WO2012105669A1 - Procédé pour la fabrication d'un matériau composite à base de carbone contenant du silicium revêtu de carbone en surface - Google Patents

Procédé pour la fabrication d'un matériau composite à base de carbone contenant du silicium revêtu de carbone en surface Download PDF

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Publication number
WO2012105669A1
WO2012105669A1 PCT/JP2012/052440 JP2012052440W WO2012105669A1 WO 2012105669 A1 WO2012105669 A1 WO 2012105669A1 JP 2012052440 W JP2012052440 W JP 2012052440W WO 2012105669 A1 WO2012105669 A1 WO 2012105669A1
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groups
group
carbon
silicon
component
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Inventor
Yukinari Harimoto
Masayasu Akasaka
Hiroshi Fukui
Katsuya Eguchi
Yoshito Ushio
Son Thanh PHAN
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DuPont Toray Specialty Materials KK
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Dow Corning Toray Co Ltd
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    • H01M4/583—Carbonaceous material, e.g. graphite-intercalation compounds or CFx
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Definitions

  • the present invention relates to a carbon surface-coated silicon-containing carbon-based composite material and a method for manufacturing the same, an electrode active material constituted by the composite material, an electrode comprising the active material, and an electricity storage device comprising the electrode.
  • Electricity storage devices and particularly lithium or lithium-ion secondary batteries are being investigated as a type of high energy density secondary battery.
  • a silicon-containing carbon material obtained by pyrolyzing a silicon polymer is used as a negative electrode material of such lithium-ion secondary batteries.
  • Japanese Unexamined Patent Application Publication No. H10-97853 and Solid State Ionics, 122, 71 (1999) describe fabricating an electrode usable in the manufacturing of a battery having a large capacity, low irreversible capacity, high density, and excellent safety behavior by using a polysilane and a coal tar pitch as precursors.
  • Patent Document 1 Japanese Unexamined Patent Application Publication No. H10-97853
  • Patent Document 2 Japanese Unexamined Patent Application Publication No. HI 0-74506
  • Patent Document 3 Japanese Unexamined Patent Application Publication No. H 10-275617
  • Patent Document 4 Japanese Unexamined Patent Application Publication No. 2004-273377
  • Non-Patent Document 1 Solid State Ionics, 122, 71 (1999)
  • Non-Patent Document 2 J. Electrochem. Soc, 144, 2410 ( 1997)
  • An object of the present invention is to provide a composite material suitable for use as an electrode of an electricity storage device, particularly for a lithium or lithium-ion secondary battery, an electrode active material constituted by the composite material, an electrode containing the active material, and an electricity storage device including the electrode.
  • the object of the present invention is achieved by a method for manufacturing a carbon surface-coated silicon-containing carbon-based composite material characterized by obtaining a cured product by crosslinking (A) a crosslinkable group-containing organic compound (hereinafter referred to as “component (A)”), and (B) a silicon-containing compound (hereinafter referred to as “component (B)”) capable of crosslinking the crosslinkable group-containing organic compound; and baking a mixture of the cured product and (C) a carbonaceous matter (hereinafter referred to as "component (C)").
  • component (A) crosslinkable group-containing organic compound
  • component (B) silicon-containing compound capable of crosslinking the crosslinkable group-containing organic compound
  • component (C) a carbonaceous matter
  • the baking is preferably performed at a temperature of from 300°C to 1 ,500°C in an inert gas or in a vacuum.
  • the crosslinkable group can be selected from the group consisting of aliphatic unsaturated groups, epoxy groups, acryl groups, methacryl groups, amino groups, hydroxyl groups, mercapto groups, and halogenated alkyl groups.
  • the component (A) may have an aromatic group.
  • the component (A) is preferably an organic compound expressed by the following general formula.
  • R 1 is a crosslinkable group; "x" is an integer greater than or equal to 1 ; and R 2 is an aromatic group with "x" valency.
  • the component (B) can be a siloxane, a silane, a silazane, a carbosilane, or a mixture thereof.
  • the component (B) is preferably a siloxane expressed by the following average unit formula.
  • R 3 each independently represent a monovalent hydrocarbon group, a hydrogen atom, a halogen atom, an epoxy group-containing organic group, an acryl group- or methacryl
  • the component (C) can be a carbon black, a carbon fiber, a carbon nanofiber, a carbon nanotube, or a mixture thereof.
  • the crosslinking may be carried out via an addition reaction, a condensation reaction, a ring-opening reaction, or a radical reaction.
  • the cured product is preferably obtained by a hydrosilylation reaction of the component (A) having aliphatic unsaturated groups and the component (B) having silicon-bonded hydrogen atoms.
  • the cured product is preferably obtained by a radical reaction of the component (A) having aliphatic unsaturated groups and the component (B) having aliphatic unsaturated groups, acryl groups, methacryl groups, or silicon-bonded hydrogen atoms.
  • a surface of the cured product is preferably covered by the component (C).
  • the present invention relates to a carbon surface-coated silicon-containing carbon-based composite material obtained via the manufacturing method described above.
  • the composite material is preferably constituted by particles having an average diameter from 5 nm to 50 ⁇ .
  • An amount of carbon in the composite material can be set to from 1 to 50 mass (weight)%.
  • the composite material preferably has a carbon coating layer having a thickness from 5 nm to 2 ⁇ .
  • the electrode active material of the present invention is constituted by the composite material described above.
  • the electrode active material is preferably constituted by particles having an average diameter from 1 to 50 ⁇ .
  • the electrode of the present invention includes the electrode active material described above, and can be suitably used for electricity storage devices, especially for lithium or lithium-ion secondary batteries.
  • the composite material of the present invention can be used as a raw material for an electrode active material having high reversible capacity, stable charge and discharge cycle characteristics, high initial charge and discharge efficiency, and little electrical potential loss when lithium is discharged. Additionally, the composite material of the present invention uses inexpensive raw materials and can be manufactured via a simple manufacturing process.
  • the electrode active material of the present invention is suitable for use in an electricity storage device, particularly as an electrode of a lithium or lithium-ion secondary battery. Moreover, the electrode of the present invention can impart high reversible capacity, stable charge and discharge cycle characteristics, and high initial charge and discharge efficiency to a battery. As a result, the electricity storage device of the present invention can have high reversible capacity, stable charge and discharge cycle characteristics, and high initial charge and discharge efficiency.
  • FIG. 1 illustrates a lithium-ion secondary battery that is an example of the electricity storage device of the present invention.
  • FIG. 2 illustrates a lithium secondary battery that is an example of the electricity storage device of the present invention.
  • FIG. 3 is an electron photomicrograph of spherical silicon-containing crosslinked particles prepared in Practical Example 1.
  • FIG. 4 is an electron photomicrograph of the carbon-coated silicon-containing carbon-based composite material prepared in Practical Example 1.
  • FIG. 5 is a transmission electron photomicrograph of a cross-section of the carbon-coated silicon-containing carbon-based composite material prepared in Practical Example 1 .
  • the composite material of the present invention can be obtained by a manufacturing method characterized by obtaining a cured product by crosslinking (A) a crosslinkable group-containing organic compound, and (B) a silicon-containing compound capable of crosslinking the crosslinkable group-containing organic compound; and baking a mixture of the cured product and (C) a carbonaceous matter.
  • the crosslinkable group in the component (A) is not particularly limited provide that it is a crosslinkable group.
  • examples thereof include aliphatic unsaturated groups, epoxy groups, acryl groups, methacryl groups, amino groups, hydroxyl groups, mercapto groups, and halogenated alkyi groups.
  • Specific examples of the aliphatic unsaturated groups include vinyl groups, propenyl groups, butenyl groups, pentenyl groups, hexenyl groups, and similar alkenyl groups; acetyl groups, propynyl groups, pentynyl groups, and similar alkynyl groups.
  • epoxy groups include glycidyl groups, glycidoxy groups, epoxycyclohexyl groups, 3-glycidoxypropyl groups, and 2-(3,4-epoxycyclohexyl) ethyl groups.
  • acryl groups include 3-acryloxypropyl groups.
  • methacryl groups include 3-methacryloxypropyl groups.
  • amino groups include 3-aminopropyl groups, and
  • N-(2-aminoethyl)-3-aminopropyl groups include hydroxyethyl groups, hydroxypropyl groups, and similar hydroxyalkyl groups; and hydroxyphenyl groups and similar hydroxyaryl groups.
  • hydroxyl groups include hydroxyethyl groups, hydroxypropyl groups, and similar hydroxyalkyl groups; and hydroxyphenyl groups and similar hydroxyaryl groups.
  • mercapto groups include
  • halogenated alkyi groups include
  • component (A) may be mixture of an organic compound having one
  • crosslinkable group in a molecule and an organic compound having at least two crosslinkable groups in a molecule.
  • a proportion of the latter compound in the mixture is not particularly limited, but, from the perspective of obtaining excellent crosslinkage, the content is preferably at least 15 mass (weight)% and more preferably at least 30 mass (weight)%.
  • the component (A) may be silicon-free or may include silicon.
  • the component (A) is silicon-free
  • the component (A) is preferably an organic compound having at least one aromatic ring in a molecule because forming a graphene structure is facilitated due to excellent efficiency when carbonizing by heating.
  • Examples of the component (A) described above include silicon-free aliphatic hydrocarbon compounds having a crosslinkable group at a molecular terminal and/or in the side molecular chains; silicon-free aliphatic hydrocarbon compounds having a crosslinkable group at a molecular terminal and/or in the side molecular chains and hetero-atoms other than carbon atoms, such as, for example, nitrogen, oxygen, or boron atoms, in the molecular chain; silicon-free aromatic hydrocarbon compounds having a crosslinkable group in the molecule; and silicon-free cyclic fatty compounds having a crosslinkable group in the molecule and also hetero-atoms other than carbon atoms, such as, for example, nitrogen, oxygen, or boron atoms.
  • al iphatic hydrocarbon compounds include compounds expressed by the following formulae:
  • R 1 represents a crosslinkable group, and examples thereof include aliphatic unsaturated groups, epoxy groups, acryl groups, methacryl groups, amino groups, hydroxyl groups, mercapto groups, and halogenated alkyl groups. Specific examples are the same as the groups described above. Additionally, “m” and “n” are integers greater than or equal to 1 ; and “x” is an integer greater than or equal to 1. [0035] Specific examples of the aromatic hydrocarbon compound include compounds expressed by the following general formula:
  • R 1 is a crosslinkable group, and examples thereof are the same as the groups described above. Additionally, “x” is an integer greater than or equal to 1.
  • R 2 represents an aromatic group with "x"-valency. Specifically, in this formula, when “x" is 1 , R 2 represents a monovalent aromatic group, and specific examples thereof include the groups described below.
  • aromatic hydrocarbon compound described above examples include a- or ⁇ -methylstyrene, a- or ⁇ -ethylstyrene, methoxystyrene, phenylstyrene, chlorostyrene, o-, m-, or p-methylstyrene, ethylstyrene, methylsilylstyrene, hydroxystyrene, cyanostyrene, nitrostyrene, aminostyrene, carboxystyrene, sulfoxystyrene, sodium styrenesulfonate, vinylpyridine, vinylthiophene, vinylpyrrolidone, vinylnaphthalene, vinylanthracene, and vinylbiphenyl.
  • R 2 represents a bivalent aromatic group, and specific examples thereof include the groups described below.
  • aromatic hydrocarbon compound described above examples include divinylbenzene, divinylbiphenyl, vinylbenzylchloride, divinylpyrindine, divinylthiophene, divinylpyrrolidone, divinylnaphthalene, divinylxylene, divinylethylbenzene, and divinylanthracene.
  • the aromatic hydrocarbon compound is preferably divinylbenzene because the pyrolyzing characteristics of the obtained cured product will be superior.
  • R 2 represents a trivalent aromatic group, and specific examples thereof include the groups described below.
  • aromatic hydrocarbon compound described above examples include trivinylbenzene and trivinylnaphthalene.
  • R 1 is a crosslinkable group, and examples thereof are the same as the groups described above.
  • cyclic compound having hetero-atoms include cyclic compounds expressed by the following formula:
  • R 1 is a crosslinkable group, and examples thereof are the same as the groups described above.
  • the component (A) including silicon is not particularly limited provided that it has a crosslinkable group, and examples thereof include silicon-containing monomers, oligomers, and polymers. Examples thereof include silanes constituted by structural units having silicon-silicon bonds, silazanes constituted by structural units having silicon-nitrogen-silicon bonds, siloxanes constituted by structural units having silicon-oxygen-silicon bonds, carbosilanes constituted by structural units having silicon-carbon-silicon bonds, and mixtures thereof.
  • silanes as the component (A) include those expressed by the following average unit formula:
  • R 3 each independently represent the crosslinkable group described above, a monovalent substituted or unsubstituted saturated aliphatic hydrocarbon group or aromatic hydrocarbon group having from 1 to 20 carbons, an alkoxy group, a hydrogen atom, or a halogen atom,
  • R 3 in the molecule are the crosslinkable group described above.
  • the saturated aliphatic hydrocarbon group is preferably an alkyl group, and the aromatic hydrocarbon group is preferably an aryl group and an aralkyl group.
  • the alkyl groups are preferably alkyl groups having from 1 to 12 carbons and more preferably alkyl groups having from 1 to 6 carbon atoms.
  • the alkyl groups are preferably any of the following: straight or branched chain alkyl groups, cycloalkyi groups, or cycloalkylene groups (alkyl groups that combine straight or branched chain alkylene groups (preferably methylene groups, ethylene groups, or similar alkylene groups having from 1 to 6 carbon atoms) with carbon rings (preferably rings having from 3 to 8 carbon atoms)).
  • the straight or branched chain alkyl groups preferably have from 1 to 6 carbon atoms and examples thereof include methyl groups, ethyl groups, n-propyl groups, isopropyl groups, butyl groups, t-butyl groups, pentyl groups, hexyl groups, and the like. Methyl groups are particularly preferable.
  • the cycloalkyi groups preferably have from 4 to 6 carbon atoms and examples thereof include cyclobutyl groups, cyclopentyl groups, cyclohexyl groups, and the like. Cyclopentyl groups and cyclohexyl groups are particularly preferable.
  • the aryl groups preferably have from 6 to 12 carbon atoms and examples thereof include phenyl groups, naphthyl groups, and tolyl groups.
  • the aralkyl groups preferably have from 7 to 12 carbon atoms.
  • Examples of aralkyl groups with from 7 to 12 carbon atoms include benzyl groups, phenethyl groups, and phenylpropyl groups.
  • the hydrocarbon group may have a substituent and examples of said substituent include fluorine atoms, chlorine atoms, bromine atoms, iodine atoms, and similar halogen atoms; hydroxyl groups; methoxy groups, ethoxy groups, n-propoxy groups, isopropoxy groups, and similar alkoxy groups having from 1 to 6 carbons; amino groups; amide groups; nitro groups; epoxy groups; and the like.
  • the substituent can be bonded at the hydrocarbon chain position, the saturated ring position, or the aromatic ring position.
  • alkoxy groups examples include methoxy groups, ethoxy groups, n-propoxy groups, and isopropoxy groups.
  • halogen atoms examples include fluorine atoms, chlorine atoms, bromine atoms, and iodine atoms.
  • the silane described above can be manufactured by methods known in the art. Examples of methods thereof include the method comprising dehalogenation of halosilanes in the presence of an alkali metal described in Macromolecules, 23, 3423 (1990), etc.; the method comprising anionic polymerization of disilenes described in Macromolecules, 23, 4494 (1990), etc.; the method comprising dehalogenation of halosilanes via electrode reduction described in J. Chem. Soc, Chem. Commun., 1 161 (1990); J. Chem. Soc, Chem.
  • silazane as the component (A) include those expressed by the following average unit formula:
  • R 3 each independently represent the crosslinkable group described above, a monovalent substituted or unsubstituted saturated aliphatic hydrocarbon group or aromatic hydrocarbon group having from 1 to 20 carbons, an alkoxy group, a hydrogen atom, or a halogen atom.
  • R 4 represents a hydrogen atom or a monovalent substituted or unsubstituted saturated aliphatic hydrocarbon group or aromatic hydrocarbon group having from 1 to 20 carbons.
  • At least one and preferably at least two R 3 in the molecule are the crosslinkable group described above.
  • saturated aliphatic hydrocarbon group the aromatic hydrocarbon group, the alkoxy group, and the halogen atoms are the same as those defined above for the silane.
  • the silazane described above can be prepared by methods known in the art. Examples of methods for preparing the silazane include those methods described in U.S. Patent Nos. 4312970, 4340619, 4395460, 4404153, 4482689, 4397828, 4540803, 4543344, 4835238, 4774312, 4929742, and 4916200. An alternate method is also described in J. Mater. Sci., 22, 2609 (1987).
  • siloxanes as the component (A) include those expressed by the following average unit formula:
  • At least one and preferably at least two R 3 in the molecule are the crosslinkable group described above.
  • saturated aliphatic hydrocarbon group the aromatic hydrocarbon group, the alkoxy group, and the halogen atoms are the same as those defined above for the silane.
  • the siloxane described above can be prepared by methods known in the art.
  • the method for preparing the siloxane is not particularly limited, but the most general methods of preparation include hydrolysis of organochlorosilanes. These and other methods are disclosed by Noll in, Chemistry and Technology of Silicones, Chapter 5 (Translated 2nd German Issue, Academic Press, 1968).
  • carbosilane as the component (A) include those expressed by the following average unit formula:
  • R 3 each independently represent the crosslinkable group described above, a monovalent substituted or unsubstituted saturated aliphatic hydrocarbon group or aromatic hydrocarbon group having from 1 to 20 carbons, an alkoxy group, a hydrogen atom, or a halogen atom.
  • R 5 and R 6 each independently represent a hydrogen atom or a monovalent substituted or unsubstituted saturated aliphatic hydrocarbon group or aromatic hydrocarbon group having from 1 to 20 carbons.
  • At least one and preferably at least two R 3 in the molecule are the crosslinkable group described above.
  • saturated aliphatic hydrocarbon group the aromatic hydrocarbon group, the alkoxy group, and the halogen atoms are the same as those defined above for the silane.
  • the carbosilane described above can be prepared by methods known in the art. Examples of methods for preparing the carbosilanes are described in Macromolecules, 21 , 30 (1988) and U.S. Patent 3293194.
  • the forms of the silane, silazane, siloxane, and carbosilane are not particularly limited, and may be solids, liquids, or paste-like forms, but, from the perspectives of handle-ability and the like, are preferably solids.
  • siloxanes constituted by units having silicon-oxygen-silicon bonds are preferable and polysiloxanes are more preferable in light of the following industrial benefits: the amount of silicon is not excessively low, such compounds have sufficient chemical stability, handling at room temperature in air is easy, raw material costs and fabrication process costs are low, and sufficient cost performance can be obtained.
  • the component (A) may be one type of the organic compound described above or may be a mixture of two or more types; and furthermore, may comprise a nitrogen-containing monomer such as acrylonitrile or the like as another component.
  • a content of the nitrogen-containing monomer is preferably not more than 50 mass (weight)%, and more preferably is in a range from 10 to 50 mass (weight)%.
  • the component (B) is a silicon-containing compound capable of crosslinking the component (A).
  • Examples of the component (B) described above include siloxanes, silanes, silazanes, carbosilanes, and mixtures thereof. Specific examples include monomers, oligomers, or polymers having Si-O-Si bonds and similar siloxanes; monomers, oligomers, or polymers having silane and Si-Si bonds and similar silanes; monomers, oligomers, or polymers having Si-(CH 2 ) n -Si bonds and similar silalkylenes; monomers, oligomers, or polymers having Si-(C 6 H 4 ) n -Si or
  • "n" is an integer greater than or equal to 1.
  • the component (B) preferably has silicon-bonded hydrogen atoms.
  • Examples of siloxanes as the component (B) include those expressed by the following average unit formula:
  • R 7 each independently represent a monovalent hydrocarbon group, a hydrogen atom, a halogen atom, an epoxy group-containing organic group, an acryl group- or methacryl group-containing organic group, an amino group-containing organic group, a mercapto group-containing organic group, an alkoxy group, or a hydroxy group
  • "a", "b", “c”, and “d” are numbers that are greater than or equal to 0 and less than or equal to 1 , and that satisfy
  • R 7 Specific examples of the monovalent hydrocarbon groups represented by R 7 include alky! groups, alkenyl groups, aralkyl groups, and aryl groups.
  • the alkyl groups are preferably alkyl groups having from 1 to 12 carbon atoms and more preferably alkyl groups having from 1 to 6 carbon atoms.
  • the alkyl groups may be any of the following: straight or branched chain alkyl groups, cycloalkyl groups, or cycloalkylene groups (alkyl groups that combine straight or branched chain alkylene groups (preferably methylene groups, ethylene groups, or similar alkylene groups having from 1 to 6 carbon atoms) with carbon rings (preferably rings having from 3 to 8 carbon atoms)).
  • the straight or branched chain alkyl groups preferably have from 1 to 6 carbon atoms and specific examples thereof include methyl groups, ethyl groups, n-propyl groups, isopropyl groups, butyl groups, t-butyl groups, pentyl groups, and hexyl groups.
  • the cycloalkyl groups preferably have from 4 to 6 carbon atoms and specific examples thereof include cyclobutyl groups, cyclopentyl groups, and cyclohexyl groups.
  • the alkenyl groups preferably have from 2 to 12 carbon atoms, and more preferably from 2 to 6 carbon atoms.
  • alkenyl groups having from 2 to 6 carbons include vinyl groups, propenyl groups, butenyi groups, pentenyl groups, and hexenyl groups, of which vinyl groups are preferable.
  • the aralkyl groups preferably have from 7 to 12 carbon atoms.
  • Specific examples of the aralkyl groups with from 7 to 12 carbon atoms include benzyl groups, phenethyl groups, and phenylpropyl groups.
  • the aryl groups preferably have from 6 to 12 carbon atoms and specific examples thereof include phenyl groups, naphthyl groups, and tolyl groups.
  • the monovalent hydrocarbon groups may have substituents.
  • substituents include fluorine atoms, chlorine atoms, bromine atoms, iodine atoms, or other halogens; hydroxyl groups; methoxy groups, ethoxy groups, n-propoxy groups, isopropoxy groups, or similar alkoxy groups.
  • substituted monovalent hydrocarbon groups include 3-chloropropyl groups, 3,3,3-trifluoropropy! groups, perfluorobutylethyl groups, and
  • halogen atoms represented by R 7 include fluorine atoms, chlorine atoms, bromine atoms, and iodine atoms, of which chlorine atoms are preferable.
  • epoxy group-containing organic groups represented by R 7 include 3-glycidoxypropyl groups, 4-glycidoxybutyl groups, or similar glycidoxyalkyl groups;
  • acryl group- or methacryl group-containing organic groups represented by R 7 include 3-acryloxypropyl groups, 3-methacryloxypropyl groups, 4-acryIoxybutyl groups, and 4-methacryloxybutyl groups, of which 3-methacryloxypropyl groups are preferable.
  • amino group-containing organic groups represented by R 7 include
  • Specific examples of the mercapto group-containing organic groups represented by R 7 include 3-mercaptopropyl groups and 4-mercaptobutyl groups.
  • alkoxy groups represented by R 7 include methoxy groups, ethoxy groups, n-propoxy groups, and isopropoxy groups, of which methoxy groups and ethoxy groups are preferable.
  • At least one group and preferably at least two groups represented by R 7 are alkenyl groups, hydrogen atoms, halogen atoms, epoxy-containing organic groups, acryl-containing organic groups, methacryl-containing organic groups, amino-containing organic groups, mercapto-containing organic groups, alkoxy groups, or hydroxy groups.
  • the aforementioned siloxanes may be structured at least from one of the structural units selected from (R ⁇ SiO ⁇ ), (R 7 2Si0 2/2 ), (R 7 Si0 3/2 ), and (Si0 4/2 ).
  • Specific examples are the following: a straight chain polysiloxane composed of (R 7 3 SiO
  • the number of repetitions of the structural units expressed by each of (R ⁇ SiO, ⁇ ), (R ⁇ SiC ⁇ ), (R 7 SiC>3/ 2 ), and (S1O4 / 2) is preferably within a range from 1 to 10,000, more preferably within a range from 1 to 1 ,000, and even more preferably within a range from 3 to 500.
  • siloxanes described above can be prepared by methods known in the art.
  • the method for preparing these siloxanes is not particularly limited, but the most general methods include hydrolysis of organochlorosilanes. These and other methods are disclosed by Noll in, Chemistry and Technology of Silicones, Chapter 5 (Translated 2nd German Issue, Academic Press, 1968).
  • the siloxanes described above may be silicon-containing copolymer compounds with polymers.
  • Examples of silicon-containing copolymer compounds that can be used as the siloxanes include silicon-containing copolymer compounds having Si-O-Si bonds and Si-Si bonds;
  • silicon-containing copolymer compounds having Si-O-Si bonds and Si-N-Si bonds;
  • silicon-containing copolymer compounds having Si-O-Si bonds and Si-(CH 2 ) n -Si bonds;
  • silicon-containing copolymer compounds having Si-O-Si bonds and Si-(C6H 4 ) overlook-Si bonds or
  • silanes can be expressed by the following general formula:
  • R 7 each independently represent a monovalent hydrocarbon group, a hydrogen atom, a halogen atom, an epoxy group-containing organic group, an acryl group- or methacryl group-containing organic group, an amino group-containing organic group, a mercapto group-containing organic group, an alkoxy group, or a hydroxy group.
  • at least one group and preferably at least two groups represented by R 7 are alkenyl groups, hydrogen atoms, halogen atoms, epoxy-containing organic groups, acryl-containing organic groups,
  • the silanes are expressed by the general formula: R ⁇ Si, or structured from at least one of the structural units selected from (R 7 3 Si), (R 7 2Si), (R 7 Si), and (Si). Specific examples are the following: a straight chain polysilane composed of (R 7 3 Si) and (R 7 2 Si) units; a cyclic polysilane composed of (R 7 2 Si) units; a branched chain polysilane (polysiline) composed of (R 7 Si) and (Si) units; a polysilane composed of (R 7 3 Si) and (R 7 Si) units; a polysilane composed of (R 7 3 Si) and (Si) units; a polysilane composed of (R 7 3 Si) and (Si) units; a polysilane composed of (R 7 Si) and (Si) units; a polysilane composed of (R 7 Si) and (Si) units; a polysilane composed of (R 7 2Si) and (R
  • the number of repetitions of the structural units expressed by each of (R 7 3 Si), (R 7 2 Si), (R 7 Si), and (Si) is preferably within a range from 2 to 10,000, more preferably within a range from 3 to 1 ,000, and even more preferably within a range from 3 to 500.
  • the silanes described above can be manufactured by methods known in the art. Examples of methods thereof include the method comprising dehalogenation of halosiianes in the presence of an alkali metal described in Macromolecules, 23, 3423 (1990), etc.; the method comprising anionic polymerization of disilenes described in Macromolecules, 23, 4494 (1990), etc.; the method comprising dehalogenation of halosiianes via electrode reduction described in J. Chem. Soc, Chem. Commun., 1 161 (1990); J. Chem. Soc, Chem.
  • the silanes described above may be silicon-containing copolymer compounds with other polymers.
  • Examples of silicon-containing copolymer compounds that can be used as the silanes include silicon-containing copolymer compounds having Si-Si bonds and Si-O-Si bonds;
  • silicon-containing copolymer compounds having Si-Si bonds and Si-N-Si bonds; silicon-containing copolymer compounds having Si-Si bonds and Si-(CH2) prevail-Si bonds; silicon-containing copolymer compounds having Si-Si bonds and Si-(C 6 H4) n -Si bonds or bonds; and the like.
  • silanes include silicon-containing compounds expressed by the general formula:
  • R 8 each represent substituted or unsubstituted monovalent hydrocarbon groups, "e” is an integer greater than or equal to 2, and R 9 is an "e"-valent organic group.
  • examples of the monovalent hydrocarbon groups represented by R 8 are the same as the monovalent hydrocarbon groups described as examples for R 7 .
  • "e” is an integer greater than or equal to 2, preferably an integer in a range from 2 to 6.
  • R 9 is a bivalent organic group.
  • R 9 is a trivalent organic group. Specific examples thereof include the groups expressed by the following formulae: Formula 8
  • silazanes are those expressed, for example, by the following average unit formula:
  • R 7 each independently represent a monovalent hydrocarbon group, a hydrogen atom, a halogen atom, an epoxy group-containing organic group, an acryl group- or methacryl group-containing organic group, an amino group-containing organic group, a mercapto group-containing organic group, an alkoxy group, or a hydroxy group.
  • at least one group and preferably at least two groups represented by R 7 are alkenyl groups, hydrogen atoms, halogen atoms, epoxy-containing organic groups, acryl-containing organic groups,
  • R 10 is a hydrogen atom or a substituted or unsubstituted monovalent hydrocarbon group
  • “a", "b", and “c” cannot be equal to 0 at the same time.
  • Examples of the monovalent hydrocarbon groups represented by R 10 are the same as the examples of the monovalent hydrocarbon groups represented by R 7 .
  • the moieties represented by R 10 are preferably hydrogen atoms or alkyl groups, and particularly are preferably hydrogen atoms or methyl groups.
  • the silazanes contain units selected from at least one of the following structural units:
  • Specific examples are the following: a straight chain polysilazane composed of (R 7 3 SiNR 10 ) and (R 7 2 SiNR' 0 ) units; a cyclic polysilazane composed of (R 7 2 SiNR 10 ) units; a branched chain polysilazane composed of (R 7 SiNR 10 ) and (SiNR 10 ) units; a polysilazane composed of (R 7 3 SiNR 10 ) and (R 7 SiNR 10 ) units; a polysilazane composed of (R 7 3 SiNR'°) and (SiNR' 0 ) units; a polysilazane composed of (R 7 SiNR 10 ) and (SiNR 10 ) units; a polysilazane composed of (R 7 2 SiNR 10 ) and (R 7 SiNR 10 ) units; a poly
  • R 7 SiNR 10 units; a polysilazane composed of (R 7 3 SiNR 10 ), (R 7 2 SiNR 10 ), and (SiNR 10 ) units; a polysilazane composed (R 7 3 SiNR 10 ), (R 7 SiNR 10 ), and (SiNR 10 ) units; a polysilazane composed (R 7 2 SiNR 10 ), (R 7 SiNR 10 ), and (SiNR 10 ) units; and a polysilazane composed of (R 7 3 SiNR 10 ),
  • (R 7 2 SiNR 10 ), (R 7 SiNR 10 ), and (SiNR 10 ) units The number of repetitions of the structural units expressed by each of (R 7 3 SiNR 10 ), (R 7 2 SiNR 10 ), (R 7 SiNR 10 ), and (SiNR 10 ) is preferably within a range from 2 to 10,000, more preferably within a range from 3 to 1 ,000, and even more preferably within a range from 3 to 500.
  • silazanes described above can be prepared by methods known in the art. Examples of methods for preparing the silazanes include those methods described in U.S. Patent Nos. 4312970, 4340619, 4395460, 4404153, 4482689, 4397828, 4540803, 4543344, 4835238, 4774312, 4929742, and 4916200. An alternate method is also described in J. Mater. Sci., 22, 2609 (1987).
  • the silazanes described above may be silicon-containing copolymer compounds with other polymers.
  • silicon-containing copolymer compounds that can be used as the polysilazanes include silicon-containing copolymer compounds having Si-N-Si bonds and Si-O-Si bonds; silicon-containing copolymer compounds having Si-N-Si bonds and Si-Si bonds;
  • silicon-containing copolymer compounds having Si-N-Si bonds and Si-(CH 2 ) n -Si bonds;
  • silicon-containing copolymer compounds having Si-N-Si bonds and Si-(C 6 H ) n -Si bonds or Si-(CH2CH 2 C6H 4 CH2CH2)n-Si bonds; and the like.
  • "n" has the same meaning as defined above.
  • R 7 each independently represent a monovalent hydrocarbon group, a hydrogen atom, a halogen atom, an epoxy group-containing organic group, an aery I group- or methacryl group-containing organic group, an amino group-containing organic group, a mercapto group-containing organic group, an alkoxy group, or a hydroxy group.
  • at least one group and preferably at least two groups represented by R 7 are alkenyl groups, hydrogen atoms, halogen atoms, epoxy-containing organic groups, acryl-containing organic groups,
  • R 1 ' is an alkylene group or an arylene group
  • "a", "b", and “c” cannot be equal to 0 at the same time.
  • the alkylene group represented by R" may be.
  • n has the same meaning as defined above.
  • the carbosilanes are structured from at least one of the structural units expressed by the following: (R 7 3 SiR"), (R 7 2 SiR n ), (R 7 SiR n ), and (SiR 11 ).
  • Specific examples include a straight chain polycarbosilane consisting of (R 7 3 SiR") and (R 7 2 SiR' ') units; a cyclic polycarbosilane consisting of (R 7 2 SiR") units; a branched chain polycarbosilane consisting of (R 7 SiR n ) and (SiR 1 1 ) units; a polycarbosilane consisting of (R 7 3 SiR n ) and (R 7 SiR n ) units; a polycarbosilane consisting of (R 7 3 SiR n ) and (SiR") units; a polycarbosilane consisting of (R 7 SiR n ) and (SiR") units; a polycarb
  • the number of repetitions of the structural units expressed by each of (R 7 3 SiR"), (R 7 2 SiR u ), (R 7 SiR n ), and (SiR 1 1 ) is preferably within a range from 2 to 10,000, more preferably within a range from 3 to 1 ,000, and even more preferably within a range from 3 to 500.
  • the carbosilanes described above can be prepared by methods known in the art. Examples of methods for preparing the carbosilanes are described in J. Dunogues, et al., Macromolecules, 21 , 3 (1988) and U.S. Patent 3293194.
  • the carbosilanes described above may be silicon-containing copolymer compounds with other polymers.
  • silicon-containing copolymer compounds that can be used as the carbosilanes include silicon-containing copolymer compounds having Si-(CH 2 ) n -Si bonds and Si-O-Si bonds; silicon-containing copolymer compounds having Si-(CH 2 ) n -Si bonds and Si-Si bonds; silicon-containing copolymer compounds having Si-(CH 2 ) n -Si bonds and Si-N-Si bonds;
  • silicon-containing copolymer compounds having Si-(CH 2 ) n -Si bonds and Si-(C 6 H 4 ) n -Si bonds;
  • silicon-containing copolymer compounds having Si-(C 6 H 4 ) n -Si bonds and Si-O-Si bonds;
  • silicon-containing copolymer compounds having Si-(C 6 H 4 ) n -Si bonds and Si-Si bonds;
  • silicon-containing copolymer compounds having Si-(C 6 H ) n -Si bonds or
  • n has the same meaning as defined above.
  • the component (b) is preferably a siloxane and more preferably a polysiloxane expressed by the following average unit formula:
  • R 7 each independently represent a monovalent hydrocarbon group, a hydrogen atom, a halogen atom, an epoxy group-containing organic group, an acryl group- or methacryl group-containing organic group, an amino group-containing organic group, a mercapto group-containing organic group, an alkoxy group, or a hydroxy group
  • "a", "b", “c”, and “d” are numbers that are greater than or equal to 0 and less than or equal to 1 , and that satisfy
  • crosslinking reaction examples include addition reactions such as a hydrosilylation reaction, a Michael addition reaction, a Diels-Alder reaction, and the like;
  • condensation reactions such as dealcoholization, dehydrogenation, dewatering, deamination, and the like; ring-opening reactions such as epoxy ring-opening, ester ring-opening, and the like; and radical reactions initiated by a peroxide, UV, or the like.
  • a mixture thereof can be hydrosilylation reacted in the presence of a hydrosilylation-reaction catalyst.
  • hydrosilylation-reaction catalyst examples include fine platinum powder, platinum black, fine platinum-carrying silica powder, fine platinum-carrying activated carbon, chloroplatinic acid, platinum tetrachloride, an alcoholic solution of chloroplatinic acid, an olefin complex of platinum, and an alkenylsiloxane complex of platinum.
  • the amount in which the hydrosilylation-reaction catalyst can be used is not particularly limited.
  • the catalyst is preferably used in such an amount that, in terms of mass (weight), the content of metal atoms in the catalyst is in a range from 0.1 to 1 ,000 ppm, and more preferably in a range from 1 to 500 ppm, with respect to a total weight of the component (A) and the component (B).
  • the respective amounts thereof are not particularly limited.
  • the contents are such that the silicon-bonded hydrogen atoms in the component (B) are in a range from 0.1 to 50 moles, preferably in a range from 0.1 to 30 moles, and more preferably in a range from 0.1 to 10 moles, per one mole of the aliphatic unsaturated groups in the component (A).
  • a reason for this is because when the amount of the component (B) is less than the lower limit of the range described above, the carbonization yield when baking the obtained cured product will tend to decline. On the other hand, when the amount exceeds the range described above, the characteristics as an electrode active material of the silicon-containing carbon-based composite material obtained by baking the obtained cured product will tend to decline.
  • component (A) comprises aliphatic unsaturated groups and the component (B) comprises aliphatic unsaturated groups, acryl groups, methacryl groups, or silicon-bonded hydrogen atoms
  • a mixture thereof can be radical reacted by a radical initiator using heat and/or light.
  • radical initiator examples include dialkyl peroxides, diacyl peroxides, peroxy esters, peroxy dicarbonates, and similar organic peroxides; and organic azo compounds.
  • organic peroxides include dibenzoyl peroxide, bis-p-chlorobenzoyl peroxide, bis-2,4-dichlorobenzoyI peroxide, di-t-butyl peroxide, dicumyl peroxide, t-butyl perbenzoate, 2,5-bis(t-butyl peroxy)-2,3-dimethylhexane, t-butyl peracetate, bis(o-methylbenzoyl peroxide), bis(m-methylbenzoyl peroxide), bis(p-methylbenzoyl peroxide), 2,3-dimethylbenzoyl peroxide, 2,4-dimethylbenzoyl peroxide, 2,6-dimethylbenzoyl peroxide, 2,3,4-tri
  • the amount in which the radical initiator can be used is not particularly limited, but is preferably in a range from 0.1 to 10 mass (weight)%, and more preferably in a range from 0.5 to 5 mass (weight)%, with respect to the total weight of the component (A) and the component (B).
  • the component (A) comprises aliphatic unsaturated groups and the component (B) comprises aliphatic unsaturated groups, aery) groups, methacryl groups, or silicon-bonded hydrogen atoms
  • the amounts thereof are not particularly limited.
  • the contents are such that the aliphatic unsaturated groups, acryl groups, methacryl groups, or silicon-bonded hydrogen atoms in the component (B) are in a range from 0.1 to 50 moles, preferably in a range from 0.1 to 30 moles, and more preferably in a range from 0.1 to 10 moles, per one mole of the aliphatic unsaturated groups in the component (A).
  • a reason for this is because when the amount of the component (B) is less than the lower limit of the range described above, the carbonization yield when baking the obtained cured product will tend to decline. On the other hand, when the amount exceeds the range described above, the characteristics as an electrode active material of the silicon-containing carbon-based composite material obtained by baking the obtained cured product will tend to decline.
  • the cured product obtained by crosslinking the component (A) and the component (B) is formed, for example, by manufacturing according to methods I or II described below, and then subjecting the product to a step of baking.
  • the subsequent baking step is preferably carried out after pulverizing the obtained precured mixture so that an average diameter of particles thereof is from 0.1 to 30 ⁇ and preferably from 1 to 20 ⁇ .
  • the cured product preferably used in the present invention is constituted by spherical particles.
  • a crosslinkable composition comprising the component (A) and the component (B) is preferably crosslinked by spraying said crosslinkable composition into hot air or crosslinked after emulsifying or dispersing said crosslinkable composition in a
  • fine particles of the cured product can be obtained by spraying a crosslinkable composition comprising the component (A), the component (B), and the hydrosilylation-reaction catalyst in particulate form into hot-air, and crossl inking by hydrosilylation reaction.
  • fine particles of the cured product can be formed by adding a crosslinkable composition comprising the component (A), the component (B), and the hydrosilylation-reaction catalyst to an aqueous solution of an emulsifier, emulsifying by agitation to form fine particles of the crosslinkable composition, and, thereafter, crosslinking by hydrosilylation reaction.
  • the emulsifier is not particularly limited, and specific examples thereof include ionic surfactants, nonionic surfactants, and mixtures of ionic surfactants and nonionic surfactants.
  • the emulsifier is preferably a mixture of one or more types of ionic surfactant and one or more types of nonionic surfactant.
  • silica colloidal silica
  • a metallic oxide such as titanium oxide
  • the diameter of the cured product particles is not particularly limited, but in order to form a silicon-containing carbon-based composite material, through baking, with an average diameter from 1 to 20 ⁇ ⁇ ⁇ , which is suitable for an electrode active material, the average diameter is preferably in a range from 5 to 30 ⁇ , and more preferably is in a range from 5 to 20 ⁇ ⁇ .
  • the cured product particles are preferably further subjected to heat treating in air at a temperature from 150°C to 300°C.
  • the silicon-containing carbon-based composite material of the present invention can be . obtained via a process of heat treating (baking) the cured product of the component (A) and the component (B) along with a carbonaceous matter (C).
  • the carbonaceous matter (C) is preferably coated on a surface of the cured product obtained by crosslinking the component (A) and the component (B) to form composite particles.
  • An amount of the component (C) coated on the surface of the cured product of the component (A) and the component (B) is preferably from 0.5 to 20 mass (weight)%, more preferably from 1 to 10 mass (weight)%, and even more preferably from 1 to 5 mass (weight)% in the composite particles.
  • the method of preparing the composite particles is not particularly limited, and examples thereof include (i) a method of mixing/agitating the cured product obtained by crosslinking the component (A) and the component (B), and the carbonaceous matter (C) while supplying mechanical energy; and, when preparing the cured particles by crosslinking the component (A) and the component (B) in an emulsified state in an aqueous dispersing medium, (ii) a method of adsorbing the carbonaceous matter (C) on the surface of the cured product by dispersing the carbonaceous matter (C) in the aqueous dispersing medium.
  • the pulverizing apparatus, mixing device, and surface treating device used when (i) mixing/agitating the cured product obtained by crosslinking the component (A) and the component (B), and the carbonaceous matter (C) while supplying mechanical energy are not particularly limited.
  • the pulverizing, mixing, and surface treating may be performed using a dry method or a wet method.
  • Examples of the pulverizing apparatus include apparatuses that pulverize by pressure or striking, such as jaw crushers, gyratory crushers, roll crushers, roll mills, automatic mortars, and the like; apparatuses where a strike plate is fixed around a high-speed rotating rotor, that pulverize products using shearing forces and the like caused by the rotor and the strike plate such as hammer mills, impact crushers, pin mills, atomizers, pulverizers, and the like; apparatuses where a roll or ball is pressed against the top of a ring and rotated, the product being pulverized by being placed between the ring and the roll or ball and crushed such as ring roller mills, ring ball mills, centrifugal roller mills, ball bearing mills, angmills, and the like; pulverizing apparatus provided with a cylindrical pulverizing chamber, that pulverize by a ball or rod being inserted into the pulverizing chamber as a
  • Examples of the mixing device include mixers that have a mixing shaft in a mixing vessel, where a mixing blade is attached to the shaft and particles are mixed such as super mixers, high-speed mixers, Henschel mixers, and the like; continuous mixers comprising a main shaft provided with a vertical cylinder having a particle insertion opening and a mixing blade, where the main shaft is supported by an upper bearing and the discharge side is free such as Flexomix mixers and the like; and continuous mixers where mixing is performed by loading raw material into an upper portion of a disk having an agitation pin, and rotating the disk at a high speed to produce shearing forces such as flow jet mixers, spiral pin mixers, and the like.
  • mixers that have a mixing shaft in a mixing vessel, where a mixing blade is attached to the shaft and particles are mixed such as super mixers, high-speed mixers, Henschel mixers, and the like
  • continuous mixers comprising a main shaft provided with a vertical cylinder having a particle insertion opening and a mixing blade,
  • Examples of the surface treating device include Hybridizer®, manufactured by Nara
  • the composite particles can be obtained by removing the water after adsorbing the carbonaceous matter (C) on the surface of the cured product by dispersing the carbonaceous matter (C) in the aqueous dispersing medium.
  • the component (A) and the component (B) are emulsified in the aqueous dispersing medium and, thereafter, the carbonaceous matter (C) is dispersed in the emulsion.
  • the baking conditions are not particularly limited, but baking is preferably carried out in an inert gas or in vacuum at a temperature of from 300°C to 1 ,500°C.
  • the inert gas include nitrogen, helium, and argon.
  • the inert gas may comprise hydrogen gas or similar reducing gases.
  • the composite material of the present invention may contain trace amounts of hydrogen.
  • the baking temperature is more preferably in a range from 500°C to 1 ,000°C.
  • Baking time is not particularly limited, but can be set to a range from 10 minutes to 10 hours, and preferably is set to a range from 30 minutes to 3 hours.
  • the heating method and type of the carbonization furnace is not particularly limited, and carbonization can be carried out in a fixed-bed type or a fluidized-bed type carbonization furnace, provided that the furnace is capable of heating the product to an appropriate temperature.
  • Specific examples of the carbonization furnace include Reidhammer furnace, tunnel furnace, single type furnace, Oxynon furnace, roller hearth kiln, pusher kiln, batch type rotary kiln, and continuous type rotary kiln.
  • the carbonaceous matter (C) is not particularly limited provided that it is constituted mainly by carbon, and examples thereof include activated carbon, natural graphite, artificial graphite, various coke powders, and mesophase carbon; vapor-grown carbon fibers, pitch-based carbon fibers, PAN (Polyacrylonitrile) -based carbon fibers, and similar carbon fibers; acetylene black, furnace black, ketjen black, gas black, and similar carbon blacks; carbon nanofiber; carbon nanotube; and the like.
  • the silicon-containing carbon-based composite material of the present invention can be constituted by particles having an average diameter from 5 nm to 50 ⁇ .
  • the average diameter is preferably from 10 nm to 40 ⁇ , more preferably from 100 nm to 30 ⁇ , and even more preferably from 1 ⁇ to 20 ⁇ .
  • An amount of the carbon included in the silicon-containing carbon-based composite material of the present invention is preferably from 1 to 50 mass (weight)%, more preferably from 5 to 30 mass (weight)%, and even more preferably from 5 to 20 mass (weight)%.
  • the silicon-containing carbon-based composite material of the present invention when the amount is within this range, even when using the silicon-containing carbon-based composite material of the present invention alone as the electrode active material, the silicon-containing carbon-based composite material will have suitable conductivity, and declines in the charge and discharge capacity of the electrode can be suppressed.
  • the surface of the silicon-containing carbon-based composite material of the present invention has a coating layer constituted from carbon.
  • a thickness of the carbon coating layer is not particularly limited, but is preferably from 5 nm to 2 ⁇ , more preferably from 10 nm to 1 ⁇ , and even more preferably from 20 nm to 100 nm.
  • the core portion covered by the carbon coating layer is the baked product of the cured product of the component (A) and the component (B).
  • the silicon-containing carbon-based composite material obtained by the process described above has silicon, carbon, and oxygen as main components and can be expressed by the following average composition formula: Sii .ooCfO g H h .
  • “f , "g”, and “h” are numbers that satisfy 0.5 ⁇ f ⁇ l 00, 0 ⁇ g ⁇ 5, and 0 ⁇ h ⁇ 10, respectively.
  • the obtained carbon surface-coated silicon-containing carbon-based composite material can be used as the electrode active material.
  • the electrode active material of the present invention can be in a particulate form and, in this case, the average diameter thereof is preferably from 1 to 50 ⁇ , more preferably from 1 to 40 ⁇ , and even more preferably from 1 to 30 ⁇ .
  • the electrode active material comprising the carbon surface-coated silicon-containing carbon-based composite material of the present invention has high reversible capacity and stable charge and discharge cycle characteristics, and can be used in the manufacturing of an electrode that has little electrical potential loss when lithium is discharged, via a simple manufacturing process.
  • the electrode active material can be suitably used as an electrode active material for nonaqueous electrolyte secondary batteries.
  • the electrode active material is particularly suitable as the active material of electrodes of lithium or lithium-ion secondary batteries.
  • the electrode of the present invention is characterized by comprising the electrode active material described above.
  • the form and method for fabricating the electrode are not particularly limited. Examples of the method for fabricating the electrode of the present invention include methods in which the electrode is fabricated by mixing the silicon-containing carbon-based composite material with a binder, and methods in which the electrode is fabricated by mixing the silicon-containing carbon-based composite material with a binder and a solvent, contact binding or coating the obtained paste on a current collector and, thereafter, drying the electrode.
  • a thickness of the paste coated on the current collector is, for example, about from 30 to 500 ⁇ and preferably about from 50 to 300 ⁇ . Means for drying after coating are not particularly limited, but heating under vacuum drying is preferable.
  • a thickness of the electrode material on the current collector after drying is about from 10 to 300 ⁇ and preferably about from 20 to 200 ⁇ .
  • the electrode can be fabricated by orienting the material in a single axial direction and forming the material into a fabric or similar structure, or bundling or weaving metal, conducting polymer, or similar conductive fibers.
  • Terminals may be incorporated as necessary when forming the electrode.
  • the current collector is not particularly limited, and specific examples thereof include metal meshes and foils made from copper, nickel, alloys thereof, and the like.
  • binder examples include fluorine-based (e.g. polyvinylidene fluoride and polytetrafluoroethylene) resins and styrene-butadiene resins.
  • An amount in which the binder is used is not particularly limited, but a lower limit thereof is in a range from 5 to 30 parts by mass (weight) and preferably in a range from 5 to 20 parts by mass (weight), per 100 parts by mass (weight) of the silicon-containing carbon-based composite material.
  • a method for preparing the paste is not particularly limited, and examples thereof include methods in which a mixed liquid (or dispersion) comprising the binder and an organic solvent is mixed with the silicon-containing carbon-based composite material.
  • a solvent that can dissolve or disperse the binder is generally used as the solvent, and specific examples thereof include N-methylpyrrolidone, ⁇ , ⁇ -dimethylformamide, and similar organic solvents.
  • An amount in which the solvent is used is not particularly limited provided that when mixed with the binder, the mixture thereof has a paste-like form, but generally the amount is in a range from 0.01 to 500 parts by mass (weight), preferably in a range from 0.01 to 400 parts by mass (weight), and more preferably in a range from 0.01 to 300 parts by mass (weight), per 100 parts by mass (weight) of the silicon-containing carbon-based composite material.
  • Additives may be compounded in the electrode of the present invention as desired.
  • a conductivity promoter may be added to the electrode during manufacturing.
  • An amount in which the conductivity promoter is used is not particularly limited, but is in a range from 2 to 60 parts by mass (weight), preferably in a range from 5 to 40 parts by mass (weight), and more preferably in a range from 5 to 20 parts by mass (weight) per 100 parts by mass (weight) of the silicon-containing carbon-based composite material. When the amount is within this range, conductivity will be excellent and declines in the charge and discharge capacity of the electrode can be suppressed.
  • Examples of the conductivity promoter include carbon blacks (e.g. ketjen black, acetylene black), carbon fibers, carbon nanotubes, and the like.
  • a single conductivity promoter may be used or a combination of two or more types of conductivity promoters can be used.
  • the conductivity promoter can, for example, be mixed with the paste comprising the silicon-containing carbon-based composite material, the binder, and the solvent.
  • Graphite or a similar electrode active material may be compounded in the electrode of the present invention as another optional additive.
  • the electricity storage device of the present invention is characterized by comprising the electrode described above.
  • Examples of the electricity storage device include lithium primary batteries, lithium secondary batteries, lithium-ion secondary batteries, capacitors, hybrid capacitors (redox capacitors), organic radical batteries, and dual carbon batteries, of which lithium or lithium-ion secondary batteries are preferable.
  • the lithium-ion secondary battery may be manufactured according to a generally known method using battery components including a negative electrode comprising the electrode described above, a positive electrode capable of storing and discharging lithium, an electrolyte solution, a separator, a current collector, a gasket, a sealing plate, a case, and the like.
  • the lithium secondary battery may be manufactured according to a generally known method using battery components including a positive electrode constituted by the electrode described above, a negative electrode constituted by metallic lithium, an electrolyte solution, a separator, a current collector, a gasket, a sealing plate, a case, and the like.
  • FIGS. 1 and 2 Preferable forms (lithium or lithium-ion secondary batteries) of the battery of the present invention are illustrated in detail in FIGS. 1 and 2.
  • FIG. 1 is a schematic breakdown cross sectional view of a lithium-ion secondary battery (button battery) that is an example of the battery of the present invention.
  • the lithium-ion secondary battery illustrated in FIG. 1 comprises a cylindrical case 1 having a bottom and an open top, a cylindrical gasket 2 that is open on both ends and has an inner circumference that is substantially the same as the outer circumference of the case 1 , a washer 3, a SUS plate 4, a current collector 5, a negative electrode 6 having the silicon-containing carbon-based composite material of the present invention as an electrode active material thereof, a separator 7, a positive electrode 8, a current collector 9, and a sealing plate 10.
  • the washer 3, having a substantially ring-like shape and a size that is slightly smaller than the inner circumference of the case 1 is housed in the case 1 of the lithium-ion secondary battery illustrated in FIG. 1.
  • the SUS plate 4, having a substantially disc-like shape and a size that is slightly smaller than the inner circumference of the case 1 is stacked on the washer 3.
  • the current collector 5 and the negative electrode 6, both having substantially disc-like shapes and sizes that are slightly smaller than the inner circumference of the case 1 are provided on the SUS plate 4.
  • the separator 7, which is a single-layer disc-like member and has a size substantially the same as the inner circumference of the case 1, is stacked on the negative electrode 6.
  • the separator 7 is impregnated with an electrolyte solution.
  • the separator 7 may be constituted by two or more disc-like members.
  • the positive electrode 8, having a size that is substantially the same as that of the negative electrode 6, and the current collector 9 having a size that is substantially the same as that of the current collector 5 are provided on the separator 7.
  • the current collector 5 is constituted by a mesh, foil, or the like made from copper, nickel, or similar metal
  • the current collector 9 is constituted by a mesh, foil, or the like made from aluminum or a similar metal.
  • the current collector 5 and the current collector 9 are bonded and integrated with the negative electrode 6 and the positive electrode 8, respectively.
  • the gasket 2 is fitted on a wall face of the case 1 and; furthermore, an inner circumferential face of the cylindrical sealing plate 10, having a bottom and an open lower face and a size that is slightly larger than that of the gasket 2, is fitted on an outer circumferential face of the gasket 2.
  • the case 1 is insulated from the sealing plate 10 by the gasket 2, and a button battery having the case 1 , the gasket 2, the washer 3, the SUS plate 4, the current collector 5, the negative electrode 6, the separator 7, the positive electrode 8, the current collector 9, and the sealing plate 10, with a common axis, is formed.
  • the positive electrode 8 in the lithium-ion secondary battery illustrated in FIG. 1 is not particularly limited and, for example, can be constituted by positive electrode active materials, conductivity promoters, binders, and the like.
  • the positive electrode active materials include LiCo0 2 , LiNi0 2 , LiMn 2 0 4 , and similar metallic oxides; LiFeP0 4 , Li 2 FeSi0 4 , and similar polyanion oxides; spinel LiMn 2 0 4 ; and the like.
  • a single positive electrode active material may be used or a combination of two or more types of positive electrode active materials can be used.
  • Examples of the conductivity promoters and the binders include those described above.
  • FIG. 2 is a breakdown cross sectional view of a lithium secondary battery (button battery) that is an example of the battery of the present invention, fabricated according to the Practical Examples.
  • the lithium secondary battery illustrated in FIG. 2 comprises a cylindrical case 1 having a bottom and an open top, a cylindrical gasket 2 that is open on both ends and has an inner circumference that is substantially the same as the outer circumference of the case 1 , a washer 3, a SUS plate 4, a negative electrode 6 constituted by metallic lithium, a separator 7, a positive electrode 8 having the silicon-containing carbon-based composite material of the present invention as an electrode active material thereof, a current collector 9', and a sealing plate 10.
  • the washer 3, having a substantially ring-like shape and a size that is slightly smaller than the inner circumference of the case 1 is housed in the case 1 of the lithium secondary battery illustrated in FIG. 2.
  • the SUS plate 4, having a substantially disc-like shape and a size that is slightly smaller than the inner circumference of the case 1 is stacked on the washer 3.
  • the negative electrode 6, having a substantially disc-like shape and a size that is slightly smaller than the inner circumference of the case 1 is provided on the SUS plate 4.
  • the separator 7, which is a single-layer disc-like member and has a size substantially the same as the inner circumference of the case 1 is stacked on the negative electrode 6.
  • the separator 7 is impregnated with an electrolyte solution.
  • the separator 7 may be constituted by two or more disc-like members.
  • the positive electrode 8 and the current collector 9', having sizes that are substantially the same as that of the negative electrode 6, are provided on the separator 7.
  • the current collector 9' is constituted by a mesh, foil, or the like made from copper, nickel, or similar metal, and is bonded and integrated with the positive electrode 8.
  • the gasket 2 is fitted on a wall face of the case 1 and; furthermore, an inner circumferential face of the cylindrical sealing plate 10, having a bottom and an open lower face and a size that is slightly larger than that of the gasket 2, is fitted on an outer circumferential face of the gasket 2.
  • the case 1 is insulated from the sealing plate 10 by the gasket 2, and a button battery having the case 1 , the gasket 2, the washer 3, the SUS plate 4, the negative electrode 6, the separator 7, the positive electrode 8, the current collector 9', and the sealing plate 10, with a common axis, is formed.
  • the electrolyte solutions included in the lithium or lithium-ion secondary batteries illustrated in FIGS. 1 and 2 are not particularly limited, and commonly known electrolyte solutions can be used.
  • a non-aqueous lithium or lithium-ion secondary battery can be manufactured by using a solution in which an electrolyte is dissolved in an organic solvent as the electrolyte solution.
  • Examples of the electrolyte include LiPF 6 , LiC10 4 , LiBF 4 , LiClF 4 , LiAsF 6 , LiSbF 6 , LiA10 4 , LiAlCl 4 , LiCl, Lil, and similar lithium salts.
  • Examples of the organic solvent include carbonates (e.g.
  • a single organic solvent may be used or a mixed solvent comprising two or more types of organic solvents can be used.
  • a concentration of the electrolyte per one liter of the electrolyte solution is, for example, about from 0.3 to 5 moles, preferably about from 0.5 to 3 moles, and more preferably about from 0.8 to 1.5 moles.
  • the separators 4 in the lithium or lithium-ion secondary batteries illustrated in FIGS. 1 and 2 are not particularly limited, and a commonly known separator can be used. Examples thereof include porous polypropylene nonwovens, porous polyethylene nonwovens, and other
  • the electricity storage device of the present invention is not limited to the examples illustrated in FIGS. 1 and 2 and, for example, can be applied to various forms such as stacked, packed, button, gum, battery pack, and rectangular batteries.
  • the electricity storage device of the present invention particularly the lithium or lithium-ion secondary battery, is suitable for use as a power supply for video cameras, computers, word processors, portable stereos, cellular phones, and other mobile, small electronic devices; a power supply for hybrid vehicles and electric vehicles; and a power supply for electricity storage.
  • the electrode active material of the present invention has high reversible capacity and stable charge and discharge cycle characteristics, and has high initial charge and discharge efficiency. Therefore, the electrode active material of the present invention is suitable for an electrode of an electricity storage device, particularly of a lithium or lithium-ion secondary battery. Additionally, the electrode active material of the present invention uses inexpensive raw materials, and can be manufactured via a simple manufacturing process. Moreover, the electrode of the present invention can impart high reversible capacity, stable charge and discharge cycle characteristics, and high initial charge and discharge efficiency to a battery. As a result, the electricity storage device of the present invention can have high reversible capacity, stable charge and discharge cycle characteristics, and high initial charge and discharge efficiency. Examples
  • JSM-5800LV manufactured by JEOL Ltd.
  • JED-2100 manufactured by JEOL Ltd.
  • Charge and discharge characteristics of the lithium secondary battery using the composite material of the present invention were measured as described below using an HJR-1 10m SM6 (manufactured by Hokuto Denko Corporation). Charging was performed using a constant current of 0.1 C (70.0 mAh/g), which is 1/10 of the theoretical capacity (700 mAh/g, expressed as 1 .OC), per 1 g (mass) of the silicon-containing carbon-based composite material. The charging was considered complete at the point when the current value became 1 /10 after the battery voltage had reached 0.02 V and the voltage had been kept constant, The charging capacity was calculated at this point.
  • a solution comprising 2.4 g of polystyrene at a degree of polymerization of about 2,000 and 3.0 g of toluene; and a silicone composition comprising 24 g of an organopolysiloxane expressed by the formula:
  • the silicone composition was crosslinked by being put in a 1 10°C oven for 30 minutes.
  • the silicon-containing crosslinked particles were uniformly dispersed in the polystyrene.
  • the silicon-containing crosslinked particles were extracted with toluene, and were confirmed to have a regular spherical shape with an average diameter of 2.5 ⁇ (FIG. 3).
  • Black particles were obtained by mixing 4.75 g of the silicon-containing crosslinked particles obtained above and 0.25 g of acetylene black for five minutes in a ball mill. The particles were placed into an SSA-S grade alumina crucible and baked in a muffle furnace for two hours at 600°C in a nitrogen atmosphere, followed by one hour at 1 ,000°C. After cooling, black particles were obtained at a 75% yield. An amount of carbon coated on the surface of the obtained carbon surface-coated silicon-containing carbon-based composite material was 6.6 mass (weight)% of the silicon-containing carbon-based composite material. Subjecting the obtained black particles to SEM observation revealed that the black particles were spherical particles having an average diameter of about 2.45 ⁇ (FIG. 4).
  • TEM transmission electron microscope
  • EDX energy dispersive x-ray analysis
  • Metallic lithium was used for the electrode as a counterelectrode; a mixed solvent comprising ethylene carbonate and diethyl carbonate at a volume ratio of 1 : 1 , in which lithium
  • a crosslinkable composition was prepared by mixing 15.49 g of DVB570 (manufactured by Nippon Steel Chemical Co., Ltd.; Main components: divinylbenzene and vinyl ethylbenzene;
  • Black particles were obtained by mixing 4.75 g of the silicon-containing crosslinked particles obtained above and 0.25 g of acetylene black for five minutes in a ball mill. As in Practical Example 1 , the cured product particles were placed into an SSA-S grade alumina crucible and baked. After cooling, black particles were obtained at a 62% yield. An amount of carbon coated on the surface of the obtained carbon surface-coated silicon-containing carbon-based composite material was 7.6 mass (weight)% of the silicon-containing carbon-based composite material.
  • the black particles were spherical particles having an average diameter of about from 1 .0 to 5.0 ⁇ , constituted mainly of the SiOC component, and that the black particles were composite particles in which the surfaces of the particles were coated with carbon particles having a diameter from 30 to 40 nm.
  • a crosslinkable composition was prepared by mixing 100 g of DVB630 (manufactured by
  • This mixture was cured in nitrogen at a temperature of 80°C for 30 minutes and then further cured for 60 minutes at 200°C. Thereafter, the cured product was cooled and crushed using a pulverizer having a clearance set to 20 ⁇ ⁇ ⁇ . Thereby, particles having an average diameter of about 15 ⁇ were obtained.
  • Black particles were obtained by mixing 4.75 g of the silicon-containing crosslinked particles obtained above and 0.25 g of ketjen black for five minutes in a ball mill. As in Practical Example 1 , the particles were placed into an SSA-S grade alumina crucible and baked. After cooling, black particles were obtained at a 62% yield. An amount of carbon coated on the surface of the obtained carbon surface-coated silicon-containing carbon-based composite material was 7.6 mass (weight)% of the silicon-containing carbon-based composite material.
  • the black particles were particles having an average diameter of about from 10.0 to 15.0 ⁇ , constituted mainly of the SiOC component, and that the black particles were composite particles in which the surfaces of the particles were coated with carbon particles having a diameter from 30 to 40 nm.
  • a crosslinkable composition was prepared by mixing 500 g of an organopolysiloxane expressed by the formula:
  • trimethylsiloxy groups (viscosity: 20 mPa- s; silicon-bonded hydrogen atoms content: 1 .58 mass (weight)%; included in an amount such that 1.2 moles of the silicon-bonded hydrogen atoms in the copolymer is included per one mole of vinyl groups in the organopolysiloxane); an isopropyl alcohol solution of chloroplatinic acid (included in an amount such that, in terms of mass (weight), l O.ppm of platinum metal was included with respect to the total weight of the organopolysiloxane and the methyl hydrogen siloxane copolymer); and 2-methyl-3-butyne-2-ol (included in an amount such that, in terms of mass (weight), 200 ppm of 2-methyl-3-butyne-2-ol was included with respect to the total weight of the RMS organopolysiloxane and the methyl hydrogen siloxane copolymer).
  • Black particles were obtained by mixing 4.75 g of the silicon-containing crosslinked particles obtained above and 0.25 g of acetylene black for five minutes in a Hybridizer®, manufactured by Nara Machinery Co., Ltd. As in Practical Example 1, the particles were placed into an SSA-S grade alumina crucible and baked. After cooling, black particles were obtained at an 80% yield. An amount of carbon coated on the surface of the obtained carbon surface-coated silicon-containing carbon-based composite material was 6.1 mass (weight)% of the silicon-containing carbon-based composite material.
  • the black particles were composite particles having an average diameter of about from 2.0 to 50.0 ⁇ in which the cores of the particles were constituted mainly of the SiOC component, and the surfaces of the particles were coated with carbon particles having a diameter from 30 to 40 nm.
  • the carbon coated silicon-containing crosslinked particles of this Practical Example were prepared the same as those in Practical Example 4.
  • the battery characteristics are shown in Table 1 .
  • the carbon coated silicon-containing crosslinked particles of this Practical Example were prepared the same as those in Practical Example 4.
  • the battery characteristics are shown in Table 1 .
  • a crosslinkable composition was prepared by mixing 15.49 g of DVB570 (manufactured by Nippon Steel Chemical Co., Ltd.; Main components: divinylbenzene and vinyl ethylbenzene;
  • the cured product particles were placed into an SSA-S grade alumina crucible and baked. After cooling, black particles were obtained at a 62% yield. Subjecting the obtained black particles to SEM and EDX observation revealed that the black particles were spherical particles having an average diameter of about from 1 .0 to 5.0 ⁇ , constituted mainly of the SiOC component.

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Abstract

L'invention porte sur un matériau composite approprié pour être utilisé comme électrode d'un dispositif d'accumulation d'électricité, en particulier pour une batterie secondaire au lithium ou au lithium-ion, sur une matière active d'électrode constituée du matériau composite, sur une électrode contenant la matière active et sur un dispositif d'accumulation d'électricité comprenant l'électrode. A l'aide d'un matériau composite à base de carbone contenant du silicium revêtu de carbone en surface servant de matière active d'électrode, le matériau composite est obtenu par : formation d'un produit durci par réticulation (A) d'un composé organique contenant un groupe réticulable et (B) d'un composé contenant du silicium pouvant réticuler le composé organique contenant un groupe réticulable ; et cuisson d'un mélange du produit durci et (C) d'une matière carbonée.
PCT/JP2012/052440 2011-01-31 2012-01-27 Procédé pour la fabrication d'un matériau composite à base de carbone contenant du silicium revêtu de carbone en surface Ceased WO2012105669A1 (fr)

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Publication number Priority date Publication date Assignee Title
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US10259972B2 (en) 2013-10-04 2019-04-16 Techneglas Llc High performance compositions and composites
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WO2014091962A1 (fr) * 2012-12-12 2014-06-19 日本電気硝子株式会社 Matériau actif d'électrode négative pour dispositifs de stockage d'électricité et procédé de fabrication associé
US20150340695A1 (en) * 2012-12-19 2015-11-26 Dic Corporation Active material for negative electrodes of nonaqueous secondary batteries, and nonaqueous secondary battery
JP6274032B2 (ja) * 2013-08-19 2018-02-07 Jsr株式会社 電極材料の製造方法、電極及び蓄電デバイス
JP2015162295A (ja) * 2014-02-26 2015-09-07 東海カーボン株式会社 シリコンオキシカーバイドセラミックス、その製造方法、シリコンオキシカーバイド複合材料および非水電解質二次電池
EP3018099A1 (fr) * 2014-11-06 2016-05-11 Commissariat A L'energie Atomique Et Aux Energies Alternatives Matériau d'électrode composite SiOC
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JP7435916B1 (ja) * 2022-05-11 2024-02-21 Dic株式会社 負極活物質の製造方法、負極活物質および二次電池

Citations (22)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3293194A (en) 1964-02-14 1966-12-20 Ici Ltd Polymerization of disilacyclobutane in the presence of a platinum catalyst
US4312970A (en) 1981-02-20 1982-01-26 Dow Corning Corporation Silazane polymers from {R'3 Si}2 NH and organochlorosilanes
US4340619A (en) 1981-01-15 1982-07-20 Dow Corning Corporation Process for the preparation of poly(disilyl)silazane polymers and the polymers therefrom
US4395460A (en) 1981-09-21 1983-07-26 Dow Corning Corporation Preparation of polysilazane polymers and the polymers therefrom
US4397828A (en) 1981-11-16 1983-08-09 Massachusetts Institute Of Technology Stable liquid polymeric precursor to silicon nitride and process
US4404153A (en) 1981-01-15 1983-09-13 Dow Corning Corporation Process for the preparation of poly(disilyl)silazane polymers and the polymers therefrom
US4482689A (en) 1984-03-12 1984-11-13 Dow Corning Corporation Process for the preparation of polymetallo(disily)silazane polymers and the polymers therefrom
US4540803A (en) 1983-11-28 1985-09-10 Dow Corning Corporation Hydrosilazane polymers from [R3 Si]2 NH and HSiCl3
US4543344A (en) 1983-11-28 1985-09-24 Dow Corning Corporation Silicon nitride-containing ceramic material prepared by pyrolysis of hydrosilazane polymers from (R3 Si)2 NH and HSiCl3
US4544803A (en) 1984-06-11 1985-10-01 Ceramic Magnetics, Inc. Positional transducer
US4774312A (en) 1987-06-08 1988-09-27 Dow Corning Corporation Polydisilacyclobutasilazanes
US4835238A (en) 1987-06-08 1989-05-30 Dow Corning Corporation Polysilacyclobutasilazanes
US4916200A (en) 1987-06-08 1990-04-10 Dow Corning Corporation Silane modified polysilacyclobutasilazanes
US4929742A (en) 1988-11-28 1990-05-29 Dow Corning Corporation Silane modified polysilacyclobutasilazanes
JPH04334551A (ja) 1991-05-10 1992-11-20 Tonen Corp ヒドロシランの重合触媒
JPH1074506A (ja) 1996-06-11 1998-03-17 Dow Corning Corp ポリシロキサンを用いるリチウムイオン電池用の電極
JPH1097853A (ja) 1996-06-11 1998-04-14 Dow Corning Corp ポリシランを用いるリチウムイオン電池用の電極
WO1998029476A1 (fr) 1996-12-27 1998-07-09 Osaka Gas Company Limited Procede de preparation de polysilanes
JPH10275617A (ja) 1997-03-25 1998-10-13 Dow Corning Corp リチウムイオン電池用電極材料の形成
JP2004273377A (ja) 2003-03-12 2004-09-30 Mitsubishi Materials Corp 充放電可能な無機化合物及びその製造方法並びにこれを用いた非水電解液二次電池
US20050136330A1 (en) * 2003-12-19 2005-06-23 Zhenhua Mao Carbon-coated silicon particle power as the anode material for lithium batteries and the method of making the same
US20090252864A1 (en) * 2003-12-19 2009-10-08 Conocophillips Company Methods of preparing composite carbon-graphite-silicon particles and using same

Patent Citations (22)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3293194A (en) 1964-02-14 1966-12-20 Ici Ltd Polymerization of disilacyclobutane in the presence of a platinum catalyst
US4340619A (en) 1981-01-15 1982-07-20 Dow Corning Corporation Process for the preparation of poly(disilyl)silazane polymers and the polymers therefrom
US4404153A (en) 1981-01-15 1983-09-13 Dow Corning Corporation Process for the preparation of poly(disilyl)silazane polymers and the polymers therefrom
US4312970A (en) 1981-02-20 1982-01-26 Dow Corning Corporation Silazane polymers from {R'3 Si}2 NH and organochlorosilanes
US4395460A (en) 1981-09-21 1983-07-26 Dow Corning Corporation Preparation of polysilazane polymers and the polymers therefrom
US4397828A (en) 1981-11-16 1983-08-09 Massachusetts Institute Of Technology Stable liquid polymeric precursor to silicon nitride and process
US4540803A (en) 1983-11-28 1985-09-10 Dow Corning Corporation Hydrosilazane polymers from [R3 Si]2 NH and HSiCl3
US4543344A (en) 1983-11-28 1985-09-24 Dow Corning Corporation Silicon nitride-containing ceramic material prepared by pyrolysis of hydrosilazane polymers from (R3 Si)2 NH and HSiCl3
US4482689A (en) 1984-03-12 1984-11-13 Dow Corning Corporation Process for the preparation of polymetallo(disily)silazane polymers and the polymers therefrom
US4544803A (en) 1984-06-11 1985-10-01 Ceramic Magnetics, Inc. Positional transducer
US4774312A (en) 1987-06-08 1988-09-27 Dow Corning Corporation Polydisilacyclobutasilazanes
US4835238A (en) 1987-06-08 1989-05-30 Dow Corning Corporation Polysilacyclobutasilazanes
US4916200A (en) 1987-06-08 1990-04-10 Dow Corning Corporation Silane modified polysilacyclobutasilazanes
US4929742A (en) 1988-11-28 1990-05-29 Dow Corning Corporation Silane modified polysilacyclobutasilazanes
JPH04334551A (ja) 1991-05-10 1992-11-20 Tonen Corp ヒドロシランの重合触媒
JPH1074506A (ja) 1996-06-11 1998-03-17 Dow Corning Corp ポリシロキサンを用いるリチウムイオン電池用の電極
JPH1097853A (ja) 1996-06-11 1998-04-14 Dow Corning Corp ポリシランを用いるリチウムイオン電池用の電極
WO1998029476A1 (fr) 1996-12-27 1998-07-09 Osaka Gas Company Limited Procede de preparation de polysilanes
JPH10275617A (ja) 1997-03-25 1998-10-13 Dow Corning Corp リチウムイオン電池用電極材料の形成
JP2004273377A (ja) 2003-03-12 2004-09-30 Mitsubishi Materials Corp 充放電可能な無機化合物及びその製造方法並びにこれを用いた非水電解液二次電池
US20050136330A1 (en) * 2003-12-19 2005-06-23 Zhenhua Mao Carbon-coated silicon particle power as the anode material for lithium batteries and the method of making the same
US20090252864A1 (en) * 2003-12-19 2009-10-08 Conocophillips Company Methods of preparing composite carbon-graphite-silicon particles and using same

Non-Patent Citations (10)

* Cited by examiner, † Cited by third party
Title
ANTHONY R. MANNING, ET AL.: "The systematic synthesis of complexes containing mu3-CS ligands as two-electron donors. The preparation and structure of [{Co(eta-C5H5)}2{Fe(PPh3)(CO)2}(mu3-S)(mu3-CS)]", J. CHEM. SOC., CHEM. COMMUN., no. 12, 1992, pages 897 - 898
ERIC BACQUE: "New polycarbosilane models. 1. Poly[(methylchlorosilylene)methylene], a novel, functional polycarbosilane", MACROMOLECULES, vol. 21, no. 1, 1988, pages 30 - 34
J. DUNOGUES ET AL., MACROMOLECULES, vol. 21, 1988, pages 3
J. ELECTROCHEM. SOC., vol. 144, 1997, pages 2410
J. MATER. SCI., vol. 22, 1987, pages 2609
KAZUAKI FURUKAWA, MASAIE FUJINO, NOBUO MATSUMOTO: "Optical properties of silicon network polymers", MACROMOLECULES, vol. 23, no. 14, 1990, pages 3423 - 3426
KENKICHI SAKAMOTO, MASARU YOSHIDA, HIDEKI SAKURAI: "Highly ordered high-molecular weight alternating polysilylene copolymer prepared by anionic polymerization of masked disilene", MACROMOLECULES, vol. 23, no. 20, 1990, pages 4494 - 4496, XP000174212, DOI: doi:10.1021/ma00222a031
KOICHI MIKAMI, ET AL.: "Anomalous threo-diastereoselectivity in allylic silane- or stannane-aldehyde condensation reactions: new interpretation of the antiperiplanar vs. synclinal problem on the transition-state conformations", J. CHEM. SOC., CHEM. COMMUN., no. 17, 1990, pages 1161 - 1163
LARCHER D, ET AL.: "Si-containing disordered carbons prepared by pyrolysis of pitch/polysilane blends: effect of oxygen and sulfur", SOLID STATE IONICS, vol. 122, no. 1-4, 1999, pages 71 - 83, XP004168362, DOI: doi:10.1016/S0167-2738(98)00557-8
NOLL: "Chemistry and Technology of Silicones", 1968, ACADEMIC PRESS

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* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP2399882A2 (fr) * 2010-06-28 2011-12-28 United Technologies Corporation Poudres composites
WO2013115114A1 (fr) * 2012-01-30 2013-08-08 Dow Corning Toray Co., Ltd. Matériau composite à base de carbone contenant du silicium
EP2768049A1 (fr) * 2013-02-15 2014-08-20 Samsung SDI Co., Ltd. Matériau actif négatif, électrode négative et batterie au lithium comprenant chacune un tel matériau
US9105922B2 (en) 2013-02-15 2015-08-11 Samsung Sdi Co., Ltd. Negative active material, and negative electrode and lithium battery each including the negative active material
US10259972B2 (en) 2013-10-04 2019-04-16 Techneglas Llc High performance compositions and composites
KR20220005639A (ko) * 2014-06-23 2022-01-13 신에쓰 가가꾸 고교 가부시끼가이샤 비수전해질 이차 전지용 부극재, 비수전해질 이차 전지용 부극 및 비수전해질 이차 전지, 및 부극 활물질 입자의 제조 방법
KR102459411B1 (ko) * 2014-06-23 2022-10-27 신에쓰 가가꾸 고교 가부시끼가이샤 비수전해질 이차 전지용 부극재, 비수전해질 이차 전지용 부극 및 비수전해질 이차 전지, 및 부극 활물질 입자의 제조 방법
CN110649234A (zh) * 2019-08-21 2020-01-03 合肥国轩高科动力能源有限公司 一种高库伦效率硅基负极材料的制备方法
US12351462B1 (en) 2024-10-25 2025-07-08 Urbix, Inc. Graphite shaping and coating devices, systems, and methods

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