Therefore, when this silicon oxide is used as a negative electrode active material, it is expected to suppress pulverization during the charge and discharge process, and ultimately suppress deterioration of the battery's cycle characteristics.
  • the median diameter of the above-mentioned silicon oxide measured by a laser diffraction particle size distribution analyzer, is in the range of 0.5 ⁇ m to 30 ⁇ m.
  • this silicon oxide is used as the negative electrode active material, not only can it suppress the decrease in the Coulomb rate, but it can also suppress pulverization and suppress the decrease in the cycle characteristics of the negative electrode.
  • the mass ratio of carbon in the conductive carbon coating to the mass of the silicon oxide is preferably within the range of 0.5 mass% to 20 mass%. This is because, when this silicon oxide is used as a negative electrode active material, it is possible to impart good conductivity to the silicon oxide while maintaining good charge/discharge capacity, and it is also possible to suppress side reactions of the silicon oxide.
  • the silicon oxide preferably has a BET specific surface area in the range of 1 m2 /g to 6 m2 /g, because when this silicon oxide is used as a negative electrode active material, it is possible to suppress a decrease in Coulombic efficiency while maintaining good output characteristics.
  • FIG. 1 is a schematic diagram of a silicon oxide powder manufacturing apparatus according to an embodiment of the present invention.
  • Vapor deposition apparatus 110 Crucible 120 Heater 130 Vapor deposition drum 141 Scraper 143 Particle guide 150 Chamber 151 Chamber body 152 Recovery section 153 Exhaust pipe 160 Raw material supply hopper 170 Raw material introduction pipe 180 Recovery container 190 Recovery pipe Gg Gas guide OP Opening RM Deposition chamber Sr Molten metal VL1 First valve VL2 Second valve
  • the silicon oxide according to the embodiment of the present invention is represented by M x SiO y .
  • M is at least one metal element selected from Li, Na, K, Mg, and Ca.
  • y is in the range of more than 0.5 and less than 1.5, and x/y is in the range of 0 or more and less than 1.
  • x is 0 or more.
  • the composition formula is M x SiO y .
  • the composition formula is SiO y . That is, silicon oxide may be represented by M x SiO y or may be represented by SiO y .
  • y is in the range of more than 0.5 and less than 1.5, and x/y is in the range of more than 0 and less than 1.
  • y is preferably in the range of more than 0.7 and less than 1.3, more preferably in the range of more than 0.9 and less than 1.1, even more preferably in the range of more than 0.95 and less than 1.05, and particularly preferably in the range of more than 1.00 and less than 1.05.
  • x/y is preferably in the range of more than 0.20 and less than 0.5, more preferably in the range of more than 0.30 and less than 0.4, and when M is Mg, it is preferably in the range of more than 0.8 and less than 1, more preferably in the range of more than 0.9 and less than 1.
  • y is in the range of more than 0.5 and less than 1.5, and x/y is 0.
  • the composition represented by M x SiO y may be referred to as metal element-containing silicon oxide, and the composition represented by SiO y may be referred to as metal element-free silicon oxide.
  • silicon oxide mainly formed from metal element-containing silicon oxide may be referred to as metal element-containing silicon oxide
  • silicon oxide mainly formed from metal element-free silicon oxide may be referred to as metal element-free silicon oxide.
  • the aluminum element is contained as an impurity at a mass concentration of 150 ppm or less
  • the iron element is contained at a mass concentration of less than 100 ppm
  • the copper element is contained at a mass concentration of less than 100 ppm.
  • the shape of the silicon oxide according to the embodiment of the present invention is not limited, and may be a powder, a lump, or another shape.
  • the silicon oxide described above preferably has a median diameter measured by a laser diffraction particle size distribution analyzer in the range of 0.5 ⁇ m to 30 ⁇ m, more preferably in the range of 1.0 ⁇ m to 20 ⁇ m, and even more preferably in the range of 1.5 ⁇ m to 10 ⁇ m. This is because when this silicon oxide is used as the negative electrode active material, not only can it suppress the decrease in the coulomb rate, but it can also suppress pulverization and suppress the decrease in the cycle characteristics of the negative electrode.
  • the mass ratio of carbon in the conductive carbon coating to the mass of the silicon oxide is preferably in the range of 0.5 mass% to 20 mass%, more preferably in the range of 0.5 mass% to 10 mass%, and even more preferably in the range of 0.5 mass% to 5 mass%. This is because, when this silicon oxide is used as a negative electrode active material, it is possible to impart good conductivity to the silicon oxide while maintaining good charge/discharge capacity, and it is also possible to suppress side reactions of the silicon oxide.
  • the silicon oxide preferably has a BET specific surface area in the range of 1 m2/g to 6 m2/g, more preferably in the range of 1.5 m2 /g to 5 m2/g, even more preferably in the range of 1.5 m2 /g to 4 m2/g, and particularly preferably in the range of 1.5 m2 /g to 3 m2/g, because when this silicon oxide is used as the negative electrode active material, it is possible to suppress a decrease in Coulombic efficiency while maintaining good output characteristics.
  • silicon oxide i.e., silicon oxide containing metal elements or silicon oxide not containing metal elements
  • the raw material used in producing metal element-free silicon oxide is a mixture of silicon and silicon dioxide.
  • the silicon and silicon dioxide may be in powder form, lump form, or other form.
  • the raw material used in producing metal element-containing silicon oxide is a mixture of silicon and at least one compound selected from the group consisting of silicon dioxide, metal silicate, and metal oxide.
  • the silicon, silicon dioxide, metal silicate, and metal oxide may be in powder form, lump form, or other form.
  • metal silicate examples include lithium silicate (e.g., lithium disilicate Li 2 Si 2 O 5 , etc.), sodium silicate (e.g., sodium disilicate Na 2 Si 2 O 5 , etc.), potassium silicate (e.g., potassium disilicate K 2 Si 2 O 5 , etc.), magnesium silicate (magnesium silicate MgSiO 3 , etc.), and calcium silicate (calcium silicate CaSiO 3 , etc.).
  • the metal silicate may be a mixture of a metal oxide and silicon oxide.
  • lithium disilicate Li 2 Si 2 O 5 may be a mixture of Li 2 O and 2SiO 2
  • sodium disilicate Na 2 Si 2 O 5 may be a mixture of Na 2 O and 2SiO 2
  • potassium disilicate K 2 Si 2 O 5 may be a mixture of K 2 O and 2SiO 2
  • magnesium silicate MgSiO 3 may be a mixture of MgO and SiO 2
  • calcium silicate CaSiO 3 may be a mixture of CaO and SiO 2.
  • metal oxides include lithium oxide (Li 2 O, etc.), sodium oxide (Na 2 O, etc.), potassium oxide (K 2 O), magnesium oxide (MgO, etc.), and calcium oxide (CaO, etc.).
  • the metal element-containing silicon oxide or metal element-free silicon oxide according to the embodiment of the present invention can be manufactured according to the manufacturing method described below.
  • any of the pretreatments or prepreparations described in (1) to (4) below is carried out.
  • the silicon is treated with water, and the aluminum and iron elements contained in the silicon are converted into a form that is less likely to vaporize during the reduced pressure heating process.
  • the mixing ratio of the various compounds is determined so that the aluminum element concentration is less than 50 ppm by mass, the iron element concentration is less than 1000 ppm by mass, and the copper element concentration is less than 200 ppm by mass.
  • the mixing ratio of (A) silicon to (B) at least one compound selected from the group consisting of (b1) silicon dioxide, (b2) metal silicate, and (b3) metal oxide is determined so that the element ratio during the reaction is O/Si in the range of more than 1 and less than 1.5.
  • the above-mentioned manufacturing method is preferably carried out using a deposition apparatus 100 as shown in FIG. 1. Therefore, first, this deposition apparatus 100 will be described, and then the above-mentioned manufacturing method will be described.
  • the deposition apparatus 100 is mainly composed of a crucible 110, a heater 120, a deposition drum 130, a scraper 141, a granular guide 143, a chamber 150, a raw material supply hopper 160, a raw material introduction pipe 170, a recovery container 180, a first valve VL1, and a second valve VL2.
  • the crucible 110 is a heat-resistant container with an opening in the center of the top wall as shown in FIG. 1, and is installed in the chamber 150.
  • a through hole (not shown) is formed in one location on the periphery of the top wall of the crucible 110, and a raw material introduction pipe 170 is inserted into this through hole.
  • the raw material in the raw material supply hopper 160 is supplied to the crucible 110 through the raw material introduction pipe 170.
  • a gas guide Gg is disposed on the upper side of the top wall of the crucible 110. This gas guide Gg is a member that guides the raw material gas generated in the crucible 110 to the evaporation drum 130, and is installed on the upper surface of the top wall so as to surround the center of the top wall as shown in FIG. 1.
  • the heater 120 is used to heat the crucible 110 to high temperatures and is positioned to surround the outer periphery of the crucible 110.
  • the deposition drum 130 is, for example, a cylindrical horizontal drum, and is disposed above the opening OP in the top wall of the crucible 110 as shown in FIG. 1, with its lower portion surrounded by a gas guide Gg.
  • the deposition drum 130 is rotated in one direction by a driving mechanism (not shown).
  • the deposition drum 130 is provided with a temperature regulator (not shown) for keeping the outer peripheral surface at a constant temperature.
  • the temperature regulator cools the outer peripheral surface temperature of the deposition drum 130 to a temperature suitable for the deposition of the deposition source gas by a cooling medium supplied from the outside.
  • the outer peripheral surface temperature of the deposition drum 130 can also affect the crystallinity of the precipitate deposited on the precipitate remaining on the deposition drum.
  • the temperature is preferably 900°C or less, more preferably in the range of 150°C to 800°C, and particularly preferably in the range of 150°C to 700°C.
  • the scraper 141 is a member that scrapes off the thin film formed on the deposition drum 130 from the deposition drum 130, and is disposed near the deposition drum 130 as shown in FIG. 1.
  • the flakes (active material particles) scraped off by the scraper 141 fall into the particle guide 143.
  • the material of the scraper 141 also affects the impurity contamination of the active material particles. From the viewpoint of suppressing this effect, the material of the scraper 141 is preferably stainless steel or ceramics, and ceramics is particularly preferable.
  • the scraper 141 is also preferably not in contact with the outer peripheral surface of the deposition drum 130. This is because it is possible to prevent the active material particles to be recovered from being contaminated by impurities that may occur due to direct contact between the deposition drum 130 and the scraper 141.
  • the granular guide 143 is, for example, a vibrating conveying member, and as shown in FIG. 1, is arranged so as to slope downward from the vicinity of the deposition drum toward the collection section 152 of the chamber 150, and receives thin film pieces scraped off by the scraper 141 arranged above it, and sends them to the collection section 152 of the chamber 150.
  • the chamber 150 is mainly composed of a chamber main body 151, a recovery section 152, and an exhaust pipe 153.
  • the chamber main body 151 is a box-shaped section having a deposition chamber RM therein, and contains the crucible 110, heater 120, deposition drum 130, scraper 141, and particle guide 143.
  • the recovery section 152 is a section that protrudes outward from the side wall of the chamber main body 151, and has a space that communicates with the deposition chamber RM of the chamber main body 151.
  • the tip section of the particle guide 143 is located in this recovery section 152.
  • the raw material supply hopper 160 is a raw material supply source, and as shown in FIG. 1, its outlet is connected to the raw material introduction pipe 170. That is, the raw material fed into the raw material supply hopper 160 is supplied to the crucible 110 via the raw material introduction pipe 170 at an appropriate timing. The raw material supplied to the crucible 110 becomes molten Sr, and then vaporizes to become raw material gas.
  • the raw material introduction pipe 170 is a round-hole nozzle for supplying the solid raw material put into the raw material supply hopper 160 to the crucible 110, and is arranged in the center of the top plate of the crucible 110 so that its mouth faces upward.
  • the collection container 180 is a container for collecting thin film pieces that have passed through the first valve VL1 and the second valve VL2.
  • the first valve VL1 and the second valve VL2 are opened and closed to adjust the amount of thin film pieces collected in the collection container 180, and are provided in the collection pipe 190 that connects the collection section 152 of the chamber 150 to the collection container 180.
  • the raw material (mixed powder or granulated material) is fed from the raw material supply hopper 160 to the crucible 110 via the raw material introduction pipe 170, or the raw material is fed directly to the crucible 110.
  • the raw material of the metal-element-free silicon oxide is as described above, and generates SiO gas, which is a raw material gas, when heated to a predetermined temperature.
  • the predetermined temperature here is a temperature between the melting point of silicon (1414°C) and the melting point of silicon dioxide (1710°C).
  • the raw material of the metal-element-containing silicon oxide is as described above, and generates SiO gas, which is a raw material gas, when heated to a predetermined temperature.
  • the predetermined temperature here is a temperature between the melting point of silicon (1414°C) and the melting point of lithium-containing silicon oxide (melting point of Li2Si2O5 : 1033 ° C, melting point of Na2Si2O5: 874°C, melting point of K2Si2O5 : 1045 °C, melting point of MgSiO3 : 1558° C , melting point of CaSiO3 : 1544° C ).
  • the pressure in the precipitation chamber RM is reduced while the crucible 110 is heated by the heater 120. If the pressure in the precipitation chamber RM is too high, the reaction that generates SiO gas from the raw materials becomes difficult to occur. For this reason, the pressure in the precipitation chamber RM is preferably 1000 Pa or less, more preferably 750 Pa or less, and particularly preferably 20 Pa or less.
  • the temperature in the precipitation chamber RM affects the reaction rate of SiO, and if the temperature is too low, the reaction rate slows down, and if the temperature is too high, there are concerns that side reactions will progress due to the melting of the raw materials and that energy efficiency will decrease. There is also a concern that the temperature will damage the crucible 110. From this perspective, the temperature in the precipitation chamber RM is preferably in the range of 1000°C to 1600°C, more preferably in the range of 1100°C to 1500°C, and particularly preferably in the range of 1100°C to 1400°C.
  • raw material gas is generated from the raw material in the crucible 110, and the raw material gas is supplied to the deposition drum 130 through the gas guide Gg.
  • the deposition drum 130 is rotated by the drive source.
  • the temperature of the outer peripheral surface of the deposition drum 130 is set lower than the temperature in the deposition chamber RM. More specifically, the temperature is set lower than the condensation temperature of the raw material gas.
  • the raw material gas generated from the crucible 110 is evaporated, precipitated, and deposited on the outer peripheral surface of the rotating deposition drum 130.
  • the deposition drum 130 is rotated multiple times while the scraper 141 is kept waiting above to form a laminated film on the deposition drum 130.
  • the scraper 141 is moved downward, and the laminated film is scraped off from the deposition drum 130 by the scraper 141.
  • the scraped off pieces of the laminated film fall along the outer circumferential surface of the deposition drum 130 into the particle guide 143.
  • the pieces of the laminated film are crushed to obtain the desired metal element-containing silicon oxide or metal element-free silicon oxide.
  • any of the pretreatments or preparations (1) to (4) described above is carried out. Therefore, in this method for producing silicon oxide, it is possible to obtain metal-element-containing silicon oxide or metal-element-free silicon oxide having low aluminum element concentration, iron element concentration, and copper element concentration. Therefore, when this metal-element-containing silicon oxide or metal-element-free silicon oxide is used as a negative electrode active material, pulverization during charging and discharging can be suppressed, and thus deterioration of the cycle characteristics of the battery can be suppressed.
  • the target silicon oxide powder was produced by carrying out the following steps in order.
  • Raw material powder preparation process Low-grade silicon (Si) powder (Al mass concentration 2000 ppm, Fe mass concentration 2500 ppm, Cu mass concentration 500 ppm, median diameter 2.5 ⁇ m) and lithium disilicate (Li 2 Si 2 O 5 ) powder (Al mass concentration 50 ppm, Fe mass concentration 15 ppm, Cu mass concentration 3 ppm, median diameter 5 ⁇ m) were prepared (see Table 1).
  • the mixed powder obtained in the above-mentioned mixing process was granulated using water.
  • the Al mass concentration in the mixed powder after granulation was 772 ppm
  • the Fe mass concentration was 936 ppm
  • the Cu mass concentration was 187 ppm (see Table 1).
  • the Al mass concentration, Fe mass concentration, and Cu mass concentration were measured according to ICP emission spectrometry.
  • the molar ratio of oxygen element to silicon element (O/Si) in the mixed powder was 0.97.
  • Lithium-containing silicon oxide was manufactured according to the above-mentioned silicon oxide powder manufacturing method using the vapor deposition apparatus 100 shown in FIG. 1.
  • the raw material heating temperature was 1300°C. This raw material heating temperature was equal to or higher than the melting point of lithium disilicate (1033°C) and equal to or lower than the melting point of silicon (1414°C).
  • the composition of the finally obtained lithium-containing silicon oxide powder was Li x SiO y , where y was 1.03 and x/y was 0.35.
  • the Al mass concentration in the lithium-containing silicon oxide powder was 150 ppm, the Fe mass concentration was 45 ppm, and the Cu mass concentration was 1 ppm (see Table 1). The Al mass concentration, the Fe mass concentration, and the Cu mass concentration were measured according to the same method as described above.
  • Cycle characteristics of a battery equipped with a negative electrode made of lithium-containing silicon oxide powder (1) Battery preparation (1-1) Negative electrode preparation The lithium-containing silicon oxide powder obtained as described above and natural graphite (median diameter 12 ⁇ m) were mixed in a mass ratio of 10:90 to form a negative electrode active material.
  • the negative electrode active material, the binder aqueous solution, and the conductive assistant were added to a Thinky Co., Ltd.-made Awatori Rentaro (registered trademark) ARE-310 so that the negative electrode active material, sodium polyacrylate (binder), and Denka Black (registered trademark) (acetylene black as a conductive assistant) were in a mass ratio of 92:3:5, and then the mixture was kneaded to prepare a slurry.
  • the slurry was applied to a copper foil having a thickness of 10 ⁇ m, and the coating was pre-dried at 80 ° C. in the air, and the slurry-coated copper foil was punched into a disk shape having a diameter of 11 mm.
  • the disk-shaped slurry-coated copper foil was then dried in vacuum at 150° C. for 12 hours to obtain the desired negative electrode.
  • (1-2) Battery Fabrication A coin cell was fabricated using the above negative electrode, Li foil as a counter electrode, a separator, and an electrolyte. A 20 ⁇ m-thick polyethylene porous film was used as the separator, and a solution of lithium hexafluorophosphate (LiPF 6 ) dissolved at a concentration of 1 mol/L in a mixture of ethylene carbonate (EC) and diethyl carbonate (DEC) in a volume ratio of 1:1 was used as the electrolyte.
  • LiPF 6 lithium hexafluorophosphate
  • Cycle Characteristics A charge/discharge test of the coin cell was performed using a secondary battery charge/discharge tester manufactured by Electrofield Co., Ltd., and the capacity retention rate after 50 cycles (the capacity retention rate after 50 cycles is the value obtained by dividing the 50th discharge capacity by the initial discharge capacity and multiplying the result by 100) was found to be 75.7% (see Table 1).
  • the conditions for the initial charge were “CC-CV 0.2C” and “10mV-0.01C”
  • the conditions for the initial discharge were “CC 0.2C” and “1.5V cut-off”
  • the conditions for the second and subsequent charge were “CC-CV 1C” and “10mV-0.01C”
  • the conditions for the second and subsequent discharge were “CC 1C” and "1.5V cut-off”.
  • the amount of current at 1 C was calculated using a theoretical capacity calculated assuming that the discharge capacity of natural graphite is 360 mAh/g and the discharge capacity of silicon oxide powder is 1900 mAh/g.
  • the target lithium-containing silicon oxide powder was obtained according to the manufacturing method described in Example 1, except that the low-grade silicon (Si) powder was replaced with a medium-grade silicon (Si) powder (Al mass concentration 1000 ppm, Fe mass concentration 600 ppm, Cu mass concentration 100 ppm, median diameter 2.5 ⁇ m).
  • the BET specific surface area of the lithium-containing silicon oxide powder was measured according to the method described in Example 1, and a negative electrode was manufactured from the lithium-containing silicon oxide powder to measure the capacity retention rate of the negative electrode.
  • the Al mass concentration in the mixed powder after granulation was 402 ppm
  • the Fe mass concentration was 232 ppm
  • the Cu mass concentration was 39 ppm
  • the molar ratio of oxygen element to silicon element in the mixed powder (O/Si) was 0.97.
  • the composition of the finally obtained lithium-containing silicon oxide powder was Li x SiO y , where y was 1.03 and x/y was 0.34.
  • the lithium-containing silicon oxide powder had an Al mass concentration of 48 ppm, an Fe mass concentration of 25 ppm, and a Cu mass concentration of 1 ppm (see Table 1).
  • the lithium-containing silicon oxide powder had a BET specific surface area of 2.3 m2 /g, and the capacity retention rate of the negative electrode after 50 cycles was 78.3% (see Table 1).
  • the target lithium-containing silicon oxide powder was obtained according to the manufacturing method described in Example 1, except that the low-grade silicon (Si) powder was replaced with high-grade silicon (Si) powder (Al mass concentration 480 ppm, Fe mass concentration 300 ppm, Cu mass concentration 50 ppm, median diameter 2.5 ⁇ m), and the BET specific surface area of the lithium-containing silicon oxide powder was measured according to the method described in Example 1, and a negative electrode was manufactured from the lithium-containing silicon oxide powder to measure the capacity retention rate of the negative electrode.
  • the Al mass concentration in the mixed powder after granulation was 209 ppm
  • the Fe mass concentration was 121 ppm
  • the Cu mass concentration was 20 ppm
  • the molar ratio of oxygen element to silicon element in the mixed powder (O / Si) was 0.97.
  • the composition of the finally obtained lithium-containing silicon oxide powder was Li x SiO y , where y was 1.03 and x / y was 0.38.
  • the lithium-containing silicon oxide powder had an Al mass concentration of 24 ppm, an Fe mass concentration of 20 ppm, and a Cu mass concentration of 2 ppm (see Table 1).
  • the lithium-containing silicon oxide powder had a BET specific surface area of 2.2 m2 /g, and the capacity retention rate of the negative electrode after 50 cycles was 81.2% (see Table 1).
  • the low-grade silicon (Si) powder was replaced with high-purity silicon (Si) powder (Al mass concentration 10 ppm, Fe mass concentration 40 ppm, Cu mass concentration 5 ppm, median diameter 2.5 ⁇ m), and the silicon oxide powder production process was performed without going through the wet granulation process from the mixing process (i.e., the mixed powder obtained in the mixing process was directly put into the crucible). Except for this, the target lithium-containing silicon oxide powder was obtained according to the production method described in Example 1, and the BET specific surface area of the lithium-containing silicon oxide powder was measured according to the method described in Example 1, and a negative electrode was produced from the lithium-containing silicon oxide powder to measure the capacity retention rate of the negative electrode.
  • the Al mass concentration in the mixed powder was 35 ppm, the Fe mass concentration was 24 ppm, the Cu mass concentration was 4 ppm, and the molar ratio (O / Si) of oxygen element to silicon element in the mixed powder was 0.97.
  • the composition of the lithium-containing silicon oxide powder finally obtained was Li x SiO y , where y was 1.02 and x/y was 0.36.
  • the mass concentration of Al in the lithium-containing silicon oxide powder was 5 ppm, the mass concentration of Fe was 15 ppm, and the mass concentration of Cu was 1 ppm (see Table 1).
  • the BET specific surface area of the lithium-containing silicon oxide powder was 2.3 m 2 /g, and the capacity retention rate of the negative electrode after 50 cycles was 83.4% (see Table 1).
  • the low-grade silicon (Si) powder was replaced with a medium-grade silicon (Si) powder (Al mass concentration 1000 ppm, Fe mass concentration 600 ppm, Cu mass concentration 100 ppm, median diameter 2.5 ⁇ m), and the silicon oxide powder production process was performed without going through the wet granulation process from the mixing process (i.e., the mixed powder obtained in the mixing process was directly put into the crucible). Except for this, the target lithium-containing silicon oxide powder was obtained according to the production method described in Example 1, and the BET specific surface area of the lithium-containing silicon oxide powder was measured according to the method described in Example 1, and a negative electrode was produced from the lithium-containing silicon oxide powder to measure the capacity retention rate of the negative electrode.
  • a medium-grade silicon (Si) powder Al mass concentration 1000 ppm, Fe mass concentration 600 ppm, Cu mass concentration 100 ppm, median diameter 2.5 ⁇ m
  • the silicon oxide powder production process was performed without going through the wet granulation process from the mixing process (i.e., the mixed powder obtained
  • the Al mass concentration in the mixed powder was 402 ppm, the Fe mass concentration was 232 ppm, the Cu mass concentration was 39 ppm, and the molar ratio (O / Si) of the oxygen element to the silicon element in the mixed powder was 0.97.
  • the composition of the finally obtained lithium-containing silicon oxide powder was Li x SiO y , where y was 1.03 and x/y was 0.36.
  • the mass concentration of Al in the lithium-containing silicon oxide powder was 337 ppm, the mass concentration of Fe was 30 ppm, and the mass concentration of Cu was 1 ppm (see Table 1).
  • the BET specific surface area of the obtained lithium-containing silicon oxide powder was 2.1 m 2 /g, and the capacity retention rate of the negative electrode after 50 cycles was 70.1% (see Table 1).
  • Example 2 The low-grade silicon (Si) powder was replaced with high-grade silicon (Si) powder (Al mass concentration 480 ppm, Fe mass concentration 300 ppm, Cu mass concentration 50 ppm, median diameter 2.5 ⁇ m), and the silicon oxide powder production process was performed without going through the wet granulation process from the mixing process (i.e., the mixed powder obtained in the mixing process was directly put into the crucible). Except for this, the target lithium-containing silicon oxide powder was obtained according to the production method described in Example 1, and the BET specific surface area of the lithium-containing silicon oxide powder was measured according to the method described in Example 1, and a negative electrode was produced from the lithium-containing silicon oxide powder to measure the capacity retention rate of the negative electrode.
  • the Al mass concentration in the mixed powder was 209 ppm, the Fe mass concentration was 121 ppm, the Cu mass concentration was 20 ppm, and the molar ratio (O / Si) of oxygen element to silicon element in the mixed powder was 0.97.
  • the composition of the finally obtained lithium-containing silicon oxide powder was Li x SiO y , where y was 1.02 and x/y was 0.35.
  • the mass concentration of Al in the lithium-containing silicon oxide powder was 205 ppm, the mass concentration of Fe was 25 ppm, and the mass concentration of Cu was 2 ppm (see Table 1).
  • the BET specific surface area of the obtained lithium-containing silicon oxide powder was 2.2 m 2 /g, and the capacity retention rate of the negative electrode after 50 cycles was 71.2% (see Table 1).
  • Example 3 The low-grade silicon (Si) powder was replaced with high-purity silicon (Si) powder (Al mass concentration 10 ppm, Fe mass concentration 40 ppm, Cu mass concentration 5 ppm, median diameter 2.5 ⁇ m), and copper (Cu) powder was added so that the amount was 3 mass% relative to the total mass of the mixed powder.
  • the silicon oxide powder production process was performed without going through the wet granulation process from the mixing process (i.e., the mixed powder obtained in the mixing process was directly put into the crucible). Except for this, the target lithium-containing silicon oxide powder was obtained according to the production method described in Example 1, and the BET specific surface area of the lithium-containing silicon oxide powder was measured according to the method described in Example 1.
  • a negative electrode was produced from the lithium-containing silicon oxide powder and the capacity retention rate of the negative electrode was measured.
  • the copper powder used was one that had passed through a sieve with a mesh size of 45 ⁇ m.
  • the Al mass concentration in the mixed powder was 34 ppm
  • the Fe mass concentration was 24 ppm
  • the Cu mass concentration was 30004 ppm
  • the molar ratio of oxygen element to silicon element in the mixed powder (O/Si) was 0.97.
  • the composition of the finally obtained lithium-containing silicon oxide powder was Li x SiO y , where y was 1.04 and x/y was 0.34.
  • the Al mass concentration in the lithium-containing silicon oxide powder was 5 ppm, the Fe mass concentration was 14 ppm, and the Cu mass concentration was 3100 ppm (see Table 1).
  • the BET specific surface area of the obtained lithium-containing silicon oxide powder was 2.4 m 2 /g, and the capacity retention rate of the negative electrode after 50 cycles was 82.0% (see Table 1).
  • Example 4 The low-grade silicon (Si) powder was replaced with high-purity silicon (Si) powder (Al mass concentration 10 ppm, Fe mass concentration 40 ppm, Cu mass concentration 5 ppm, median diameter 2.5 ⁇ m), and copper (Cu) powder was added so that the amount was 0.08 mass% relative to the total mass of the mixed powder.
  • the silicon oxide powder production process was performed without going through the wet granulation process from the mixing process (i.e., the mixed powder obtained in the mixing process was directly put into the crucible). Except for this, the target lithium-containing silicon oxide powder was obtained according to the production method described in Example 1, and the BET specific surface area of the lithium-containing silicon oxide powder was measured according to the method described in Example 1.
  • a negative electrode was produced from the lithium-containing silicon oxide powder and the capacity retention rate of the negative electrode was measured. Note that the powder used was one that had passed through a sieve with a mesh of 45 ⁇ m.
  • the Al mass concentration in the mixed powder was 35 ppm
  • the Fe mass concentration was 24 ppm
  • the Cu mass concentration was 804 ppm
  • the molar ratio of oxygen element to silicon element in the mixed powder (O/Si) was 0.97.
  • the composition of the finally obtained lithium-containing silicon oxide powder was Li x SiO y , where y was 1.04 and x/y was 0.39.
  • the Al mass concentration in the lithium-containing silicon oxide powder was 5 ppm
  • the Fe mass concentration was 15 ppm
  • the Cu mass concentration was 110 ppm (see Table 1).
  • the BET specific surface area of the obtained lithium-containing silicon oxide powder was 2.4 m 2 /g, and the capacity retention rate of the negative electrode after 50 cycles was 82.5% (see Table 1).
  • the target lithium-containing silicon oxide powder was obtained according to the production method described in Example 1, and the BET specific surface area of the lithium-containing silicon oxide powder was measured according to the method described in Example 1, and a negative electrode was produced from the lithium-containing silicon oxide powder and the capacity retention rate of the negative electrode was measured.
  • the iron powder used was one that had passed through a sieve with a mesh size of 45 ⁇ m.
  • the Al mass concentration in the mixed powder was 35 ppm
  • the Fe mass concentration was 18555 ppm
  • the Cu mass concentration was 4 ppm
  • the molar ratio of oxygen element to silicon element in the mixed powder (O/Si) was 0.97.
  • the composition of the finally obtained lithium-containing silicon oxide powder was Li x SiO y , where y was 1.03 and x/y was 0.35.
  • the Al mass concentration in the lithium-containing silicon oxide powder was 5 ppm, the Fe mass concentration was 250 ppm, and the Cu mass concentration was 2 ppm (see Table 1).
  • the BET specific surface area of the obtained lithium-containing silicon oxide powder was 2.3 m 2 /g, and the capacity retention rate of the negative electrode after 50 cycles was 80.2% (see Table 1).
  • the target lithium-containing silicon oxide powder was obtained according to the production method described in Example 1, and the BET specific surface area of the lithium-containing silicon oxide powder was measured according to the method described in Example 1, and a negative electrode was produced from the lithium-containing silicon oxide powder and the capacity retention rate of the negative electrode was measured.
  • the iron powder one that had passed through a sieve with a mesh of 45 ⁇ m was used.
  • the Al mass concentration in the mixed powder was 35 ppm
  • the Fe mass concentration was 3730 ppm
  • the Cu mass concentration was 4 ppm
  • the molar ratio of oxygen element to silicon element in the mixed powder (O/Si) was 0.97.
  • the composition of the finally obtained lithium-containing silicon oxide powder was Li x SiO y , where y was 1.02 and x/y was 0.32.
  • the Al mass concentration in the lithium-containing silicon oxide powder was 5 ppm, the Fe mass concentration was 120 ppm, and the Cu mass concentration was 1 ppm (see Table 1).
  • the BET specific surface area of the obtained lithium-containing silicon oxide powder was 2.2 m 2 /g, and the capacity retention rate of the negative electrode after 50 cycles was 81.0% (see Table 1).
  • the low-grade silicon (Si) powder was replaced with medium-grade silicon (Si) powder (Al mass concentration 1000 ppm, Fe mass concentration 600 ppm, Cu mass concentration 100 ppm, median diameter 2.5 ⁇ m), and lithium disilicate (Li 2 Si 2 O 5 ) powder was replaced with magnesium silicate (MgSiO 3 ) powder (Al mass concentration 50 ppm, Fe mass concentration 15 ppm, Cu mass concentration 3 ppm, median diameter 5 ⁇ m). Except for this, the medium-grade silicon (Si) powder and magnesium silicate were mixed in a mass ratio of 58.8:100, and the target magnesium-containing silicon oxide powder was obtained according to the manufacturing method described in Example 1.
  • the BET specific surface area of the magnesium-containing silicon oxide powder was measured according to the method described in Example 1, and a negative electrode was manufactured from the magnesium-containing silicon oxide powder to measure the capacity retention rate of the negative electrode.
  • the Al mass concentration in the mixed powder after granulation was 495 ppm
  • the Fe mass concentration was 231 ppm
  • the Cu mass concentration was 39 ppm
  • the molar ratio of oxygen element to silicon element (O/Si) in the mixed powder was 0.97.
  • the composition of the magnesium-containing silicon oxide powder finally obtained was Mg x SiO y , where y was 1.02 and x/y was 0.98.
  • the Al mass concentration in the magnesium-containing silicon oxide powder was 38 ppm, the Fe mass concentration was 27 ppm, and the Cu mass concentration was 2 ppm (see Table 1).
  • the raw material heating temperature in the silicon oxide powder production process was 1500 ° C. This raw material heating temperature is equal to or higher than the melting point of silicon (1414 ° C.) and equal to or lower than the melting point of magnesium silicate (1558 ° C.).
  • the BET specific surface area of the resulting magnesium-containing silicon oxide powder was 2.3 m 2 /g, and the capacity retention rate of the negative electrode after 50 cycles was 75.3% (see Table 1).
  • the silicon oxide powder production process was carried out without going through the wet granulation process from the mixing process (i.e., the mixed powder obtained in the mixing process was directly put into the crucible), but the target magnesium-containing silicon oxide powder was obtained according to the production method described in Example 6, and the BET specific surface area of the magnesium-containing silicon oxide powder was measured according to the method described in Example 1, and a negative electrode was produced from the magnesium-containing silicon oxide powder and the capacity retention rate of the negative electrode was measured.
  • the Al mass concentration in the mixed powder was 495 ppm, the Fe mass concentration was 231 ppm, and the Cu mass concentration was 39 ppm (see Table 1).
  • the composition of the magnesium-containing silicon oxide powder finally obtained was Mg x SiO y , where y was 1.03 and x/y was 0.95.
  • the Al mass concentration in the magnesium-containing silicon oxide powder was 345 ppm, the Fe mass concentration was 29 ppm, and the Cu mass concentration was 2 ppm (see Table 1).
  • the raw material heating temperature in the silicon oxide powder manufacturing process was 1500° C. This raw material heating temperature was equal to or higher than the melting point of silicon (1414° C.) and equal to or lower than the melting point of magnesium silicate (1558° C.).
  • the BET specific surface area of the obtained magnesium-containing silicon oxide powder was 2.2 m 2 /g, and the capacity retention rate of the negative electrode after 50 cycles was 69.3% (see Table 1).
  • the low-grade silicon (Si) powder was replaced with high-purity silicon (Si) powder (Al mass concentration 10 ppm, Fe mass concentration 40 ppm, Cu mass concentration 5 ppm, median diameter 2.5 ⁇ m), and lithium disilicate (Li 2 Si 2 O 5 ) powder was replaced with magnesium silicate (MgSiO 3 ) powder (Al mass concentration 50 ppm, Fe mass concentration 15 ppm, Cu mass concentration 3 ppm, median diameter 5 ⁇ m), high purity silicon powder and magnesium silicate were mixed in a mass ratio of 47.8:100, and the silicon oxide powder production process was performed without going through the wet granulation process from the mixing process (i.e., the mixed powder obtained in the mixing process was directly put into the crucible).
  • the magnesium-containing silicon oxide powder of interest was obtained according to the production method described in Example 1, and the BET specific surface area of the magnesium-containing silicon oxide powder was measured according to the method described in Example 1, and a negative electrode was produced from the magnesium-containing silicon oxide powder and the capacity retention rate of the negative electrode was measured.
  • the Al mass concentration in the mixed powder was 31 ppm
  • the Fe mass concentration was 24 ppm
  • the Cu mass concentration was 4 ppm
  • the molar ratio of oxygen element to silicon element (O/Si) in the mixed powder was 0.97.
  • the composition of the magnesium-containing silicon oxide powder finally obtained was Mg x SiO y , where y was 1.01 and x/y was 0.94.
  • the mass concentration of Al in the magnesium-containing silicon oxide powder was 5 ppm, the mass concentration of Fe was 15 ppm, and the mass concentration of Cu was 1 ppm (see Table 1).
  • the raw material heating temperature in the silicon oxide powder production process was 1500° C. This raw material heating temperature was equal to or higher than the melting point of silicon (1414° C.) and equal to or lower than the melting point of magnesium silicate (1558° C.).
  • the BET specific surface area of the magnesium-containing silicon oxide powder obtained was 2.5 m 2 /g, and the capacity retention rate of the negative electrode after 50 cycles was 77.2% (see Table 1).
  • Example 8 Except for adding copper (Cu) powder so that it was 3 mass% relative to the total mass of the mixed powder, the target magnesium-containing silicon oxide powder was obtained according to the manufacturing method described in Example 6, and the BET specific surface area of the magnesium-containing silicon oxide powder was measured according to the method described in Example 1, and a negative electrode was manufactured from the magnesium-containing silicon oxide powder and the capacity retention rate of the negative electrode was measured. Note that, as the copper powder, one that passed through a 45 ⁇ m mesh sieve was used. In addition, the Al mass concentration in the mixed powder was 30 ppm, the Fe mass concentration was 24 ppm, the Cu mass concentration was 30004 ppm, and the molar ratio of oxygen element to silicon element (O/Si) in the mixed powder was 0.97.
  • the composition of the magnesium-containing silicon oxide powder finally obtained was Mg x SiO y , where y was 1.03 and x/y was 0.97.
  • the magnesium-containing silicon oxide powder had an Al mass concentration of 5 ppm, an Fe mass concentration of 14 ppm, and a Cu mass concentration of 3100 ppm (see Table 1).
  • the lithium-containing silicon oxide powder had a BET specific surface area of 2.4 m2 /g, and the capacity retention rate of the negative electrode after 50 cycles was 75.1% (see Table 1).
  • Example 9 Except for adding copper (Cu) powder so that it was 0.08 mass% relative to the total mass of the mixed powder, the target magnesium-containing silicon oxide powder was obtained according to the manufacturing method described in Example 6, and the BET specific surface area of the magnesium-containing silicon oxide powder was measured according to the method described in Example 1, and a negative electrode was manufactured from the magnesium-containing silicon oxide powder and the capacity retention rate of the negative electrode was measured. Note that, as the copper powder, one that passed through a 45 ⁇ m mesh sieve was used. In addition, the Al mass concentration in the mixed powder was 31 ppm, the Fe mass concentration was 24 ppm, the Cu mass concentration was 804 ppm, and the molar ratio of oxygen element to silicon element (O/Si) in the mixed powder was 0.97.
  • the composition of the magnesium-containing silicon oxide powder finally obtained was Mg x SiO y , where y was 1.02 and x/y was 0.98.
  • the magnesium-containing silicon oxide powder had an Al mass concentration of 5 ppm, an Fe mass concentration of 15 ppm, and a Cu mass concentration of 120 ppm (see Table 1).
  • the magnesium-containing silicon oxide powder had a BET specific surface area of 2.2 m2 /g, and the capacity retention rate of the negative electrode after 50 cycles was 75.6% (see Table 1).
  • the magnesium-containing silicon oxide powder was obtained according to the manufacturing method described in Example 6, except that iron (Fe) powder was added to the high purity silicon powder so as to be 5 mass% relative to the total amount of powder, and the BET specific surface area of the magnesium-containing silicon oxide powder was measured according to the method described in Example 1, and a negative electrode was manufactured from the magnesium-containing silicon oxide powder and the capacity retention rate of the negative electrode was measured.
  • iron powder one that had passed through a sieve with a mesh of 45 ⁇ m was used.
  • the Al mass concentration in the mixed powder was 31 ppm, the Fe mass concentration was 18498 ppm, the Cu mass concentration was 4 ppm, and the molar ratio of oxygen element to silicon element in the mixed powder (O/Si) was 0.97.
  • the composition of the magnesium-containing silicon oxide powder finally obtained was Mg x SiO y , where y was 1.02 and x/y was 0.95.
  • the magnesium-containing silicon oxide powder had an Al mass concentration of 5 ppm, an Fe mass concentration of 290 ppm, and a Cu mass concentration of 2 ppm (see Table 1).
  • the magnesium-containing silicon oxide powder had a BET specific surface area of 2.3 m2 /g, and the capacity retention rate of the negative electrode after 50 cycles was 74.0% (see Table 1).
  • the magnesium-containing silicon oxide powder was obtained according to the manufacturing method described in Example 6, except that iron (Fe) powder was added to the high purity silicon powder so as to be 1 mass% relative to the total amount of powder, and the BET specific surface area of the magnesium-containing silicon oxide powder was measured according to the method described in Example 1, and a negative electrode was manufactured from the magnesium-containing silicon oxide powder and the capacity retention rate of the negative electrode was measured. Note that, as the iron powder, one that passed through a sieve with a mesh of 45 ⁇ m was used.
  • the Al mass concentration in the mixed powder was 31 ppm
  • the Fe mass concentration was 3719 ppm
  • the Cu mass concentration was 4 ppm
  • the molar ratio of oxygen element to silicon element (O/Si) in the mixed powder was 0.97.
  • the composition of the magnesium-containing silicon oxide powder finally obtained was Mg x SiO y , where y was 1.03 and x/y was 0.96.
  • the magnesium-containing silicon oxide powder had an Al mass concentration of 4 ppm, an Fe mass concentration of 130 ppm, and a Cu mass concentration of 1 ppm (see Table 1).
  • the magnesium-containing silicon oxide powder had a BET specific surface area of 2.4 m2 /g, and the capacity retention rate of the negative electrode after 50 cycles was 74.6% (see Table 1).
  • the low-grade silicon (Si) powder was brought into contact with water, and the silicon oxide powder production step was performed without going through the wet granulation step from the mixing step (i.e., the mixed powder obtained in the mixing step was directly put into the crucible). Except for this, the target lithium-containing silicon oxide powder was obtained according to the manufacturing method described in Example 1, and the BET specific surface area of the lithium-containing silicon oxide powder was measured according to the method described in Example 1, and a negative electrode was produced from the lithium-containing silicon oxide powder and the capacity retention rate of the negative electrode was measured.
  • the Al mass concentration in the mixed powder was 772 ppm, the Fe mass concentration was 936 ppm, the Cu mass concentration was 187 ppm, and the molar ratio of oxygen element to silicon element in the mixed powder (O/Si) was 0.97.
  • the composition of the finally obtained lithium-containing silicon oxide powder was Li x SiO y , where y was 1.01 and x/y was 0.34.
  • the Al mass concentration in the lithium-containing silicon oxide powder was 150 ppm, the Fe mass concentration was 52 ppm, and the Cu mass concentration was 1 ppm (see Table 1).
  • the BET specific surface area of the lithium-containing silicon oxide powder was 2.3 m 2 /g, and the capacity retention rate of the negative electrode after 50 cycles was 75.8% (see Table 1).
  • the medium-grade silicon (Si) powder was brought into contact with water, and the silicon oxide powder production step was carried out without going through the wet granulation step from the mixing step (i.e., the mixed powder obtained in the mixing step was directly put into the crucible). Except for this, the lithium-containing silicon oxide powder of interest was obtained according to the manufacturing method described in Example 2, and the BET specific surface area of the lithium-containing silicon oxide powder was measured according to the method described in Example 1, and a negative electrode was produced from the lithium-containing silicon oxide powder and the capacity retention rate of the negative electrode was measured.
  • the Al mass concentration in the mixed powder was 402 ppm, the Fe mass concentration was 232 ppm, the Cu mass concentration was 39 ppm, and the molar ratio of oxygen element to silicon element in the mixed powder (O/Si) was 0.97.
  • the composition of the finally obtained lithium-containing silicon oxide powder was Li x SiO y , where y was 1.03 and x/y was 0.36.
  • the Al mass concentration in the lithium-containing silicon oxide powder was 62 ppm, the Fe mass concentration was 39 ppm, and the Cu mass concentration was 1 ppm (see Table 1).
  • the BET specific surface area of the lithium-containing silicon oxide powder was 2.2 m 2 /g, and the capacity retention rate of the negative electrode after 50 cycles was 77.8% (see Table 1).
  • the high-grade silicon (Si) powder was brought into contact with water, and the silicon oxide powder production step was carried out without going through the wet granulation step from the mixing step (i.e., the mixed powder obtained in the mixing step was directly put into the crucible). Except for this, the lithium-containing silicon oxide powder of interest was obtained according to the manufacturing method described in Example 3, and the BET specific surface area of the lithium-containing silicon oxide powder was measured according to the method described in Example 1, and a negative electrode was produced from the lithium-containing silicon oxide powder and the capacity retention rate of the negative electrode was measured.
  • the Al mass concentration in the mixed powder was 209 ppm, the Fe mass concentration was 121 ppm, the Cu mass concentration was 20 ppm, and the molar ratio of oxygen element to silicon element in the mixed powder (O/Si) was 0.97.
  • the composition of the finally obtained lithium-containing silicon oxide powder was Li x SiO y , where y was 1.02 and x/y was 0.35.
  • the Al mass concentration in the lithium-containing silicon oxide powder was 32 ppm, the Fe mass concentration was 25 ppm, and the Cu mass concentration was 1 ppm (see Table 1).
  • the BET specific surface area of the lithium-containing silicon oxide powder was 2.3 m 2 /g, and the capacity retention rate of the negative electrode after 50 cycles was 79.8% (see Table 1).
  • low-grade silicon (Si) powder and lithium disilicate powder were mixed in a mass ratio of 79.8:150 to prepare a mixed powder, and the silicon oxide powder production step was performed without going through the wet granulation step from the mixing step (i.e., the mixed powder obtained in the mixing step was directly put into the crucible). Except for this, the target lithium-containing silicon oxide powder was obtained according to the manufacturing method described in Example 1, and the BET specific surface area of the lithium-containing silicon oxide powder was measured according to the method described in Example 1, and a negative electrode was produced from the lithium-containing silicon oxide powder to measure the capacity retention rate of the negative electrode.
  • the Al mass concentration in the mixed powder was 772 ppm, the Fe mass concentration was 879 ppm, the Cu mass concentration was 176 ppm, and the molar ratio (O/Si) of oxygen element to silicon element in the mixed powder was 1.03.
  • the composition of the lithium-containing silicon oxide powder finally obtained was Li x SiO y , where y was 1.02 and x/y was 0.36.
  • the mass concentration of Al in the lithium-containing silicon oxide powder was 148 ppm, the mass concentration of Fe was 25 ppm, and the mass concentration of Cu was 1 ppm (see Table 1).
  • the BET specific surface area of the lithium-containing silicon oxide powder was 2.2 m 2 /g, and the capacity retention rate of the negative electrode after 50 cycles was 75.8% (see Table 1).
  • the mixing step medium-grade silicon (Si) powder and lithium disilicate powder were mixed in a mass ratio of 79.8:150 to prepare a mixed powder, and the silicon oxide powder production step was performed without going through the wet granulation step from the mixing step (i.e., the mixed powder obtained in the mixing step was directly put into the crucible). Except for this, the lithium-containing silicon oxide powder of interest was obtained according to the manufacturing method described in Example 2, and the BET specific surface area of the lithium-containing silicon oxide powder was measured according to the method described in Example 1, and a negative electrode was produced from the lithium-containing silicon oxide powder to measure the capacity retention rate of the negative electrode.
  • the Al mass concentration in the mixed powder was 402 ppm, the Fe mass concentration was 218 ppm, the Cu mass concentration was 37 ppm, and the molar ratio (O/Si) of the oxygen element to the silicon element in the mixed powder was 1.03.
  • the composition of the lithium-containing silicon oxide powder finally obtained was Li x SiO y , where y was 1.03 and x/y was 0.34.
  • the mass concentration of Al in the lithium-containing silicon oxide powder was 50 ppm, the mass concentration of Fe was 24 ppm, and the mass concentration of Cu was 1 ppm (see Table 1).
  • the BET specific surface area of the lithium-containing silicon oxide powder was 2.2 m 2 /g, and the capacity retention rate of the negative electrode after 50 cycles was 78.1% (see Table 1).
  • the mixing step high-grade silicon (Si) powder and lithium disilicate powder were mixed in a mass ratio of 79.8:150 to prepare a mixed powder, and the silicon oxide powder production step was performed without going through the wet granulation step from the mixing step (i.e., the mixed powder obtained in the mixing step was directly put into the crucible). Except for this, the target lithium-containing silicon oxide powder was obtained according to the manufacturing method described in Example 3, and the BET specific surface area of the lithium-containing silicon oxide powder was measured according to the method described in Example 1, and a negative electrode was produced from the lithium-containing silicon oxide powder to measure the capacity retention rate of the negative electrode.
  • the Al mass concentration in the mixed powder was 209 ppm, the Fe mass concentration was 114 ppm, the Cu mass concentration was 19 ppm, and the molar ratio (O/Si) of oxygen element to silicon element in the mixed powder was 1.03.
  • the composition of the lithium-containing silicon oxide powder finally obtained was Li x SiO y , where y was 1.03 and x/y was 0.36.
  • the mass concentration of Al in the lithium-containing silicon oxide powder was 27 ppm, the mass concentration of Fe was 20 ppm, and the mass concentration of Cu was 1 ppm (see Table 1).
  • the BET specific surface area of the lithium-containing silicon oxide powder was 2.3 m 2 /g, and the capacity retention rate of the negative electrode after 50 cycles was 81.0% (see Table 1).
  • the mixing step medium-grade silicon (Si) powder and lithium disilicate powder were mixed in a mass ratio of 56:150 to prepare a mixed powder, and the silicon oxide powder production step was performed without going through the wet granulation step from the mixing step (i.e., the mixed powder obtained in the mixing step was directly put into the crucible). Except for this, the target lithium-containing silicon oxide powder was obtained according to the manufacturing method described in Example 2, and the BET specific surface area of the lithium-containing silicon oxide powder was measured according to the method described in Example 1, and a negative electrode was produced from the lithium-containing silicon oxide powder to measure the capacity retention rate of the negative electrode.
  • the Al mass concentration in the mixed powder was 402 ppm, the Fe mass concentration was 174 ppm, the Cu mass concentration was 29 ppm, and the molar ratio (O/Si) of the oxygen element to the silicon element in the mixed powder was 1.25.
  • the composition of the lithium-containing silicon oxide powder finally obtained was Li x SiO y , where y was 1.04 and x/y was 0.35.
  • the mass concentration of Al in the lithium-containing silicon oxide powder was 40 ppm, the mass concentration of Fe was 21 ppm, and the mass concentration of Cu was 1 ppm (see Table 1).
  • the BET specific surface area of the lithium-containing silicon oxide powder was 2.3 m 2 /g, and the capacity retention rate of the negative electrode after 50 cycles was 79.1% (see Table 1).
  • the negative electrode formed from silicon oxide powder manufactured with the aluminum element mass concentration in the mixed raw material being less than 50 ppm, the iron element concentration being less than 1000 ppm, and the copper element concentration being less than 200 ppm had a higher capacity retention rate than the negative electrode formed from silicon oxide powder manufactured with the aluminum element mass concentration being 50 ppm or more, the iron element concentration being 1000 ppm or more, and the copper element concentration being 200 ppm or more. It was also clear that the lower the aluminum element concentration, iron element concentration, and copper element concentration in the obtained silicon oxide powder, the higher the capacity retention rate (see Example 4).
  • the negative electrode formed from silicon oxide powder produced through water treatment of silicon powder had a higher capacity retention rate than the negative electrode formed from silicon oxide powder produced without water treatment of silicon powder. It was also clear that the lower the aluminum element concentration, iron element concentration, and copper element concentration in the obtained silicon oxide powder, the higher the capacity retention rate (see Examples 7 to 9).
  • the lithium-containing silicon oxide powder obtained in Example 1 was charged into a rotary kiln, and carbon coating treatment was performed on the lithium-containing silicon oxide powder by thermal CVD in which argon gas and propane gas were passed through at 700°C.
  • the mass ratio of carbon to the mass of the lithium-containing silicon oxide powder was 2 mass%.
  • the mass ratio was calculated from the result of the carbon amount quantitatively evaluated by analyzing carbon dioxide gas by oxygen stream combustion-infrared absorption method using a carbon concentration analyzer (CS400 manufactured by Leco).
  • CS400 carbon concentration analyzer
  • the lithium-containing silicon oxide powder obtained in Example 2 was charged into a rotary kiln, and carbon coating treatment was performed on the lithium-containing silicon oxide powder by thermal CVD in which argon gas and propane gas were passed through at 700°C.
  • the mass ratio of carbon to the mass of the lithium-containing silicon oxide powder was 2 mass%.
  • the mass ratio was calculated from the result of the carbon amount quantitatively evaluated by analyzing carbon dioxide gas by oxygen stream combustion-infrared absorption method using a carbon concentration analyzer (CS400 manufactured by Leco).
  • the BET specific surface area of the carbon-coated lithium-containing silicon oxide powder was measured according to the method described in Example 1, and a negative electrode was produced from the carbon-coated lithium-containing silicon oxide powder to measure the capacity retention rate of the negative electrode.
  • the BET specific surface area of the obtained carbon-coated lithium-containing silicon oxide powder was 2.1 m 2 /g, and the capacity retention rate of the negative electrode after 50 cycles was 82.5% (see Table 2).
  • the lithium-containing silicon oxide powder obtained in Example 3 was charged into a rotary kiln, and carbon coating treatment was performed on the lithium-containing silicon oxide powder by thermal CVD in which argon gas and propane gas were passed through at 700°C.
  • the mass ratio of carbon to the mass of the lithium-containing silicon oxide powder was 2 mass%.
  • the mass ratio was calculated from the result of the carbon amount quantitatively evaluated by analyzing carbon dioxide gas by oxygen stream combustion-infrared absorption method using a carbon concentration analyzer (CS400 manufactured by Leco).
  • the BET specific surface area of the carbon-coated lithium-containing silicon oxide powder was measured according to the method described in Example 1, and a negative electrode was produced from the carbon-coated lithium-containing silicon oxide powder to measure the capacity retention rate of the negative electrode.
  • the BET specific surface area of the obtained carbon-coated lithium-containing silicon oxide powder was 2.0 m 2 /g, and the capacity retention rate of the negative electrode after 50 cycles was 87.3% (see Table 2).
  • the lithium-containing silicon oxide powder obtained in Example 4 was charged into a rotary kiln, and carbon coating treatment was performed on the lithium-containing silicon oxide powder by thermal CVD in which argon gas and propane gas were passed through at 700°C.
  • the mass ratio of carbon to the mass of the lithium-containing silicon oxide powder was 2 mass%.
  • the mass ratio was calculated from the result of the carbon amount quantitatively evaluated by analyzing carbon dioxide gas by oxygen stream combustion-infrared absorption method using a carbon concentration analyzer (CS400 manufactured by Leco).
  • the BET specific surface area of the carbon-coated lithium-containing silicon oxide powder was measured according to the method described in Example 1, and a negative electrode was produced from the carbon-coated lithium-containing silicon oxide powder to measure the capacity retention rate of the negative electrode.
  • the BET specific surface area of the obtained carbon-coated lithium-containing silicon oxide powder was 2.1 m 2 /g, and the capacity retention rate of the negative electrode after 50 cycles was 88.9% (see Table 2).
  • Comparative Example 13 The lithium-containing silicon oxide powder obtained in Comparative Example 1 was charged into a rotary kiln, and the lithium-containing silicon oxide powder was subjected to carbon coating treatment by thermal CVD in which argon gas and propane gas were passed through at 700°C.
  • the mass ratio of carbon to the mass of the lithium-containing silicon oxide powder was 2 mass%.
  • the mass ratio was calculated from the result of the carbon amount quantitatively evaluated by analyzing carbon dioxide gas by oxygen stream combustion-infrared absorption method using a carbon concentration analyzer (CS400 manufactured by Leco).
  • the BET specific surface area of the carbon-coated lithium-containing silicon oxide powder was measured according to the method described in Example 1, and a negative electrode was produced from the carbon-coated lithium-containing silicon oxide powder to measure the capacity retention rate of the negative electrode.
  • the BET specific surface area of the obtained carbon-coated lithium-containing silicon oxide powder was 1.9 m 2 /g, and the capacity retention rate of the negative electrode after 50 cycles was 78.9% (see Table 2).
  • Comparative Example 14 The lithium-containing silicon oxide powder obtained in Comparative Example 2 was charged into a rotary kiln, and the lithium-containing silicon oxide powder was subjected to carbon coating treatment by thermal CVD in which argon gas and propane gas were passed through at 700°C. The mass ratio of carbon to the mass of the lithium-containing silicon oxide powder was 2 mass%. The mass ratio was calculated from the result of the carbon amount quantitatively evaluated by analyzing carbon dioxide gas by oxygen stream combustion-infrared absorption method using a carbon concentration analyzer (CS400 manufactured by Leco).
  • CS400 carbon concentration analyzer
  • the BET specific surface area of the carbon-coated lithium-containing silicon oxide powder was measured according to the method described in Example 1, and a negative electrode was produced from the carbon-coated lithium-containing silicon oxide powder to measure the capacity retention rate of the negative electrode.
  • the BET specific surface area of the obtained carbon-coated lithium-containing silicon oxide powder was 2.0 m 2 /g, and the capacity retention rate of the negative electrode after 50 cycles was 79.6% (see Table 2).
  • Comparative Example 15 The lithium-containing silicon oxide powder obtained in Comparative Example 3 was charged into a rotary kiln, and the lithium-containing silicon oxide powder was subjected to carbon coating treatment by thermal CVD in which argon gas and propane gas were passed through at 700°C.
  • the mass ratio of carbon to the mass of the lithium-containing silicon oxide powder was 2 mass%.
  • the mass ratio was calculated from the result of the carbon amount quantitatively evaluated by analyzing carbon dioxide gas by oxygen stream combustion-infrared absorption method using a carbon concentration analyzer (CS400 manufactured by Leco).
  • the BET specific surface area of the carbon-coated lithium-containing silicon oxide powder was measured according to the method described in Example 1, and a negative electrode was produced from the carbon-coated lithium-containing silicon oxide powder to measure the capacity retention rate of the negative electrode.
  • the BET specific surface area of the obtained carbon-coated lithium-containing silicon oxide powder was 2.2 m 2 /g, and the capacity retention rate of the negative electrode after 50 cycles was 87.1% (see Table 2).
  • Comparative Example 16 The lithium-containing silicon oxide powder obtained in Comparative Example 4 was charged into a rotary kiln, and carbon coating treatment was performed on the lithium-containing silicon oxide powder by thermal CVD in which argon gas and propane gas were passed through at 700°C.
  • the mass ratio of carbon to the mass of the lithium-containing silicon oxide powder was 2 mass%.
  • the mass ratio was calculated from the result of the carbon amount quantitatively evaluated by analyzing carbon dioxide gas by oxygen stream combustion-infrared absorption method using a carbon concentration analyzer (CS400 manufactured by Leco).
  • the BET specific surface area of the carbon-coated lithium-containing silicon oxide powder was measured according to the method described in Example 1, and a negative electrode was produced from the carbon-coated lithium-containing silicon oxide powder to measure the capacity retention rate of the negative electrode.
  • the BET specific surface area of the obtained carbon-coated lithium-containing silicon oxide powder was 2.2 m 2 /g, and the capacity retention rate of the negative electrode after 50 cycles was 87.5% (see Table 2).
  • Comparative Example 17 The lithium-containing silicon oxide powder obtained in Comparative Example 5 was charged into a rotary kiln, and the lithium-containing silicon oxide powder was subjected to carbon coating treatment by thermal CVD in which argon gas and propane gas were passed through at 700°C.
  • the mass ratio of carbon to the mass of the lithium-containing silicon oxide powder was 2 mass%.
  • the mass ratio was calculated from the result of the carbon amount quantitatively evaluated by analyzing carbon dioxide gas by oxygen stream combustion-infrared absorption method using a carbon concentration analyzer (CS400 manufactured by Leco).
  • the BET specific surface area of the carbon-coated lithium-containing silicon oxide powder was measured according to the method described in Example 1, and a negative electrode was produced from the carbon-coated lithium-containing silicon oxide powder to measure the capacity retention rate of the negative electrode.
  • the BET specific surface area of the obtained carbon-coated lithium-containing silicon oxide powder was 2.1 m 2 /g, and the capacity retention rate of the negative electrode after 50 cycles was 85.4% (see Table 2).
  • Comparative Example 18 The lithium-containing silicon oxide powder obtained in Comparative Example 6 was charged into a rotary kiln, and carbon coating treatment was performed on the lithium-containing silicon oxide powder by thermal CVD in which argon gas and propane gas were passed through at 700°C.
  • the mass ratio of carbon to the mass of the lithium-containing silicon oxide powder was 2 mass%.
  • the mass ratio was calculated from the result of the carbon amount quantitatively evaluated by analyzing carbon dioxide gas by oxygen stream combustion-infrared absorption method using a carbon concentration analyzer (CS400 manufactured by Leco).
  • the BET specific surface area of the carbon-coated lithium-containing silicon oxide powder was measured according to the method described in Example 1, and a negative electrode was produced from the carbon-coated lithium-containing silicon oxide powder to measure the capacity retention rate of the negative electrode.
  • the BET specific surface area of the obtained carbon-coated lithium-containing silicon oxide powder was 2.0 m 2 /g, and the capacity retention rate of the negative electrode after 50 cycles was 86.0% (see Table 2).
  • the silicon oxide powder obtained in Example 5 was charged into a rotary kiln, and the magnesium-containing silicon oxide powder was subjected to carbon coating treatment by thermal CVD in which argon gas and propane gas were passed through at 700°C.
  • the mass ratio of carbon to the mass of the magnesium-containing silicon oxide powder was 2 mass%.
  • the mass ratio was calculated from the result of the carbon amount quantitatively evaluated by analyzing carbon dioxide gas by oxygen stream combustion-infrared absorption method using a carbon concentration analyzer (CS400 manufactured by Leco).
  • CS400 carbon concentration analyzer manufactured by Leco
  • the BET specific surface area of the carbon-coated magnesium-containing silicon oxide powder was measured according to the method described in Example 1, and a negative electrode was produced from the carbon-coated magnesium-containing silicon oxide powder to measure the capacity retention rate of the negative electrode.
  • the BET specific surface area of the obtained carbon-coated magnesium-containing silicon oxide powder was 2.1 m 2 /g, and the capacity retention rate of the negative electrode after 50 cycles was 81.2% (see Table
  • the BET specific surface area of the carbon-coated magnesium-containing silicon oxide powder was measured according to the method described in Example 1, and a negative electrode was manufactured from the carbon-coated magnesium-containing silicon oxide powder to measure the capacity retention rate of the negative electrode.
  • the BET specific surface area of the obtained carbon-coated magnesium-containing silicon oxide powder was 2.0 m 2 /g, and the capacity retention rate of the negative electrode after 50 cycles was 78.3% (see Table 2).
  • the lithium-containing silicon oxide powder obtained in Example 6 was charged into a rotary kiln, and carbon coating treatment was performed on the lithium-containing silicon oxide powder by thermal CVD in which argon gas and propane gas were passed through at 700°C.
  • the mass ratio of carbon to the mass of the lithium-containing silicon oxide powder was 2 mass%.
  • the mass ratio was calculated from the result of the carbon amount quantitatively evaluated by analyzing carbon dioxide gas by oxygen stream combustion-infrared absorption method using a carbon concentration analyzer (CS400 manufactured by Leco).
  • CS400 carbon concentration analyzer
  • the BET specific surface area of the carbon-coated lithium-containing silicon oxide powder was measured according to the method described in Example 1, and a negative electrode was produced from the carbon-coated lithium-containing silicon oxide powder to measure the capacity retention rate of the negative electrode.
  • the BET specific surface area of the obtained carbon-coated lithium-containing silicon oxide powder was 2.3 m 2 /g, and the capacity retention rate of the negative electrode after 50 cycles was 83.3% (see Table 2).
  • Comparative Example 20 The lithium-containing silicon oxide powder obtained in Comparative Example 8 was charged into a rotary kiln, and carbon coating treatment was performed on the lithium-containing silicon oxide powder by thermal CVD in which argon gas and propane gas were passed through at 700°C.
  • the mass ratio of carbon to the mass of the lithium-containing silicon oxide powder was 2 mass%.
  • the mass ratio was calculated from the result of the carbon amount quantitatively evaluated by analyzing carbon dioxide gas by oxygen stream combustion-infrared absorption method using a carbon concentration analyzer (CS400 manufactured by Leco).
  • the BET specific surface area of the carbon-coated lithium-containing silicon oxide powder was measured according to the method described in Example 1, and a negative electrode was produced from the carbon-coated lithium-containing silicon oxide powder to measure the capacity retention rate of the negative electrode.
  • the BET specific surface area of the obtained carbon-coated lithium-containing silicon oxide powder was 2.2 m 2 /g, and the capacity retention rate of the negative electrode after 50 cycles was 81.0% (see Table 2).
  • Comparative Example 21 The lithium-containing silicon oxide powder obtained in Comparative Example 9 was charged into a rotary kiln, and the lithium-containing silicon oxide powder was subjected to carbon coating treatment by thermal CVD in which argon gas and propane gas were passed through at 700°C.
  • the mass ratio of carbon to the mass of the lithium-containing silicon oxide powder was 2 mass%.
  • the mass ratio was calculated from the result of the carbon amount quantitatively evaluated by analyzing carbon dioxide gas by oxygen stream combustion-infrared absorption method using a carbon concentration analyzer (CS400 manufactured by Leco).
  • the BET specific surface area of the carbon-coated lithium-containing silicon oxide powder was measured according to the method described in Example 1, and a negative electrode was produced from the carbon-coated lithium-containing silicon oxide powder to measure the capacity retention rate of the negative electrode.
  • the BET specific surface area of the obtained carbon-coated lithium-containing silicon oxide powder was 2.0 m 2 /g, and the capacity retention rate of the negative electrode after 50 cycles was 81.5% (see Table 2).
  • Comparative Example 22 The lithium-containing silicon oxide powder obtained in Comparative Example 10 was charged into a rotary kiln, and the lithium-containing silicon oxide powder was subjected to carbon coating treatment by thermal CVD in which argon gas and propane gas were passed through at 700°C.
  • the mass ratio of carbon to the mass of the lithium-containing silicon oxide powder was 2 mass%.
  • the mass ratio was calculated from the result of the carbon amount quantitatively evaluated by analyzing carbon dioxide gas by oxygen stream combustion-infrared absorption method using a carbon concentration analyzer (CS400 manufactured by Leco).
  • the BET specific surface area of the carbon-coated lithium-containing silicon oxide powder was measured according to the method described in Example 1, and a negative electrode was produced from the carbon-coated lithium-containing silicon oxide powder to measure the capacity retention rate of the negative electrode.
  • the BET specific surface area of the obtained carbon-coated lithium-containing silicon oxide powder was 2.1 m 2 /g, and the capacity retention rate of the negative electrode after 50 cycles was 80.0% (see Table 2).
  • Comparative Example 23 The lithium-containing silicon oxide powder obtained in Comparative Example 11 was charged into a rotary kiln, and the lithium-containing silicon oxide powder was subjected to carbon coating treatment by thermal CVD in which argon gas and propane gas were passed through at 700°C.
  • the mass ratio of carbon to the mass of the lithium-containing silicon oxide powder was 2 mass%.
  • the mass ratio was calculated from the result of the carbon amount quantitatively evaluated by analyzing carbon dioxide gas by oxygen stream combustion-infrared absorption method using a carbon concentration analyzer (CS400 manufactured by Leco).
  • the BET specific surface area of the carbon-coated lithium-containing silicon oxide powder was measured according to the method described in Example 1, and a negative electrode was produced from the carbon-coated lithium-containing silicon oxide powder to measure the capacity retention rate of the negative electrode.
  • the BET specific surface area of the obtained carbon-coated lithium-containing silicon oxide powder was 2.2 m 2 /g, and the capacity retention rate of the negative electrode after 50 cycles was 80.2% (see Table 2).
  • the lithium-containing silicon oxide powder obtained in Example 7 was charged into a rotary kiln, and carbon coating treatment was performed on the lithium-containing silicon oxide powder by thermal CVD in which argon gas and propane gas were passed through at 700°C.
  • the mass ratio of carbon to the mass of the lithium-containing silicon oxide powder was 2 mass%.
  • the mass ratio was calculated from the result of the carbon amount quantitatively evaluated by analyzing carbon dioxide gas by oxygen stream combustion-infrared absorption method using a carbon concentration analyzer (CS400 manufactured by Leco).
  • the BET specific surface area of the carbon-coated lithium-containing silicon oxide powder was measured according to the method described in Example 1, and a negative electrode was produced from the carbon-coated lithium-containing silicon oxide powder to measure the capacity retention rate of the negative electrode.
  • the BET specific surface area of the obtained carbon-coated lithium-containing silicon oxide powder was 2.1 m 2 /g, and the capacity retention rate of the negative electrode after 50 cycles was 80.4% (see Table 2).
  • the lithium-containing silicon oxide powder obtained in Example 8 was charged into a rotary kiln, and carbon coating treatment was performed on the lithium-containing silicon oxide powder by thermal CVD in which argon gas and propane gas were passed through at 700°C.
  • the mass ratio of carbon to the mass of the lithium-containing silicon oxide powder was 2 mass%.
  • the mass ratio was calculated from the result of the carbon amount quantitatively evaluated by analyzing carbon dioxide gas by oxygen stream combustion-infrared absorption method using a carbon concentration analyzer (CS400 manufactured by Leco).
  • CS400 carbon concentration analyzer
  • the BET specific surface area of the carbon-coated lithium-containing silicon oxide powder was measured according to the method described in Example 1, and a negative electrode was produced from the carbon-coated lithium-containing silicon oxide powder to measure the capacity retention rate of the negative electrode.
  • the BET specific surface area of the obtained carbon-coated lithium-containing silicon oxide powder was 2.0 m 2 /g, and the capacity retention rate of the negative electrode after 50 cycles was 82.0% (see Table 2).
  • the lithium-containing silicon oxide powder obtained in Example 9 was charged into a rotary kiln, and carbon coating treatment was performed on the lithium-containing silicon oxide powder by thermal CVD in which argon gas and propane gas were passed through at 700°C.
  • the mass ratio of carbon to the mass of the lithium-containing silicon oxide powder was 2 mass%.
  • the mass ratio was calculated from the result of the carbon amount quantitatively evaluated by analyzing carbon dioxide gas by oxygen stream combustion-infrared absorption method using a carbon concentration analyzer (CS400 manufactured by Leco).
  • the BET specific surface area of the carbon-coated lithium-containing silicon oxide powder was measured according to the method described in Example 1, and a negative electrode was produced from the carbon-coated lithium-containing silicon oxide powder to measure the capacity retention rate of the negative electrode.
  • the BET specific surface area of the obtained carbon-coated lithium-containing silicon oxide powder was 2.1 m 2 /g, and the capacity retention rate of the negative electrode after 50 cycles was 85.1% (see Table 2).
  • the lithium-containing silicon oxide powder obtained in Example 10 was charged into a rotary kiln, and the lithium-containing silicon oxide powder was subjected to carbon coating treatment by thermal CVD in which argon gas and propane gas were passed through at 700°C.
  • the mass ratio of carbon to the mass of the lithium-containing silicon oxide powder was 2 mass%.
  • the mass ratio was calculated from the result of the carbon amount quantitatively evaluated by analyzing carbon dioxide gas by oxygen stream combustion-infrared absorption method using a carbon concentration analyzer (CS400 manufactured by Leco).
  • CS400 carbon concentration analyzer
  • the lithium-containing silicon oxide powder obtained in Example 11 was charged into a rotary kiln, and the lithium-containing silicon oxide powder was subjected to carbon coating treatment by thermal CVD in which argon gas and propane gas were passed through at 700°C.
  • the mass ratio of carbon to the mass of the lithium-containing silicon oxide powder was 2 mass%.
  • the mass ratio was calculated from the result of the carbon amount quantitatively evaluated by analyzing carbon dioxide gas by oxygen stream combustion-infrared absorption method using a carbon concentration analyzer (CS400 manufactured by Leco).
  • the BET specific surface area of the carbon-coated lithium-containing silicon oxide powder was measured according to the method described in Example 1, and a negative electrode was produced from the carbon-coated lithium-containing silicon oxide powder to measure the capacity retention rate of the negative electrode.
  • the BET specific surface area of the obtained carbon-coated lithium-containing silicon oxide powder was 2.0 m 2 /g, and the capacity retention rate of the negative electrode after 50 cycles was 82.3% (see Table 2).
  • the lithium-containing silicon oxide powder obtained in Example 12 was charged into a rotary kiln, and carbon coating treatment was performed on the lithium-containing silicon oxide powder by thermal CVD in which argon gas and propane gas were passed through at 700°C.
  • the mass ratio of carbon to the mass of the lithium-containing silicon oxide powder was 2 mass%.
  • the mass ratio was calculated from the result of the carbon amount quantitatively evaluated by analyzing carbon dioxide gas by oxygen stream combustion-infrared absorption method using a carbon concentration analyzer (CS400 manufactured by Leco).
  • the BET specific surface area of the carbon-coated lithium-containing silicon oxide powder was measured according to the method described in Example 1, and a negative electrode was produced from the carbon-coated lithium-containing silicon oxide powder to measure the capacity retention rate of the negative electrode.
  • the BET specific surface area of the obtained carbon-coated lithium-containing silicon oxide powder was 2.1 m 2 /g, and the capacity retention rate of the negative electrode after 50 cycles was 86.2% (see Table 2).
  • the lithium-containing silicon oxide powder obtained in Example 13 was charged into a rotary kiln, and carbon coating treatment was performed on the lithium-containing silicon oxide powder by thermal CVD in which argon gas and propane gas were passed through at 700°C.
  • the mass ratio of carbon to the mass of the lithium-containing silicon oxide powder was 2 mass%.
  • the mass ratio was calculated from the result of the carbon amount quantitatively evaluated by analyzing carbon dioxide gas by oxygen stream combustion-infrared absorption method using a carbon concentration analyzer (CS400 manufactured by Leco).
  • the BET specific surface area of the carbon-coated lithium-containing silicon oxide powder was measured according to the method described in Example 1, and a negative electrode was produced from the carbon-coated lithium-containing silicon oxide powder to measure the capacity retention rate of the negative electrode.
  • the BET specific surface area of the obtained carbon-coated lithium-containing silicon oxide powder was 1.9 m 2 /g, and the capacity retention rate of the negative electrode after 50 cycles was 83.8% (see Table 2).

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