TW201235296A - Method for manufacturing a carbon surface-coated silicon-containing carbon-based composite material - Google Patents

Abstract

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. Using a carbon surface-coated silicon-containing carbon-based composite material as an electrode active material, the composite material obtained by: forming 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.

Description

201235296 VI. Description of the Invention: [Technical Field of the Invention] A composite material containing carbonaceous base and a method for producing the same,

An electrode comprising the active material and an electrical storage device comprising the electrode. [Prior Art] The present invention relates to a surface coated with carbon on a secondary battery as a kind of high in many cases, which is studied by using a thermoelectric storage device and particularly a secondary or clock ion energy density secondary battery. The ruthenium-containing carbon material obtained by dissolving the ruthenium polymer serves as a negative electrode material of the lithium ion secondary batteries. For example, Japanese Unexamined Patent Application Publication No. H10-97853 and Solid State Ionics, 122, 71 (1999) describe that manufacturing can be used for manufacturing by using Jumeng and coal tar pitch as precursors. Electrode for batteries with low capacity, low irreversible capacity, high density and excellent safety. In addition, the uncensored patent application publication No. H1 0-74506, the unexamined patent application publication No. 〇1〇 275617, and the Japanese uncensored patent application publication No. 2〇〇4_273377 No. and J_ Electrochem. Soc., 144, 2410 (1997) describe obtaining a large capacity, low irreversible capacity by using a hot sulphide polymer and subsequently introducing lithium to form an electrode for a lithium or lithium ion secondary battery. High density and excellent safety performance of the battery. However, such lithium or lithium ion secondary batteries comprising electrodes comprising a ruthenium-containing carbon material have problems in that the actual performance of the charge and discharge cycle characteristics and their similar characteristics is insufficient. PRIOR ART DOCUMENT 161 877 doc doc pp pp pp pp pp pp pp pp 97 97 97 97 97 97 97 97 97 97 97 97 97 97 97 97 97 97 97 97 97 97 97 97 97 97 97 97 97 97 97 97 97 97 97 97 97 97 Japanese Unexamined Patent Application Publication No. Hei No. 275617 Patent Document 4: Unexamined Patent Application Publication No. 273377 Non-Patent Document Non-Patent Document 1. Solid State Ionics, 122 , 71 (1999) Non-Patent Document 2: J. Electrochem. Soc., 144, 2410 (1997) [Invention] It is an object of the present invention to provide an electrical storage device, particularly a lithium or lithium ion secondary battery. a composite material of the electrode; an electrode active material composed of the composite material; an electrode containing the active material; and an electrical storage device including the electrode. Solution to Problem The object of the present invention is achieved by a method for producing a carbon-coated composite material containing a carbon-coated surface, which is characterized by the organic compound containing a crosslinkable group ( Hereinafter, it is referred to as "component (A)") and (b) a ruthenium-containing compound (hereinafter referred to as "component (B)") capable of crosslinking the crosslinkable group-containing organic compound is crosslinked to obtain curing. a product; and a mixture of the cured product and (C) a carbonaceous material (hereinafter referred to as "component"). 161877.doc 201235296 The baking is preferably at 30 (rc to endowment temperature in vacuum) (4) The intermediate group can be composed of optional free aliphatic unsaturated groups, epoxy groups, propylene olefins, acryl groups, amine groups, mercapto groups, sulfhydryl groups and dentate groups. Component (A) may have an aromatic group. Component (4) is preferably an organic compound represented by the following formula (R^xR2 is in this formula, R1 is a crosslinkable group; "χ" is greater than Or equal to the number of forks' and R2 is an aromatic group having a "χ" price. The component w can be cut by W, I, stone m carbon (four) or a mixture thereof. B) is preferably a decane represented by the following average unit formula: (R33Si〇1/2)a(R32Si〇2/2)b(R3Si〇3/2)c(s.〇^)d Wherein 'R3 each independently represents a monovalent hydrocarbon group, a hydrogen atom, an organic group of a 3-epoxy group of a functional atom, an organic group containing an amino group of an acryl-fluorenyl group or a methacryl group, and an anthracene group-containing organic group; An organic group, an alkoxy group or a hydroxyl group. "a", "bj, rc" and "d" are greater than or equal to and less than or equal to 1 and satisfy ra"+"b"+"c"+"d" =1. However, 'a, rb, and rc' cannot be 〇 at the same time. Component (C) can be carbon black, carbon fiber, carbon nanofiber, carbon nanotube or a mixture thereof. The addition reaction, the condensation reaction, the ring opening reaction or the radical reaction is carried out. 161877.doc 201235296 The cured product is preferably composed of a component having an aliphatic unsaturated group (A) and a component having a hydrogen atom bonded to the ruthenium ( B) obtained by a hydrogenation reaction of hydrazine. The cured product is preferably bonded to hydrogen having an aliphatic unsaturated group, an aliphatic unsaturated group, an acryl fluorenyl group, a fluorenyl fluorenyl group or a hydrazine. The surface of the cured product is preferably obtained by the component (C). The present invention relates to a carbon-coated composite material having a carbon-coated surface, which is The composite material is preferably composed of particles having an average diameter of 5 nm to 50 μη ΐ 2. The amount of carbon in the composite material can be set by mass (% by weight) to 5 〇 mass% by weight. The composite material preferably has The carbon coating layer having a thickness of 5 nm to 2 μm. The electrode active material of the present invention is composed of the above composite material. The electrode active material is preferably composed of particles having an average diameter of from 1 μm to 5 μm. The electrode of the invention comprises the above electrode active material and is applicable to an electrical storage device, especially a lithium or lithium ion secondary battery. EFFECT OF THE INVENTION The composite material of the present invention can be used as a raw material of an electrode active material having a high reversible capacity, stable charging and extremely small enthalpy, high initial charge and discharge efficiency, and a tube-shaped wire at the time of release of the bell. Further, the present invention uses inexpensive raw materials and can be produced by a simple manufacturing method. t Ming electrode material (four) suitable for lithium or lithium ion - blowing thunder 'small device 仵; t it is suitable for the electrode of the human battery. In addition, the electrode of the present invention can impart 161877.doc 201235296 battery south reversible capacity, stability: charge and discharge cycle characteristics, and high initial charge and discharge efficiency. Accordingly, the electrical storage device of the present invention can have high reversible capacity, stable charge and discharge cycle characteristics, and high initial charge and discharge efficiency. [Embodiment] Composite material The composite material of the present invention can be obtained by a production method characterized in that the (A) organic compound having a crosslinkable group and (B) can be made to have a crosslinkable group. The organic compound crosslinked ruthenium containing compound is crosslinked to obtain a cured product; and a mixture of the cured product and (c) a carbonaceous material is baked. The crosslinkable group in the component (A) is not particularly limited, and it is limited to being a crosslinkable group. Examples thereof include an aliphatic unsaturated group, an epoxy group, an acrylonitrile group, a methyl propyl (tetra) group, an amine group, a trans group, a recording group, and a functional group. Specific examples of the aliphatic unsaturated group include a vinyl group, a propenyl group, a butenyl group, a pentenyl group, a hexenyl group, and the like alkenyl group; an ethyl group, a propynyl pentynyl group, and the like. Specific examples of the epoxy group include glycidyl glycidoxy group, epoxycyclohexyl group, 3 glycidoxypropyl group, and 2-(3,4-epoxycyclohexyl)ethyl group. Specific examples of the acrylonitrile group include a propylene methoxy propyl group. Specific examples of the methacrylonitrile group include 3-methacryloxypropyl group. Specific examples of amine groups & include 3-aminopropyl and N-(2•aminoethyl)-3-aminopropyl. Specific examples of the hydroxyl group include a hydroxyethyl 'hydroxypropyl group and a similar hydroxyalkyl group; and a hydroxyphenyl group and a similar hydroxyaryl group. Specific examples of sulfhydryl groups include 3-sulfopropyl. Specific examples of the dentate alkyl group include a % gas propyl group. 16l877.doc 201235296

At least 15 mass% by weight, and more preferably at least 3 mass% by weight. Component (A) may be free of rhodium or may include Shi Xi. When component (A) does not contain ruthenium, component (A) is preferably an organic compound having at least one aromatic ring in the molecule because the excellent efficiency in carbonization by heating is advantageous for forming a graphene structure. Examples of the above component (A) include a hydrazine-free aliphatic hydrocarbon compound having a crosslinkable group at a molecular terminal and/or a molecular side chain; a molecular terminal and/or a molecular side chain having a crosslinkable group and a hydrazine-free aliphatic hydrocarbon compound having a hetero atom other than a carbon atom (such as a nitrogen, oxygen or boron atom) in a molecular chain; an aromatic hydrocarbon-free compound having a crosslinkable group in a molecule; and a molecule A ruthenium-free cyclic aliphatic compound having a crosslinkable group and a hetero atom having a non-carbon atom such as a nitrogen, oxygen or boron atom. Specific examples of the aliphatic hydrocarbon compound include a compound represented by the formula: R^CHOm-R1 CH3-(CH2)m-(CHR1)n-CH3 CH3-(CH2)m-(CH=CH)n-CH3 CH3- (CH2)m-(C=C)n-CH3 R1-0(CH2CH2〇)m(CH2CH2CH2〇)n-R1 Formula 1

161877.doc 201235296 In the formula, R1 represents a crosslinkable group, and examples thereof include an aliphatic unsaturated group, a %oxy group, a @稀醯 group, a methyl propylene group, an amine group, a thiol group. , sulfhydryl and halogenated alkyl. Specific examples are the same as the above groups. Further, 'm' and 'n' are greater than or equal to r integer; i "xj is an integer greater than 1. Specific examples of the aromatic hydrocarbon compound include a person represented by the following formula: ° (RW. In the above, R1 is a crosslinkable group, and an example thereof is the same as the above group. Further, "X" is an integer greater than or equal to 1 eR2 represents an aromatic group having an "X" valence. Specifically, in this formula Wherein, when Γχ" is 1, R2 represents a monovalent aromatic group' and specific examples thereof include the following groups: Formula 2 O', 〇〇~, 〇〇, 〇!]0 Specific examples of the above aromatic hydrocarbon compound Including α- or β-methylstyrene, α- or β-ethylstyrene, nonyloxystyrene, phenylstyrene, gas styrene, o-, m- or p-methylstyrene, ethylbenzene Ethylene, methyl decyl styrene, hydroxy styrene, cyanostyrene, nitrostyrene, amino styrene, carboxy styrene, thio styrene, sodium styrene sulfonate, ethylene base 0 bite , vinyl" phenanthrene, vinyl pirone, vinyl naphthalene, vinyl anthracene and vinyl biphenyl. 161877.doc -10- 201235296 Further, in the formula, when "X" is 2, R2 represents a divalent aromatic group, and specific examples thereof include the following groups: Specific examples of the above aromatic hydrocarbon compound include a diphenyl group, Diethylbiphenyl, vinyl benzoyl chloride, divinyl pyridine, divinyl phenanthrene, monoethyl carbaryl ketone |, diethyl tea, diethylene dimethyl Divinylethylbenzene and divinyl hydride. The aromatic hydrocarbon compound is preferably diethylbenzene benzene because the obtained cured product has excellent pyrolysis characteristics. Further, in the formula, when "X" is 3, R2 represents a trivalent aromatic group, and specific examples thereof include the following groups.

Specific examples of the above aromatic hydrocarbon compound include trivinylbenzene and trivinylnaphthalene. Further, specific examples of the aromatic compound containing a hetero atom include an aromatic compound represented by the following formula: 161877.doc -11 - 201235296 Formula 5, R1

N

N In the formula, r is an additional and ° crosslinking group, and examples thereof are the same as the above groups. a specific compound of a cyclic compound having a hetero atom, which is not a cyclic compound:

In the formula, R1 is a crosslinkable group, and an example thereof is the same as the above group. The component (A) of the parenthesis is not particularly limited, and its restriction is that it has a crosslinkable group, and examples thereof include a stone-containing monomer, an oligomer, and a polymer. Examples thereof include a structural unit composed of cut-and-money (4), a structural unit having a stone-H bond, and a structure consisting of a structural unit having an oxygen-stone bond, and a structure having a W winter material. The unit constitutes a broken stone and a mixture thereof. Examples of the stone as the component (4) include a substance represented by the following average unit formula: 161877.doc -12· 201235296 R34Si or a substance represented by the following average unit formula (R33Si) a(R32Si)b(R3Si)c(Si)d. In this formula, 3 groups, a hydrocarbyl group or an aromatic hydrocarbon group having 1 to 20 carbons, and an alkoxy group R each independently represent the above crosslinkable group A substituted or unsubstituted monovalent saturated aliphatic, hydrogen or dentate atom. However, "a" b", "C" and "d J are each 0 or a positive a" + 1)" + "." + " (1" = 1, and at least one and preferably at least two R3 in the molecule are the above-mentioned crosslinkable groups. The saturated aliphatic hydrocarbon group is preferably an alkyl group, and the (tetra) hydrocarbon group is preferably an aryl group and an aralkyl group. The group is preferably a group having 1 to 12 carbons and more preferably a group having (1) carbon atoms, and the group is preferably any of the following: a chain or branching bond, a cyclyl or a ring-like base (combined with a money or branching bond (preferably a methylene group, an ethyl group or a similar alkyl group having from j to 6 carbon atoms) and a carbocyclic ring (preferably an alkyl group having a ring of 3 to 8 carbon atoms). The linear or branched alkyl group preferably has from 丨 to 6 carbon atoms, and examples thereof include a methyl group, an ethyl group, and a n-propyl group. a methyl group, an isopropyl group, a butyl group, a tert-butyl group, a pentyl group, a hexyl group and the like. A methyl group is particularly preferred. The cycloalkyl group preferably has 4 to 6 carbon atoms, and examples thereof include a cyclobutyl group. a group, a pentyl group, a cyclohexyl group and the like. A cyclopentyl group and a cyclohexyl group are particularly preferred. The aryl group preferably has 6 to 12 carbon atoms, and examples thereof include a phenyl group and a naphthalene 161877.doc • 13 - 201235296 and tolyl. Examples of the aralkyl group preferably having 7 to 12 carbon atoms and having an aralkyl group having from 12 to 12 carbon atoms include a benzyl group, a phenethyl group and a strepylpropyl group. a substituent, and examples of the substituent include a fluorine atom, a gas atom, a bromine atom, an iodine atom, and the like; a hydroxyl group; a methoxy group, an oxy group a propoxy group, an isopropoxy group, and a similar alkoxy group having 1 to 6 carbons; an amine group; an amidino group; a nitro group; an epoxy group; and a similar base group. The substituent may be bonded to a hydrocarbon chain. Position, saturated ring position or aromatic ring position Examples of the alkoxy group include a methoxy group, an ethoxy group, a n-propoxy group and an isopropoxy group. Examples of the atom of the atom include a fluorine atom, a gas atom, a bromine atom and iodine. The above decane can be produced by a method known in the art. Examples of the method include the following method: Macromolecules, 23, 3423 (1990), etc., which are included in the presence of a metal to cause the base stone to burn away _ Method of macromolecules, 23, 4494 (1990), etc., comprising a method for polymerizing a diterpene anion; J. Chem. Soc., Chem. Commun., 1161 (1990) and J. Chem. Soc. , Chem. Commun., 897 (1992), etc., comprising a method for de-toothing a hydrazine by electrode reduction; a method comprising calcining a halogen group in the presence of magnesium (see W098/29476, etc.) A method comprising dehydrogenating hydroquinone in the presence of a metal catalyst (see Kokai H04-33455) 1 etc); and other methods. Examples of the indane alkane as the component (A) include those represented by the following average unit formula: 161877.doc • 14· 201235296 (R33SiNR4)a(R32SiNR4)b(R3SiNR4)e(SiNR4)d. In the formula, 'R3' each independently represents the above crosslinkable group, a substituted or unsubstituted monovalent saturated aliphatic hydrocarbon group or an aromatic hydrocarbon group having 1 to 20 carbons, an alkoxy group, a hydrogen atom or a dentate atom. R4 represents a hydrogen atom or a substituted or unsubstituted monovalent saturated aliphatic hydrocarbon group or aromatic hydrocarbon group having 1 to 20 carbons. "a", "b", "Cj and "dj are each a positive or positive number, however "a" + rb" + "c" + "d" = 1. At least one and preferably at least two R3 of the molecules are the above-mentioned crosslinkable groups. The saturated aliphatic hydrocarbon group, aromatic hydrocarbon group, alkoxy group and dentate atom herein are the same as defined above for decane. The above described oxazazane can be prepared by methods known in the art. Examples of the method for preparing the arsenic-sintering include U.S. Patent Nos. 4,312,970, 4,340,619, 4,395,460, 4,404,153, 4, 482, 689, 4, </ </ RTI> 4, </ RTI> 4, 540, 803, 4, 454, 344, 4, 385, 238, s. Methods described in No. 12, No. 4,929,742 and No. 4,916,200. Alternative methods are also described in J. Mater. Sci., 22, 2609 (1987). Examples of the oxane as the component (A) include a substance represented by the following average unit formula: (R33Si〇1/2)a(R32Si〇2/2)b(R3Si〇3/2)c(Si〇4 /2)d. In the formula, R 3 independently represents the above-mentioned crosslinkable group, a substituted or unsubstituted monovalent saturated aliphatic hydrocarbon group or an aromatic hydrocarbon having 1 to 20 carbons. 161877.doc •15-201235296

"c" is a non-base group, an alkoxy group, a hydrogen atom or a halogen atom. "equal to 1 and satisfying "a" "a", "b" and "d" are numbers greater than or equal to 〇 and less than + "c" + "d" = 1, however, they can be 0 at the same time. At least one and preferably at least two R3 of the molecules are the above-mentioned crosslinkable groups. The saturated aliphatic hydrocarbon group, aromatic hydrocarbon group, alkoxy group and functional element atom herein are the same as defined above for decane. The above oxiranes can be prepared by methods known in the art. The method for preparing the oxane is not particularly limited, but most common preparation methods include hydrolyzing the organic gas decane. These and other methods are by N〇u, Chemistry and Technology 〇f Silicones, Chapter 5 (translated from the second issue,

Academic Press, 1968). Examples of the carbon decane as the component (A) include a substance represented by the following average unit formula: (R33SiCR5R6)a(R32SiCR5R6)b(R3siCR5R^)c(SiCR^R6)d 0 In the formula, 'R3 each independently The above-mentioned crosslinkable group, a substituted or unsubstituted monovalent saturated aliphatic hydrocarbon group or an aromatic hydrocarbon group having 1 to 20 carbons, an alkoxy group, a hydrogen atom or a dentate atom. R5 and R6 each independently represent a hydrogen atom or a substituted or unsubstituted monovalent saturated aliphatic hydrocarbon group or aromatic hydrocarbon group having 1 to 2 carbon atoms. a", "b", "c" and "dj are each a positive or positive number, however, at least one of the "ugly" + "b" + "c" + "d" = 1 〇 molecules and preferably at least two R3 is the above crosslinkable group 161877.doc -16·201235296. The saturated aliphatic hydrocarbon group, the aromatic hydrocarbon group, the alkoxy group and the self atomic atom here are the same as defined above for decane. The above carbon decane can be produced by a method known in the art. An example of a method for preparing a carbon decane is described in Macromolecules, 2 ι, 3 〇 (i US Pat. No. 3,293,194. The form of the stone scorpion, the sulphur sulphur 1 oxy sulphur and the carbon (4) is not particularly limited and may be solid, liquid or The paste form is preferably a solid from the viewpoint of handling ability and the like. In the polymer compound of the fluorenyl group, it is complicated by the following industrial interests, and the money house composed of the unit having the stone eve n bond is It is not too low, and the compounds are sufficiently chemically stable, easy to handle in air at room temperature, low in raw material cost and production, and sufficient cost performance. The cost component (8) may be the above-mentioned organic compound or may be a mixture of two or more kinds of "not" and further may contain a nitrogen-containing monomer (such as a similar monomer) as AH &amp; v ^ ^ *, "乍 is another component. In this case, the content of the nitrogen-containing monomer is in the range of {not more than 50 mass% by weight' and more preferably in the range of 10 mass% by weight to 50 mass%. Magic/〇 to two t(B) for being able to make component (4) Examples of the above component (B) include a knife &amp;'# nitrogen &amp; 'carbon #烧# and its mixed oxime examples include a monomer having a Si-0-Si bond and a similar oxime, preferably Polymer or polymer spring 'has stone courtyard and Si-Si bond and similar to Si Xizhuo monomer, polymer or poly-plate. eJ_. Thai °, with Si-(CH2)n-Si bond and similar A single alkyl group 161877.doc 201235296 body, oligomer or polymer; monomer with Si-(C6H4)n-Si or Si-(CH2CH2C6H4CH2CH2)n-Si bond and similar aryl group, oligomerization Or a polymer having Si-N-Si bonds and similar monomers, oligomers or polymers; having at least two selected from the group consisting of Si-O-Si bonds, Si-Si bonds, Si-(CH2) a rhestone-containing copolymer of n-Si bond, Si-(C6H4)n-Si bond and Si-N-Si bond; and a mixture thereof. Note that in the formula, "n" is greater than or equal to An integer of 1. The component (Β) preferably has a hydrazine-bonded hydrogen atom. Examples of the ascorbic acid of the component (Β) include a substance represented by the following average unit formula: (R 3Si〇i/2)a (R72Si〇2/2)b(R7Si〇3/2)c(Si〇4/2)d. In this formula, R7 is independent An organic group containing a monovalent hydrocarbon group, a hydrogen atom, a functional atom, an epoxy group-containing organic group, an acryl-containing fluorenyl group or a mercaptopropenyl group, an amine group-containing organic group, a mercapto group-containing organic group , alkoxy or hydroxy. "a", "b", "c" and "d" are greater than or equal to 〇 and less than or equal to 1 and satisfy "a" + "b" + "Cj + "d" = 1 The number. However, 'a', 'b' and 'c' cannot be both. Specific examples of the monovalent hydrocarbon group represented by R7 include an alkyl group, an alkenyl group, an aryl group and a aryl group. The alkyl group is preferably an alkyl group having 1 to 12 carbon atoms and more preferably an alkyl group having 1 to 6 carbon atoms. The alkyl group may be any of the following: a linear or branched alkyl group, a cycloalkyl group or a cycloalkyl group (combined linear or branched chain alkyl group (preferably an anthracene group, an ethyl group or an ethyl group) A group of a similar alkyl group of 6 carbon atoms and a carbocyclic ring (preferably a ring having 3 to 8 carbon atoms). The linear or branched alkyl group preferably has 1 to 6 carbon atoms, and specific examples thereof include a methyl group, an ethyl group, a n-propyl group, an isopropyl group, a butyl group, and a 161877.doc -18·201235296 group. Amyl and hexyl. The cycloalkyl group preferably has 4 to 6 carbon atoms, and specific examples thereof include a cyclobutyl group, a cyclopentyl group and a cyclohexyl group. The alkenyl group preferably has 2 to 12 carbon atoms, and more preferably 2 to 6 carbon atoms. Specific examples of the alkenyl group having 2 to 6 carbons include a vinyl group, a propenyl group, a butenyl group, a pentenyl group, and a hexenyl group, of which a vinyl group is preferred. The aralkyl group preferably has 7 to 12 carbon atoms. Specific examples of the aralkyl group having 7 to 12 carbon atoms include a phenylhydrazine group, a phenethyl group, and a phenylpropyl group. The aryl group preferably has 6 to 12 carbon atoms, and specific examples thereof include a phenyl group, a naphthyl group, and an anthracenylphenyl group. The monovalent hydrocarbon group may have a substituent. Specific examples of such substituents include a fluorine atom, a gas atom, a bromine atom, an iodine atom or other halogen; a hydroxyl group; a methoxy group, an ethoxy group, a n-propoxy group, an isopropoxy group or the like. Examples of such substituted monovalent hydrocarbon groups include 3-vapor propyl, 3,3,3-trifluoropropyl, perfluorobutylethyl and total octylethyl. Specific examples of the halogen atom represented by R7 include a fluorine atom, a gas atom, a bromine atom, and an iodine atom, of which a gas atom is preferred. Specific examples of the epoxy group-containing organic group represented by R7 include 3-glycidoxypropyl group, 4-glycidoxybutyl group or a similar glycidoxy group; 2-(3,4-ring) Oxycyclohexyl)-ethyl, 3·(3 4_epoxycyclohexyl)propyl or similar epoxycyclohexylalkyl; and 4-epoxyethyl butyl, 8-epoxy Home base octyl or similar oxiranyl alkyl. Glycidyloxyalkyl is preferred, and 3-glycidoxypropyl is especially preferred. Specific examples of the organic group containing an acryl-fluorenyl group or a mercaptopropenyl group represented by R7 include 3-propenyloxypropyl group, 3-methacryloxypropyl group, and 4: propylene oxide oxybutyl group Base and 4_mercaptopropenyloxybutyl group, of which 3·mercapto 161877.doc •19- 201235296 propylene oxypropyl is preferred. Specific examples of the amino group-containing organic group represented by R7 include 3-aminopropyl, 4-aminobutyl, and N-(2-aminoethyl)-3-aminopropyl, wherein 3_ Aminopropyl and N-(2-aminoethyl)-3-aminopropyl are preferred. Specific examples of the mercapto group-containing organic group represented by R7 include a 3-mercaptopropyl group and a 4-decylbutyl group. Specific examples of the alkoxy group represented by R include a decyloxy group, an ethoxy group, a n-propoxy group and an isopropoxy group. Among them, a methoxy group and an ethoxy group are preferred. In one molecule, at least one group represented by R7 and preferably at least two groups represented by R7 are an alkenyl group, a hydrogen atom, a halogen atom, an organic group containing an epoxy group, and an organic group containing an acryl group. a group, an organic group containing a methacryl group, an organic group containing an amine group, an organic group containing a mercapto group, an alkoxy group or a hydroxyl group. a", "b", "c" and equal to 1 and satisfy "a" + "b" + dj is a number greater than or equal to 〇 and less than or c" + "d" = 1. However, "b" and "Cj cannot be equal to 〇 at the same time. The above-mentioned oscillating chamber may be at least selected from the structures of (R'SiOw), (R72Si〇2/2), (R7Si〇3/2) and (SiOw). One of the units. A specific example is a straight-bonded polyoxo-oxygenate composed of (R 3Si〇丨/2) and (R 2Si〇2/2) units; a ring composed of (R^SiO2, 2) units. a polyoxyalkylene; a branched polyoxyalkylene consisting of (^^〇3^ and (siOw) units; a poly-wei burning consisting of (R73Si〇m) and (R7Si〇3/2) units; R73Si()&quot;2) and (si〇^ unit consisting of a polysulfide; a polysulfide consisting of (R7Si〇3/2) and (Si()4/2) units; by (R72Si聚2/2) and (R7Si〇3/2) units consisting of polysulfide; 161877.doc -20- 201235296 polyoxyalkylene consisting of (R^SiO2/2) and (SiOw2) units; (R^SiOi, 2), (R^SiO2, 2) and (R7Si〇3/2) units of polyfluorene oxide; from (R'SiOm), (R^SiO2, 2) and (si〇4 /2) a polysiloxane composed of units; a polyfluorene oxide composed of (R^SiO丨η), (R7Si〇3/;2) and (Si〇4/2) units; (R72Si02/2) , (R7Si〇3/2) and (Si 〇4/2) a polyoxyalkylene composed of units; and polyfluorene composed of (R73Si01/2), (R72Si〇2/2), (R7Si〇3/2) and (si〇4/2) units The number of repeating units of the structural unit represented by each of (R73Si〇i, 2), (R72Si〇2/2), (R7Si〇3/2), and (SiCU/2) is preferably from 1 to 10,000. Within the range 'more preferably in the range of 1 to 1, 〇〇〇, and even more preferably in the range of 3 to 500. The above-mentioned austenite can be prepared by a method known in the art. The method of the institute is not particularly limited 'but most common methods include the hydrolysis of organic gas oxalate. These and other methods are by Noll in chemistry and

Technology 〇f Silicones, Chapter 5 (translated from German, second issue, Academic Press, 1968). The above oxime may be a ruthenium-containing copolymer compound formed with a polymer. Examples of the ruthenium-containing copolymer compound which can be used as a cerium oxide include a ruthenium-containing copolymer compound having a Si_〇-Si bond and a Si-Si bond; a ruthenium-containing copolymer compound having a Si_0_si bond and a Si_N_Si bond; and having a Si-O-Si bond And a ruthenium-containing copolymer compound having a Si-(CH2)n-Si bond; a shi-containing copolymer having a Si-0-Si bond and a Si-(C6H4)n-Si bond or a Si-(CH2CH2C6H4CH2CH2)n-Si bond; And its analogues. In the equation, "η" has the same meaning as defined above. Further, decane may be represented by the following formula: R74Si 161877.doc 201235296 or represented by the following average unit formula: (R73Si)a(R72Si)b(R7Si)e(Si)d. In the formula, R7 each independently represents a monovalent hydrocarbon group, a hydrogen atom, a halogen atom, an epoxy group-containing organic group, an acryl-containing fluorenyl group or a mercaptopropenyl group-containing organic group, and an amine group-containing organic group. a group, an organic group containing a mercapto group, an alkoxy group or a hydroxyl group. In one molecule, at least one group represented by R7 and preferably at least two groups represented by R7 are an alkenyl group, a hydrogen atom, a halogen atom, an organic group containing a oxy group, and an acryl-containing group. An organic group, an organic group containing a methyl propyl group, an organic group containing an amine group, an organic group containing a mercapto group, an alkoxy group or a hydroxyl group. Ra", "b", "C" and "d" are numbers greater than or equal to 0 and less than or equal to 1 and satisfying "a" + "b" + "c" + "d" = l. However, ra", rb" and "c" cannot be equal to 0 at the same time. The stone court is represented by the general formula R74Si or consists of at least one structural unit selected from the group consisting of (R'si), (R'Si), (R7Si) and (Si). Specific examples are as follows: linear polydecane composed of (R'Si) and (R%Si) units; cyclic polydecane composed of (foot 7) units; composed of (R7Si) and (Si) units Branch chain polysiline; polydecane composed of (R'si) and (R7Si) units; polydecane composed of (R'Si) and (Si) units; (R7si) and (Si) units a polyoxane composed of (R%Si) and (R7Si) units; a polydecane composed of (R72Si) and (Si) units; (R73Si), (8) mountain and (R7si) units a polydecane composed of (R^Si), (R%Si) and (Si) units; a polyfluorene composed of (R^Si), (R7Si) and (Si) units; a polydecane composed of R72si), (R7si) and (si) units; or a polydecane composed of (R73Si), 161877.doc •22-201235296 (R72Si), (R7Si) and (Si) units. The number of repetitions of the structural unit represented by each of (R73Si), (R^Si), (R7Si), and (Si) is preferably in the range of 2 to 10,000, more preferably in the range of 3 to 1,000, and even More preferably in the range of 3 to 500. The above decane can be produced by a method known in the art. A method of the method includes the following method: Macromolecules, 23, 3423 (1990), etc., which comprises a method of de-toothing _-decane in the presence of an alkali metal;

Macromolecules, 23, 4494 (1990), etc., comprising a method for polymerizing a diterpene anion; j. Chem. Soc., Chem. Commun., 1161 (1990) and J. Chem. Soc., Chem. Commun , 897 (1992), etc., comprising a method for desulfurization of a quinone by electrode reduction; a method comprising dehalogenating a halodecane in the presence of a town (see W〇98/29476, etc.); A method in which hydroquinone is dehydrated in the presence of a metal catalyst (see Kokai H04-334551, etc.); and other methods. The above calcination may be a rhodium-containing copolymer compound formed with other polymers. Examples of the ruthenium-containing copolymer compound which can be used as a ceramsite include a ruthenium-containing copolymer compound having a Si_Si bond and a Si_o-si bond; a ruthenium-containing copolymer compound having a Si_Si bond and a Si_N_si bond; having a Si_Si bond and a Si_(CH2)n_Si bond Bismuth-containing copolymer compound with Si-Si bond and Si-(C6H4)n-Si bond or Si-(CH2CH2C6H4CH2CH2)n-

a ruthenium-containing copolymer compound of Si bond; and the like. Examples of other zephyr include an ytterbium-containing compound represented by the following formula: [(R8)2HSi]eR9. In the formula, R8 each represents a substituted or unsubstituted monovalent hydrocarbon group. "e" is an integer greater than or equal to 2, and R9 is an "e" organic group. 161877.doc -23- 201235296 In this formula, an example of the monovalent hydrocarbon group represented by R8 is the same as the monovalent hydrocarbon group described as an example of the ruler 7. "e" is an integer greater than or equal to 2, preferably an integer in the range of 2 to 6. When R9 is a re" organic group and "e" is equal to 2, R9 is a divalent organic group. "Specific examples thereof include an alkylene group, an alkylene group, an alkyl group, an aryl group, and an aryloxy group. Aryl and extended aryl-alkylene-arylene. More specific examples include the group represented by the formula: -(:112 €112-, -(:112&lt;:112(:112-, -(:112(:11(€113)_, -(:11) =(:11-, -CeC-, _CH2CH2OCH2CH2-, -CH2CH2CH2OCH2CH2-.

When "e" is equal to 3, R9 is a trivalent organic group. Specific examples thereof include a group represented by the following formula:

161877.doc • 24· 201235296

Examples of the hydrazine-sintering are, for example, those represented by the following average unit formula: In the formula t, R7 each independently represents a monovalent hydrocarbon group, a hydrogen atom, a functional atom, an epoxy group-containing organic group, an acryl-containing group or An organic group of a methacrylic acid group, an organic group containing an amine group, an organic group based on an alkoxy group or a transatom group. In a molecule, at least one of the groups represented by the group and preferably at least two groups represented by R7 is an alkenyl group, a hydrogenogen + 'funge atom', an epoxy group-containing organic group, and a propylene-containing group. An organic group based on an organic group, an organic group containing a methacrylic group, an organic group containing an amine group, an organic group containing a mercapto group, an alkoxy group or a hydroxyl group. RIG is a hydrogen atom or a substituted or unsubstituted early-valent hydrocarbon group. "a", "b", "C" and "d" are greater than or equal to 〇 and less than or equal to 1 and satisfy the number of ra"+rb"+"C"+"d"=1. However, the examples of 'a'' and 'cj' and 'Cj' cannot be equal to 单价e*Rl〇's monovalent hydrocarbon group are the same as the example of the monovalent hydrocarbon group represented by R7. The moiety represented by RQ is preferably a hydrogen atom or an alkyl group. And particularly preferably a wind atom or a methyl group. The shixi nitrogen sinter contains a unit selected from at least one of the following structural units: (R 3SlNRl0), (R72SiNRi.), (R7SiNR10) and (SiNR丨0). A specific example is The following is a linear polycyanide composed of (R72SiNRi〇) unit; a cyclic polyazide composed of (R^SiNR10) units; a branching polycondensate composed of (R7SiNR10) and (SiNR10) units. a nitrogen alkane; a polyazane composed of (I^SiNR10) and (R7SiNRi〇) units; a polysulfide consisting of 161877.doc -25·201235296 (R73SiNR10) and (SiNR10) units; by (R7SiNRio) And (S1NR10) unit consisting of polyfluorene nitrogen; poly(azinane) composed of (R72SiNRio) and (R7SiNR10) units; polyazane consisting of (R72SiNRi.) and (SiNRio) units; (R73SiNR10), (R72SiNRi〇) and (R7SiNR10) units consisting of polyazane; by (R73SiNRi〇), (R7 a polyazane composed of 2SiNRi〇) and (SiNR10) units; a polyazane composed of (R'siNR10), (R7siNR10) and (SiNR10) units; (R72siNR10), (R7SiNR10) and (SiNR10) units a polyazane composed of (R73SiNRi), (R72SiNR1Q), (R7SiNR1Q), and (SiNR1Q) units. From (R73SiNR10), (R72SiNR10), (R7SiNR10), and (SiNR10) The number of repetitions of the structural unit represented by each of them is preferably in the range of 2 to 10,000, more preferably in the range of 3 to 1,000, and even more preferably in the range of 3 to 500. Prepared by methods known in the art. Examples of methods for preparing decazinones include U.S. Patent Nos. 4,312,970, 4,460,619, 4,395,460, 4,404,153, 4,482,689, 4,397,828, 4,540,803, 4,543,344 No. 4,835,238, 4,774,312, 4,929,742, and 4,916,200. Alternative methods are also described in J. Mater. Sci., 22, 2609 (1987). A ruthenium-containing copolymer compound formed with other polymers. Examples of the ruthenium-containing copolymer compound which can be used as the polyazane include a ruthenium-containing copolymer compound having a Si-N-Si bond and a Si-0-Si bond; a ruthenium containing Si-N-Si bond and Si-Si bond Copolymerized compound; ruthenium-containing copolymer compound having Si-N-Si bond and Si-(CH2)n-Si bond; having Si-N-Si bond and Si-(C6H4)n-Si bond or Si-(CH2CH2C6H4CH2CH2)n a ruthenium-containing copolymer compound of -Si bond; and the like 161877.doc -26 - 201235296. In the equation, "n" has the same meaning as defined above. The carbon decane is represented, for example, by the following average unit formula: (R73SiR&quot;)a (R72SiR, b(R7siR, c(siR7)d. In the formula, 'R7 each independently represents a monovalent hydrocarbon group, a hydrogen atom, a halogen atom, and an epoxy group. An organic group, an organic group containing an acrylonitrile group or a methyl propylene group, an organic group containing an amine group, an organic group containing a thiol group, an alkoxy group or a thiol group. , at least one group represented by R7 and preferably at least two groups represented by R7 are an alkenyl group, a hydrogen atom, a dentate atom, an organic group containing an epoxy group, an organic group containing an acryl group. , an organic group containing a methyl propylene group, an organic group containing an amine group, an organic group containing a thiol group, an alkoxy group or a hydroxyl group. Rn is an alkyl group or an aryl group. "a", And d" are greater than or equal to 〇 and less than or equal to 1 and satisfy the number of "3" + "13" + "(:" + "£1"=1. However, "&amp;", "b" and " c" cannot be equal to 〇 at the same time. The alkyl group represented by ... can be represented, for example, by the formula -(CHA•, and the extended aryl group represented by Rn can be represented, for example, by the formula -(C6扎^. In the equation t "η" has the same meaning as defined above. The carbosilane is composed of at least one structural unit represented by the following: (R^SiRii), (R72SiR&quot;), (R7SiRll), and (SiR11). Specific examples include (R) a linear polycarbosilane composed of sSiR and (R^SiR11) units; a cyclic polycarbodecane composed of (R^SiR11) units; a branched chain polycarbon decane composed of *(R7SiRll) and (siRll) units; *( a polycarbodecane composed of R73SiRn) and (R7SiRll) units; a polycarbodecane composed of (R^SiRn) and (SiRn) units, a polycarbodecane composed of (R SiR ) and (SiR11) units; (R72SiRii) 161877.doc -27- 201235296 and (R7SiR&quot;) units of polycarbon decane; poly (carbonate) consisting of (R^SiR1) and (SiRM) units; from (R73SiRn), (R72SiRn) and (R7SiR&quot;) a polycarbosilane composed of units; a polycarbodecane composed of (R73SiRn), (R72SiR&quot;) and (SiR11) units; a polycarbon decane composed of (R^SiR11), (R7SiRn) and (SiR&quot;units; Polycarbonate composed of (R72SiRn), (R7SiR&quot;) and (SiR丨丨) units; by (R73S a polycarbosilane composed of iRn), (R72SiRn), (R7SiRn) &amp; (SiRn) units; and a similar structural unit represented by each of (R73SiRu), (R72SiR&quot;), (R7SiRn), and (SiRu) The number of repetitions of the structural unit is preferably in the range of 2 to 10,000, more preferably in the range of 3 to 1,000, and even more preferably in the range of 3 to 500. The above carbon decane can be produced by a method known in the art. Examples of methods for preparing carbon stone sinter are described in J. Dunogues et al., Macromolecules, 21, 3 (1988) and U.S. Patent 3,293,194. The above carbon calcination may be a rhodium-containing copolymer compound formed with other polymers. Examples of the ruthenium-containing copolymer compound which can be used as a carbonaceous sinter include a ruthenium-containing copolymer compound having a Si—(CH 2 ) n—Si bond and a Si—O—Si bond; having a Si—(CH 2 ) n—Si bond and a SiGe-containing copolymer of Si-Si bond; a ruthenium-containing copolymer compound having a Si-(CH2)n-Si bond and a Si-N-Si bond; having a Si-(CH2)n-Si bond and Si-(C6H4) a ruthenium-containing copolymer compound having an n-Si bond; a ruthenium-containing copolymer compound having a Si-(C6H4)n-Si bond and a Si-0-Si bond; having a Si-(C6H4)n-Si bond and a Si-Si bond a ruthenium copolymer compound; a rhodamine-containing copolymer compound having a Si-(C6H4)n-Si bond or a Si-(CH2CH2C6H4CH2CH2)n-Si bond and a Si-N-Si bond; and the like. In the equation, "η" has the same meaning as defined above. 161877.doc -28· 201235296 Component (B) is preferably a decane, and more preferably a fluorene represented by the following average unit formula Oxyalkane: (R73Si〇W2)a(R72Si〇2/2)b(R7Si〇3/2)c(si〇4/2)d. In the formula, R7 each independently represents a monovalent hydrocarbon group, a hydrogen atom, a halogen atom, an epoxy group-containing organic group, an acryl-containing fluorenyl group or a mercaptopropenyl group-containing organic group, and an amine group-containing organic group. An organic group containing a mercapto group, an alkoxy group or a trans group. "a", "b", rc", and rd" are numbers greater than or equal to 且 and less than or equal to 1 and satisfying "a" + rb" + "c" + rd"=1. However, "a", "b" and rc" cannot be both at the same time. Specific examples of the crosslinking reaction include an addition reaction such as a hydrazine hydrogenation reaction, a Michael addition reaction, a Diels-Alder reaction, and the like; a condensation reaction such as dehydration Reaction, dehydrogenation reaction, dehydration reaction, deamination reaction and the like; ring opening reaction such as epoxy ring opening, ester ring opening and the like; and freedom caused by peroxide, UV or the like Base reaction. Specifically, when the component (A) has an aliphatic unsaturated group and the component (B) has a fluorene-bonded hydrogen atom, a mixture thereof can be subjected to a hydrazine hydrogenation reaction in the presence of a hydrazine hydrogenation catalyst. Specific examples of the hydrazine hydrogenation catalyst include fine platinum powder, matte black, fine bismuth-containing cerium oxide powder, fine platinum-containing activated carbon, gas platinum acid, platinum tetrachloride, gas solution of chloroplatinic acid, and olefins of platinum And the thin base of the broken crystals of platinum. The amount by which the rhodium hydrogenation catalyst can be used is not particularly limited. However, the catalyst is preferably such that the amount of metal atoms in the catalyst is from 〇1 ppm to 161877.doc -29- 201235296 1 by mass (by weight) relative to the total weight of component (A) and component (B). In the range of 000 ppm and better in 0

The amount in the range of Ppm to 500 ppm and the component (B) have a ruthenium-bonded hydrogen

At the time, the characteristics of the electrode active material as the ruthenium-carbon-containing composite obtained by baking the obtained cured product tend to be degraded. When the component (A) has an aliphatic unsaturated group atom, the respective amounts thereof are not particularly limited. (B) The hydrazine-bonded hydrogen atom is 0.1 mole to 5 Å per 1 mole and group. In the molar range, when the component (A) contains an aliphatic unsaturated group and the component contains an aliphatic unsaturated group, an acryloyl group, a fluorenyl fluorenyl group or a hydrazine-bonded hydrogen atom, a mixture thereof can be used. The heat and/or light utilizes a free radical initiator to cause a free radical reaction. Specific examples of the radical initiator include dialkyl peroxide, didecyl peroxide, peroxy ester, peroxydicarbonate, and similar organic peroxides' and organic azo compounds. Specific examples of organic peroxides include diphenyl ketone peroxide, bis-p-chlorobenzamide peroxide, bis-2,4-dibenzophenone peroxide, and di-tert-butyl peroxide. Oxide, dicumyl peroxide, tert-butyl perbenzoate, 2,5-bis(t-butylperoxy)-2,3-dimethylhexane, peracetic acid tributyl Ester, bis(o-methylbenzhydryl peroxide), bis(metamethoxybenzhydryl peroxide), bis(p-methylbenzoyl peroxide), 2,3-dimethyl Benzobenzamide peroxide, 2,4-dimethyl 161877.doc • 30· 201235296 benzoyl hydrazino peroxide, 2,6-dimethylphenyl hydrazino peroxide, 2, 3, 4-dimethylphenylhydrazinyl peroxide, 2,4,6-trimethylsulfonylcarbenyl peroxide, and similar methyl-substituted benzoyl peroxide; second benzoic acid Vinegar, monoisopropyl peroxide, 2,5-dimercapto-2,5-di(t-butylperoxy)hexane, tert-butyl peroxyacetate monoester and Oxyacetic acid third vinegar; and mixtures thereof. Further, specific examples of the organic azo compound include 2,2·-azobisisobutyronitrile, 2,2,-azobis(4-methoxy-2,4-indenyl valeronitrile), 2, 2 '-Azobis(2,4-dioxyl valeronitrile), 2,2,-azobis-isobutylvaleronitrile and hydrazine, hydrazine 1-azobis(1-cyclohexanecarbonitrile). The amount of the radical initiator which can be used is not particularly limited 'but preferably relative to the total weight of the component (Α) and the component (Β) in the range of 〇"mass (%)% to 1% by mass%) Internal, and more preferably in the range of 0.5% by mass to 5% by mass. When component (A) contains an aliphatic unsaturated group and component (Β) contains an aliphatic unsaturated group, an acryloyl group, a methacryloyl group or a hydrazine-bonded hydrogen atom, it is not particularly limited. . However, the content thereof is such that the aliphatic unsaturated group, the acrylonitrile group, the methyl propyl sulfhydryl group in the component (Β) are bonded to the aliphatic group in each 1 molar component (Α). The unsaturated group is in the range of 5 Torr to Moule, preferably in the range of (U Mo to 30 Mo, and more preferably in the range of 1 Mo to 1 Mo. The reason is When the amount of the component (Β) is less than the lower limit of the above range, the carbonization yield tends to decrease when the obtained cured product is baked. In the other aspect, when the amount exceeds the above (4), the obtained product is obtained by baking the obtained cured product. The characteristics of the electrode active material of the carbon-cut composite material tend to be degraded. 161877.doc -31 - 201235296 When a cured product obtained by crosslinking component (A) with component (B) is formed, curing The product is formed, for example, by being produced according to the following method 1 or 11 and then subjecting the product to a baking step. j: after mixing the component (A) with the component, the mixture is allowed to be at a temperature not exceeding 3 Torr and Preferably, it is pre-cured at a temperature of from 〇 to 300 C. It is preferred to pulverize the obtained pre-cured mixture to make the particles flat. The lower baking step is performed after the average diameter is 4J 4111 to 3 〇μηη and preferably 1 pm to 2 〇μηι. π: In particular, the cured product preferably used in the present invention is composed of spherical particles. Forming the spherical particles, the crosslinkable composition comprising the component (4) and the component (Β) is preferably crosslinked by spraying the curable composition into hot air or Crosslinking occurs after the crosslinked composition is emulsified or dispersed in an incompatible medium. When one of the component (Α) and the component (Β) has an aliphatic unsaturated group and the other has a cleavage hydrogen bond In the case of an atom, the fine particles of the solidified product can be sprayed into the hot air by the particle-form cross-linking composition containing the component (4) and the component (Β) hydrogenation catalyst, and the gasification reaction is carried out by the gasification reaction Further, the fine particles of the cured product can be added to the aqueous emulsifier by stirring the crosslinkable composition comprising the component (4), the component (Β) and the crushed hydrogenation (tetra) agent by stirring. Emulsified to form fine particles of the crosslinkable composition and then formed by cross-linking by hydrogenation reaction. Particularly limited, specific examples include ionic surfactants, nonionic surfactants, and ionic boundaries, surfactants, and, in particular, are produced by cross-linking the composition with water. From the standpoint of excellent uniform dispersion and stability of the oil-in-water emulsion, the emulsifier is preferably a mixture of one or more ionic surfactants 161877.doc-32·201235296 with one or more nonionic surfactants. Further, by using a combination of cerium oxide (gelatinous cerium oxide) or a metal oxide (such as titanium oxide) and an emulsifier and carbonizing while the cerium oxide remains on the surface of the cured product = particle, it can be on the carbon surface. A stable layer is formed thereon, and the enzymatic yield can be asked 'and the surface oxidation can be inhibited when the carbon material is placed. The diameter of the solidified product particles is not particularly limited, but the average diameter of the composite material having an average diameter of i (four) to 2 g, which is suitable for the electrode active material, is preferably in the range of 5 μm to 30 μηι. Inside, and more preferably in the range of 5 μη to 20 μπι. In order to achieve cross-linking of the cured product particles obtained as described above and to improve the yield of carbonization by baking, the cured product particles are preferably further heat-treated in air at 15 (TC to 30 (TC temperature). The ruthenium-containing carbon-containing composite material of the present invention can be heat-treated together with the carbonaceous material (c) by the component (4) and the component (E1) product (for the process, it is preferably included before the baking process) The carbon material (6) is coated on the surface of the cured product obtained by crosslinking the components () and the knives (8) to form composite particles. In the composite particles, the curing is applied to the component (VIII) and the component (b). The amount of component (C) on the surface of the product is preferably from 质量5 mass% by weight to 2% by mass%, more preferably in lg (weight to 1 G mass% by weight, and even better) It is from 1 mass% by weight to 5 mass%. The method for preparing the composite is not "manufactured and its (iv) includes (1) at the age of supply mechanical energy / (d) "component (4) is crosslinked with component (B) a method of curing a product with a carbonaceous material f(C); and by making component (4) with a group 161877.doc -33·201235296 When the (B) is crosslinked in an aqueous dispersion medium to prepare a solidified particle in an emulsified state, the carbonaceous substance (C) is adsorbed on the cured product by dispersing the carbonaceous substance (C) in the aqueous dispersion medium. Surface method. When (1) mixing/stirring a solidified product obtained by crosslinking component (A) with component (B) and a carbonaceous material (c), a mixing device and a mixing device are used. The surface treatment device is not particularly limited. The pulverization, mixing, and surface treatment may be performed using a dry method or a wet method. Examples of the pulverizing device include a device that is pulverized by pressure or impact, such as a particle crusher, a gyratory crusher, a newspaper. a crusher, a roughing machine, an automatic grinder, and the like; a device in which an impact plate is fixed around a rotor that rotates at a high speed and pulverizes the product using a shear force generated by a rotor and an impact plate, and the like, such as a hammer mill, Impact crusher, needle mill ' atomizer, pulverizer and the like; the roller or ball is pressed on the top of the ring and rotated so that the product is crushed by being placed between the ring and the roller or the ball and impeding pressure Attack Annular grinder, universal grinder, centrifugal, roller grinder, centrifugal, ball mill (4), % as in 1), angle mill (angmill) and the like; equipped with a cylindrical crushing chamber and inserted into the crushing chamber t a pulverizing device that is pulverized by a ball or a rod that is rotated or vibrated, such as a pot mill, a ball mill, a vibrating mill, a lamp star ball mill, and the like; and has a cylindrical pulverization to and a ball or a bead Inserting the pulverized chamber towel as a pulverizing device, such as a tower grinder, an attritor, sand, which is broken and is pulverized by shearing force and friction generated by a disc-like or ring-feeding mechanism inserted into a crushing medium. A mill and the like 'and a medium that is ejected from a nozzle (such as high-dust air or the like) and impinges particles in the form of ultra-high-speed jets and the product is crushed by smashing particles by 161877.doc -34· 201235296 Devices such as jet mills and the like. Examples of mixing devices include mixers having a mixing shaft in a mixing vessel, wherein mixing blades are attached to the shaft and mixing particles, such as a super mixer, a high-speed mixer, a Henschel mixing (Henschel mixer) and the like; comprising a continuous mixer having a main shaft having a vertical cylinder having a particle insertion opening and a mixing blade, wherein the main shaft is open by the upper bearing branch and the discharge side is open, such as a Flexomix mixer and the like; and a continuous mixer that performs mixing by loading a raw material on an upper portion of a disk having a stirring needle and rotating the disk at a high speed to generate a shearing force, such as flow jet mixing , screw needle mixer and the like. Examples of surface treatment devices include Hybridizer® (by Nara Machinery)

Co" Ltd.), Mechanofusion® and NobiltaTM (by Hosokawa)

Micron Ltd.) and the like. When (ii) a cured product particle is prepared by crosslinking component (A) and component (B) in an emulsified state in an aqueous dispersion medium, the composite particle can be obtained by causing a carbonaceous substance (C) It is obtained by dispersing in an aqueous dispersion medium and adsorbing the carbonaceous substance (c) on the surface of the cured product and then removing the water. In this case, it is preferred to emulsify the component (A) and the component (B) in an aqueous dispersion medium, and then to disperse the carbonaceous substance (C) in the emulsion. The baking conditions are not particularly limited, but the baking is preferably carried out in an inert gas or in a vacuum at a temperature of 3 Å &lt;&gt;c to i, 5 Torr. Examples of inert gases include nitrogen, helium, and argon. Please note that the inert gas may contain hydrogen or a reducing gas such as 16I877.doc •35- 201235296. Thus, the composite of the present invention may contain traces of nitrogen. The baking temperature is more preferably in the range of 500 ° C to 1,000 ° C. The baking time is not particularly limited' but can be set in the range of 10 minutes to 10 hours, and preferably set in the range of 30 minutes to 3 hours. The heating method and the type of the carbonization furnace are not particularly limited, and the carbonization can be carried out in a fixed bed type or a fluidized bed type carbonization furnace, with the proviso that the furnace can heat the product to an appropriate temperature. Specific examples of carbonization furnaces include Reidhammer furnace, tunnel furnace, single type furnace, Oxynon furnace, bottom kiln, pusher raft, batch type rotation Kiln and continuous rotary kiln. The carbonaceous substance (C) is not particularly limited, and its limitation is that it is mainly composed of carbon, and examples thereof include activated carbon, natural graphite, artificial graphite, various coke powders and mesophase carbon; vapor grown carbon fiber, pitch-based Carbon fiber, PAN (polyacrylonitrile) based carbon fiber and similar carbon fiber; acetylene black, furnace black, ketjen black, gas black and similar carbon black; carbon nanofiber; carbon nanotube; Things. The ruthenium-containing carbon-containing composite material of the present invention may be composed of particles having an average diameter of 5 ^^(7) to "μπι. The average diameter is preferably from 1 〇^^ claw to buckle, more preferably from 100 nm to 30 μηΐ, and even better. For the carbon-based composite towel of the present invention, the amount of carbon is preferably: mass (weight: 50 mass% by weight, more preferably 5 mass% by weight to 3 〇) In the mass (weight) / and even more preferably from 5 mass% by weight to 2 〇 mass (when the amount is within this range) even if the composite material containing the invention is used alone as an electrode In the case of the active material, the composite material containing the stellite carbon-based I61877.doc -36 - 201235296 material also has a suitable electrical conductivity and can suppress the decrease in the charge and discharge capacity of the electrode. The surface of the ruthenium-containing carbon-containing composite material of the present invention has The coating of carbon. The thickness of the carbon coating is not particularly limited, but is preferably 5 nm to 2 μηη, more preferably 1〇11111 to 10111, and even more preferably 2〇11〇1 to 1〇〇11111. The core part covered by the carbon coating is the component and component (Β) The baked product of the cured product. The ruthenium-carbon-containing composite obtained by the above process has ruthenium, carbon and oxygen as main components and can be represented by the following average composition formula: SiuoC^Hh. In the formula, rf", "g" and "h" are numbers respectively satisfy 〇.5 &lt;f&lt;l〇〇, 〇sg&lt;5 and score &lt;1〇. Preferably, 1.5&lt;f&lt;70, and more preferably, 2.0&lt;f&lt;50. The obtained carbon-coated ruthenium-containing carbon-containing composite material can be used as an electrode active material. The electrode active material of the present invention may be in the form of particles, and in this case, the average diameter thereof is Preferably, it is i^„1 to 5〇μηη, more preferably i pm to 40 μπι′ and even more preferably 1 0111 to 3〇μηη. The composite material comprising the surface-carbon coated carbon-containing carbon-containing composite of the present invention. The electrode active material has high reversible capacity and stable charge and discharge cycle characteristics, and can be used to manufacture an electrode having a small potential loss when lithium is released through a simple manufacturing process. Thus, the electrode active material can be suitably used as an electrode of a nonaqueous electrolyte primary battery. Active material. The electrode active material It is suitable as an active material for an electrode of a lithium or a chain ion secondary battery. Electrode The electrode of the present invention is characterized by comprising the above electrode active material. The electrode is manufactured 161877.doc • 37· 201235296 The method is not particularly limited. The method of manufacturing the electrode of the present invention Real ==:: Carbon-based composite and adhesive to make electrode * solvent, contact sticky = dry electrode to make 2 collectors and then dry... &quot; outside' paste applied to the current collector The thickness is, for example, about 30 um 5 π A Α "claw to 500, and preferably about 50 from the claw to 30 〇. The method of post-drying is not particularly limited, but under vacuum drying. The thickness of the electrode material on the current collector after drying is about 1 〇 (4) material and preferably about 2 至 to 2 〇〇. When an electrode comprising a compound of 石 碳 carbon-based Ί f can be fabricated by orienting the material in a single direction and forming the material into a fabric or similar structure or a bundle of violet or woven metal, conductive poly-taste or similar conductive fibers. . The terminals may be incorporated as needed when forming the electrodes. The current collector is not particularly limited, and specific examples thereof include metal meshes and foils made of copper, brocade, gold, and the like. Specific examples of the binder include a gas-based (for example, polyvinylidene chloride and polytetramethylene) and the amount of the styrene-butadiene bismuth ruthenium binder is not particularly limited, but the lower limit is per 1 〇〇 mass (by weight) parts of the rhodium-containing carbon-based opening material 5 parts by weight to 3 parts by mass and preferably 5 parts by weight to 2G mass by weight Within the scope. When the amount of the binder used exceeds these ranges, for example, the adhesive strength of the composite material containing the stellite carbon-based on the surface of the current collector will be insufficient; and an insulating layer which may cause an increase in the internal resistance of the electrode may be formed. The method of preparing the paste is not particularly limited, and examples thereof include a method of mixing a mixed liquid (or dispersion) containing a binder and an organic solvent with a composite material containing a carbon-based composite material. As the solvent, a solvent which can dissolve or disperse the binder is used, and specific examples thereof include N-methyl (IV), N,N-dimethylmethamine and the like. The amount of the solvent to be used is not particularly limited. When the binder is mixed, the mixture has a paste form, but the amount is generally (10) by mass (by weight) to 5 Å per 10 parts by mass of the composite material containing the stellite carbon group. 0 mass (by weight) parts range β, preferably in the range of _ mass (weight) parts to weight loss (weight) parts, and more preferably in the range of _ mass (weight) parts to 30,000 mass parts . Additives may be compounded in the electrodes of the present invention as needed. For example, an electric (four) promoter can be added to the electrode during manufacture. The amount of the electric (iv) accelerator to be used is not particularly limited, but is in the range of 2 parts by mass to 60 parts by mass, preferably 5 parts per gram by weight of the composite material containing the stellite carbon-based composite. The mass (by weight) parts are in the range of 4 G mass parts by weight, and more preferably in the range of 5 parts by mass to 20 parts by mass. When the amount is within this range, the electrical conductivity will be excellent and the charge and discharge capacity of the electrode can be suppressed from decreasing. Examples of the mountain conductivity promoter include carbon black (e.g., ketjen black, acetylene black), vascular tubes, and the like. A [conductivity enhancer may be used or a combination of two or more conductivity enhancers may be used. The conductivity promoter may, for example, be mixed with a paste comprising a carbon-cutting group (tetra) m彳 and a solvent. The graphite or similar electrode active material may be compounded in the electrode of the present invention as another optional additive. Electrical storage device 161877.doc 39- 201235296 The electrical storage device of the present invention is characterized by comprising the above electrode. Examples of the member include a primary battery, a secondary battery, a clock-ion two-electric hybrid capacitor (redox capacitor), an organic free = cell, and a clock or ion secondary battery is preferred. The clock*-human pool can be manufactured using a battery assembly according to a generally known method, and the :: battery assembly includes a negative electrode including the above electrode, a positive electrode capable of being stored and discharged, an electrolyte solution, a separator, a current collector 'sealing 塾, Sealing plates, housings and the like. The secondary battery can be manufactured by using a battery assembly including a positive electrode composed of the above electrode, a negative electrode 'electrolyte solution composed of a metal, a separator current collector, a sealing port, a sealing plate, according to a generally known method. , outer casing and the like. BRIEF DESCRIPTION OF THE DRAWINGS Figures 1 and 2 illustrate a preferred embodiment of the battery of the present invention (a clock or a clock-ion primary battery). BRIEF DESCRIPTION OF THE DRAWINGS Figure 1 is a schematic exploded cross-sectional view showing a lithium ion secondary battery (button battery) as an example of the battery of the present invention. The lithium ion secondary battery illustrated in Fig. 1 comprises a cylindrical outer casing 1 having a bottom portion and an open top portion, a cylindrical seal 2 having open ends and an inner circumference substantially the same as the outer circumference of the outer casing 5. 3. SUS plate 4, current collector 5, composite material having the ruthenium-carbon-containing composite material of the present invention as the electrode active material, the negative electrode 6, the separator 7, the positive electrode 8, the current collector 9 and the sealing plate 10 〇 have a substantial ring The plastic ring 3 having a shape slightly smaller than the inner circumference of the outer casing 1 is disposed in the outer casing i of the lithium ion secondary battery illustrated in Fig. 1 and has a substantially disc-like shape and a slightly smaller size than the outer casing 1 The internal 161877.doc 201235296 perimeter of the simple board 4 is stacked on the washer 3. The current collectors and the negative electrodes 6 each having a substantially disc-like shape and having a size slightly smaller than the outer inner circumference &amp; are placed on the SUS plate 4. A spacer 7 which is a single-layer disk-like member and whose size is substantially the same as the inner circumference of the outer casing 1 is stacked on the negative electrode 6. Electricity. The solution solution is impregnated with the separator 7. Note that the spacer 7 may be composed of two or more disc-like members. A positive electrode 8 having substantially the same size as the negative electrode 6 and a current collector 9 having a size substantially the same as that of the current collector 5 are provided on the spacer 7. The current collector 5 is composed of a mesh 'foil or the like made of copper, nickel or the like, and the current collector 9 is composed of a net made of slag or a similar metal, pig or the like. The current collector 5 and the current collector 9 are bonded to the negative electrode 6 and the positive electrode 8, respectively, and formed integrally. * In the ion secondary battery illustrated in Fig. 1, (4) 塾 2 is mounted on the wall surface of the outer casing 1, and further 'a cylindrical sealing plate having a bottom and an open type and having a size slightly larger than the sealing cymbal 2 〇 The inner circumferential surface is mounted on the outer circumferential surface of the gasket 2. Thereby, the outer casing #7 (7) is isolated by the gasket 2, and is formed with a casing 1, a gasket 2, a gasket 3, a SUS plate 4, a current collector 5, a negative electrode 6, a separator 7, a positive electrode 8, and a set having a common axis. The button battery of the electric appliance 9 and the sealing plate 10. The positive electrode 8 in the lithium ion secondary battery illustrated in Fig. 1 is not particularly limited, and may be composed of, for example, a positive electrode active material, a conductivity promoter, a binder, and the like. Examples of the positive electrode active material include Lic® 2, LiNiO 2 , LiMn 204, and the like metal oxides; [King #~, Li2FeSi〇4, and the like polyanion oxide; spinel LiMn2〇4; and the like. A single positive electrode active material can be used or a combination of two or more positive energies can be used. Examples of the conductivity promoter and the binder include the above substances. Fig. 2 is an exploded cross-sectional view showing a lithium secondary battery (button battery) as an example of the battery of the present invention, which is manufactured according to an actual example. The lithium secondary battery illustrated in FIG. 2 includes a cylindrical gasket having a bottom portion and an open top portion, and a cylindrical gasket 2 having an inner circumference substantially the same as an outer circumference of the outer casing 1, and a ring 3 The grabbing plate 4, the negative electrode 6 composed of metal, the separator 7, and the complex containing the stone-bearing carbon group of the present invention. The material serves as the positive electrode 8 of the electrode active material, the current collector 9, and the sealing plate 10°. The gasket 3 having a substantially annular shape and slightly smaller in size than the inner circumference of the outer casing 1 is placed in the lithium secondary as illustrated in FIG. The outer casing of the battery is in the middle. The SUS plate 4 having a substantially disc-like shape and having a size slightly smaller than the inner circumference of the outer casing i is stacked on the gasket 3. A negative electrode 6 having a substantially disc-like shape and having a size slightly smaller than the inner circumference of the outer casing 1 is provided on the sus plate 4. A spacer 7 as a single-layer disc-like member and having a size substantially the same as the inner circumference of the outer casing k is stacked on the negative electrode 6. The separator 7 is impregnated with an electrolyte solution. Note that the spacer 7 may be composed of two or more disc-like members. The positive electrode 8 and the current collector 9 having substantially the same size as the negative electrode 6 are provided on the spacer 7. The current collector 9 is composed of a mesh made of copper, nickel or the like, a foil or the like, and is bonded to the positive electrode 8 and formed integrally. In the lithium secondary battery illustrated in FIG. 2, the gasket 2 is mounted on the wall surface of the casing 2; and further, the interior of the cylindrical sealing plate 1b having a bottom and an open bottom and having a size slightly larger than that of the gasket 2 The circumferential surface is mounted on the outer circumferential surface of the seal 2 of 161877.doc •42· 201235296. Thereby, the outer casing and the sealing plate 1 are separated by the gasket 2, and are formed with the outer casing 1, the gasket 2, the gasket 3, the SUS plate 4, the negative electrode 6 'isolator 7, the positive electrode 8, the current collector having the common axis. 9, and the button battery of the sealing plate 10. The electrolyte solution included in the bell or chain ion secondary battery illustrated in Fig. 1 and Fig. 2 is not particularly limited, and a generally known electrolyte solution can be used. For example, a non-aqueous lithium or lithium ion secondary battery can be produced by using a solution in which an electrolyte is dissolved in an organic solvent as an electrolyte solution. Examples of the electrolyte include LiPF6, LiC104, UBF4, LiClF4, LiAsF6,

Examples of the organic solvent of LiSbF6, LiAl〇4, LiAiCl4, Lic, and similar lithium salts include carbonates (for example, propyl carbonate, ethyl carbonate, diethyl carbonate), lactones (for example, γ-butyrolactone), Chain ethers (eg, dioxyloxyethane, dioxane, diethyl ether), cyclic ethers (eg, tetrahydrofuran, 2-methyltetrahydrofuran, dioxane, 4-methyldioxa) Cyclopentane), cycline (such as sulfolane), sulfoxide (such as disulfoxide), nitrile (such as acetonitrile, bisnitrile, benzoquinone), guanamine (such as N'N-dimethyl Indoleamine, n, n-dimethyl ethanoamine, polyoxyalkylene glycol (such as diethylene glycol) and similar aprotic two agents. A single organic solvent may be used or a mixed solvent containing two or more organic solvents may be used. The concentration per 1 liter of the electrolyte solution electrolyte is, for example, about 3 to 5 moles, preferably about 5 to 3 moles, and more preferably about 0.8 to 1.5 moles. The spacer * in the lithium or lithium ion secondary battery illustrated in Fig. 1 and Fig. 2 is not particularly limited' and a commonly known spacer can be used. Examples thereof include porous polypropylene non-woven fabrics, porous polyethylene non-woven fabrics, and other porous membranes of 161, 877 - 00 - 201235296. The electrical storage device of the present invention is not limited to the ones illustrated in Figs. 1 and 2 and can be applied, for example, to various forms such as a stacked battery, a packaged battery button battery, a gUM battery, a battery pack, and a rectangular battery. The utility model relates to an electric storage element, in particular a chain or a clock ion secondary battery, which is suitable for use as a video camera, a computer, a word processor, a portable stereo device, and a honeycomb type, and is characterized by light weight, high capacity and high energy density. Power supplies for telephones and other mobile small electronic devices; power supplies for hybrid and electric vehicles; and power supplies for electrical storage. Industrial Applicability The electrode active material of the present invention has a high reversible capacity stable charge and discharge cycle characteristics and high initial charge and discharge efficiency. The electrode active material of the present invention is suitable for an electric storage device, particularly an electrode of a light or _ sub-secondary battery. Further, the electrode active material of the present invention uses an inexpensive raw material and can be manufactured by a simple manufacturing process. Further, the electrode of the present invention can impart a reversible amount of electricity between cells, stable charge and discharge cycle characteristics, and high initial charge: discharge efficiency. Therefore, the electric storage device of the present invention can have high reversible capacity, stable charging and discharging cycle characteristics, and high initial charging and discharging efficiency. EXAMPLES: The composite electrode active materials, electrodes and electrical storage devices of the present invention are described in more detail hereinafter, but the invention is not limited to such examples. In these examples, battery characteristics were observed and evaluated via X-ray diffraction, scanning electron microscopy, transmission electron microscopy, and energy dispersive X-ray analysis as described below. 161877.doc 201235296 x-ray diffraction device: RINT 2000 (manufactured by Rigaku Corporation) X-ray generator: target Cu tube voltage: 40 kV tube current: 40 mA 20=10-90 divergence slit: 2/3° divergence height : 10 mm scattering slit: 2/3° receiving slit: 0.3 mm

Scanning Electron Microscope: SEM Device: JSM-5800LV (manufactured by JEOL Ltd.)

Transmission Electron Microscopy: TEM Device: JEOL 2100F TEM (manufactured by JEOL Ltd.) Energy Dispersive X-ray Analysis: EDX Device: 】 £0-2100 (Evaluated by Qiao 0 [1^(1.)) Battery characteristics are as follows HJR-110m SM6 (manufactured by Hokuto Denko Corporation) measures the charge and discharge characteristics of a lithium secondary battery using the composite material of the present invention. Charging is performed using a constant current of 0.1 C (70.0 mAh/g), which is 1 per constant current. The theoretical capacity of the g (mass) ruthenium-based composite material (700 mAh/g, expressed as 1_0 C) is 1/10. When the battery voltage reaches 0.02 V and the voltage remains constant, the current value becomes 1/10. It is considered that the charging is complete. At this time, the charging capacity is calculated. In addition, the discharging is performed at a constant current of C1 C and is considered complete when the voltage is 161877.doc •45-201235296, and the voltage is calculated to be 1·5 v. The cycle characteristics were evaluated under the same conditions. The initial charge and discharge efficiency (CE%) is expressed as a percentage of the discharge valley amount relative to the charge capacity in the first cycle, and the capacity retention rate after the cycle test is 1 cycle after the charge capacity. Relative to the initial charge The percentage (%) of the electric capacity is expressed. Practical Example 1 Preparation of a ruthenium-containing crosslinked particle mixture comprising 2.4 g of a polystyrene having a polymerization degree of about 2 Å and a solution of 3 〇g of fluorene and a polyoxazine containing the following Composition: 24 g of an organic polyoxane represented by the formula: [(CH2=CH)(CH3)2Si〇1/2](} 25(C6H5Si〇3/2). 75, 2.4 g is represented by the following formula The organopolyoxane: (CH3)2HSiO[(C6H5)2Si〇]Si(CH3)2H, and 2.4 g of an organopolyoxane represented by the formula: C6H5Si[OSi(CH3)2H]3' forms uniform Solution. Subsequently, the resulting solution is mixed with 0.01 g of 1,3-divinyltetramethyldiazepine oxime complex and 〇ig methyl gin (u dif-yl-2-propynyloxy) decane. And uniformly stirring the components at room temperature. Thereafter, the polyoxonium composition was crosslinked by being placed in an oven for 30 minutes to obtain a gel-like substance having white turbidity. Heating under reduced pressure This gel-like substance was obtained by removing toluene' and obtaining a white solid product. The cross section of the solid observed under SEM showed that the cross-linked particles were uniformly dispersed in polystyrene. Extraction of ruthenium-containing crosslinked particles with toluene It was confirmed that it had a regular spherical shape with an average diameter of 2.5 μm (Fig. 3). 161877.doc • 46 · 201235296 Preparation of a carbon-coated cerium-containing carbon-based composite material obtained by mixing 4·75 g in a ball mill as above The ruthenium-containing crosslinked particles and 0.25 g of acetylene black were obtained for 5 minutes to obtain black particles. The particles were placed in a ssa_S grade alumina crucible and baked in a muffle furnace at 60 (rc under nitrogen atmosphere for 2 hours, followed by baking at 1 〇〇 (rc) After cooling, black particles with a yield of 75% were obtained. The amount of carbon coated on the surface of the carbon-coated ruthenium-carbon-containing composite material obtained was 6.6 mass of the ruthenium-carbon-containing composite. (% by weight) SEM observation of the obtained black particles revealed that the black particles were spherical particles having an average diameter of about 2 45 μm (Fig. 4). Further, a transmission electron microscope (hereinafter referred to as "ΤΕΜ") and energy dispersion χ were used. The cross section of the observation material by ray analysis (hereinafter referred to as "EDx") shows that the black particles are composite particles 'where the core of the particles is mainly composed of si〇c components, and the surface of the particles is coated with a diameter of 3 〇 nm to 40 nm. Carbon particles (Fig. 5) Electrode fabrication 107.58 mass parts by weight of the ruthenium-containing carbon-containing composite material obtained above and 6.94 mass parts by weight of acetylene black were mixed in a mortar for 15 minutes. Thereafter, 12.00 mass was added. (weight) Ethylene and further mixing the components for 15 minutes. Subsequently, the solvent N_mercapto-2-pyrrolidone was mixed to obtain a slurry-like mixture, which was then applied to the copper foil roll by a knife method at a thickness of about 25 〇 4 claws. Thereafter, the coated foil roll was dried under vacuum at 851 for not less than 12 hours, and an electrode having a thickness of about 4 〇μη ΐ 2 was obtained. Manufacturing and Evaluation of Secondary Battery Using Metal Lithium as a Counter Electrode for Electrodes Using a mixed solvent of ethyl carbonate and diethyl carbonate in a volume ratio of 1:1 161S77.doc -47·201235296 (in which lithium hexafluorophosphate is dissolved at a ratio of 1 mol/L) as an electrolyte solution; The woven fabric was used as a separator to manufacture a button-type lithium secondary battery. Subsequently, the battery characteristics of the lithium secondary battery were evaluated according to the above-described evaluation method of the battery characteristics. The battery characteristics are shown in Table i. Practical Example 2 Preparation of ruthenium-containing crosslinked particles by Mix 15_49 g DVB570 (by Nippon Steel Chemical Co

Manufactured by Ltd.; main component: divinylbenzene and vinylethylbenzene; ratio of divinylbenzene included in main component: 60 mass% by weight) and 9.5 ig two molecular ends using triterpene a decyloxy-terminated fluorenylhydroxanthene copolymer (viscosity: 20 mPa.s; 矽 bond hydrogen atom content: ι·58 mass% by weight; including the amount of vinyl in every 1 mole of DVB 570 A crosslinkable composition is prepared by including a hydrogen atom in a 1 molar copolymer. Thereafter, add 25 g of 10 mass% by weight of polyoxyethylene secondary alkyl ether (San〇nic

SS120' is an aqueous solution manufactured by Sanyo Chemical Industries, Ltd.; HLB = 14.5). Subsequently, a water-based emulsion of a crosslinkable composition was prepared by emulsifying the mixture by using a homodisperser (h〇m〇_disper) (rotation speed: 5000 rpm). Subsequently, '1,3-divinyl group will be separately prepared. Water-based emulsion of platinum-based catalyst with tetramethyl dioxoxane platinum complex as main component (average diameter of emulsion = 0.05 μηι; initial metal concentration = 〇 5 mass% by weight) and crosslinkable The water-based emulsion of the composition is uniformly mixed in mass (by weight) relative to the crosslinkable composition comprising 20 ppm of platinum metal, and mixed at 60 ° C 161877.doc • 48· 201235296 Μ·ηι 5 μπι 60 minutes. Thereafter, the cured product particles having an average diameter are prepared by removing water. Preparation of carbon-coated ruthenium-containing carbon-containing composite material Black particles were obtained by mixing 4.75 g of the cross-linked particles obtained as above and 〇25 g of B-fast black for 5 minutes in a ball mill. . As in the practical example, the solidified product particles are placed in SSA rhyme oxidized (four) steel and fed. After cooling, black particles having a yield of 62% were obtained. The amount of carbon coated on the surface of the resulting surface (4) coated carbon-containing composite material was 7.6 mass% by weight of the composite containing the stellite carbon-based material. The black particles were observed by rsem, TEM and EDX. The black particles were spherical particles with an average diameter of about 丨〇 to 5 〇μη, mainly composed of Si0C components, and the black particles were composite particles, and the surface coating of the particles. There are carbon particles having a diameter of 3〇11〇1 to 4〇nm. The manufacture and evaluation of the electrode and the secondary battery using the ruthenium-carbon-containing composite material described in this practical example were carried out in the same manner as in the practical example. The battery characteristics are shown in Table 1. Practical Example 3 Preparation of ruthenium-containing crosslinked particles by mixing 100 g of DVB630 (by Nippon Steel Chemical Co.,

Manufactured by Ltd.; main components: divinylbenzene and vinyl ethyl stupid; ratio of divinylbenzene included in main component: 63 6 mass% by weight), 153.4 g of two molecular ends with triterpenes Alkoxy-terminated dimethyloxoxime-fluorenylhydroquinone copolymer (viscosity: 45 mPa.s; 矽 bond hydrogen atom content: 0.76 mass% by weight; DVB 630630 161877.doc • 49· 201235296 vinyl, including hydrazine-bonded hydrogen atoms in ruthenium copolymer), isopropyl alcohol solution of phenolic acid (including the amount of DVB63 〇 and dimethyl hydrazine relative to DVB The total weight of the oxyalkylene-methylhydroquinoxane copolymer comprises 1 〇ppm of platinum metal) and 〇"g 2-methyl-3-butyne-2-ol to prepare a crosslinkable composition. The mixture was cured in nitrogen at a temperature of 8 Torr for 3 Torr, followed by 2 Torr. The underarm is further cured for 60 minutes. Thereafter, the solidified product was cooled and crushed using a pulverizer having a gap set to μΠ1. Thereby, particles having an average diameter of about 15 μm are obtained. Preparation of carbon-coated ruthenium-containing carbon-containing composite material Black particles were obtained by mixing 4.75 g of the ruthenium-containing cross-linking particles obtained above with 〇.25 g Ketjen black in a ball mill. As in Practical Example 1, the particles were placed in SSA-S grade alumina steel and baked. After cooling, black particles having a yield of 62% were obtained. The amount of carbon coated on the surface of the carbon-coated ruthenium-containing composite material of the obtained surface was 7.6 mass% by weight of the ruthenium-carbon-containing composite. SEM, TEM and EDχ observation of the obtained black particles showed that the black particles were particles having an average diameter of about 1 〇〇 (1111 to 15 〇μηη, mainly composed of SiOC components, and the black particles were composite particles in which the surface of the particles was coated. Carbon particles having a diameter of 30 nm to 40 nm were coated. The manufacture and evaluation of the electrode and secondary battery using the ruthenium-carbon-containing composite material described in this practical example were carried out in the same manner as in Practical Example 1. Table 1 The battery characteristics are shown in the middle. Practical Example 4 Preparation of ruthenium-containing cross-linking particles by mixing 500 g of organic polyoxane represented by the formula [(CH3)2(CH2=CH)SiO]2(C6H5)2Si, 951 g The end of the molecule is trimethyl decyloxy 161877.doc • 50· 201235296 capped sulfhydryl arsonane copolymer (viscosity: 20 mPa, s; 矽 bond hydrogen atom content: 1.58 mass% by weight; Included in an amount such that each 1 mole of the organic polychlorinated ethylene group, including a 1.2 molar copolymer in the argon atomic argon atom), gas platinum acid isopropanol solution (including the amount of mass ( By weight, relative to organopolyoxane and methylhydrooxane Total weight of the material, including 10 ppm metallized), and 2-methyl-3-butyn-2-ol (inclusive, by mass, by weight, relative to RMS organopolyoxane and decyl hydrazine) The total weight of the oxyalkylene copolymer, including 200 ppm 2-mercapto-3-butyn-2-ol, was prepared to prepare a crosslinkable composition. Subsequently, the mixture was sprayed to a hot air inlet temperature of 200° using a rotary nozzle. C spray dryer (diameter = 2 meters, height = 4 meters). Thereafter, the product is collected from the spray dryer using a cyclone, thereby producing a spherical solidification with a diameter of 2 μm to 50 μm. Preparation of a carbon-coated ruthenium-containing carbon-containing composite material by mixing 4.75 g of the ruthenium-containing crosslinked particles obtained above and 0.25 g of acetylene black 5 in Hybridizer® (manufactured by Nara Machinery Co., Ltd.) In the actual example 1, the particles were placed in an SSA_S grade alumina crucible and baked. After cooling, black particles having a yield of 8% by weight were obtained, and the resulting surface was coated. The amount of carbon on the surface of the composite material containing the ruthenium-based carbon-based composite material is 6 .1 mass (weight) 0 / 〇. SEM, TEM and EDX observation of the obtained black particles showed that the black particles were composite particles having an average diameter of about 2.00 μπ to 50.0 μπ, wherein the core of the particles was mainly composed of SiOC components, and The surface of the particle is coated with carbon particles having a diameter of 30 nm to 40 nm. The electrode of the composite material containing the ruthenium carbon group described in this practical example and the manufacture and evaluation of the secondary battery of 161877.doc 51 201235296 The actual example is performed in the same manner. The battery characteristics are shown in Table i. Practical Example 5 The spray-coated cerium-containing crosslinked particles of this practical example were prepared in the same manner as in Practical Example 4, except that the compounding amount of acetylene black was changed to 〇 · 〇 5 g. The battery characteristics are shown in Table 1. Practical Example 6 The carbon-coated cerium-containing crosslinked particles of this practical example were prepared in the same manner as in Practical Example 4, except that the compounding amount of acetylene black was changed to 〇.15 g. The battery characteristics are shown in Table 1. Practical Example 7 The spray-coated cerium-containing crosslinked particles of this practical example were prepared in the same manner as in Practical Example 4, except that the compounding amount of acetylene black was changed to 〇·5 〇 g. The battery characteristics are shown in Table 2. Practical Example 8 In addition to changing acetylene black to vapor grown carbon fiber (hereinafter referred to as "VGCF"; diameter = 125 nm; length = ι〇μηη; BET surface area = 13 cm2/g), this practical example of carbon coating The ruthenium-containing crosslinked particles were prepared in the same manner as in Practical Example 4. Battery characteristics are shown in Table 2. Practical Example 9 The carbon-coated cerium-containing crosslinked particles of this practical example were prepared in the same manner as in Practical Example 8 except that the compounding amount of VGCF was changed to 〇.〇5 g. Practical example 10 161877.doc •52· 201235296 In addition to changing VGCF to carbon nanotubes (average diameter = 11 nm; maximum length = 10 μιη; BET surface area = 300 m2 / g), this practical example of carbon coating The ruthenium-containing crosslinked particles were prepared in the same manner as in Practical Example 8. The battery characteristics are shown in Table 2. Comparative Example 1 Preparation of Jane Crosslinked Particles By mixing 15.49 g of DVB570 (by Nippon Steel Chemical Co.,

Manufactured by Ltd.; main components: divinylbenzene and vinylethylbenzene; ratio of diethylbenzene in the main component: 60 mass (weight) ◦ / 〇) and 9.5 1 g two molecular ends A thiol oxime oxy-copolymer which is terminated with trimethyl sulfonium oxide (viscosity: 20 mPa*s; hydrogen atom content of Shi Xi bond · · 1 58 mass% by weight; The ethylene group in the DVB 570, including the hydrogen atom in the 1 molar copolymer, is used to prepare the crosslinkable composition. Thereafter, 25 g of 10 mass% polyoxyethylene secondary alkyl ether (San〇nic) was added.

SS120, an aqueous solution manufactured by Sanyo Chemical Industries, Ltd.; HLB = 14.5). Subsequently, a water-based emulsion of the crosslinkable composition was prepared by emulsifying the mixture using a homodisperser (rotation speed: 5 rpm). Subsequently, a water-based emulsion of a platinum-based catalyst prepared by using a 1,3-divinyltetramethyldioxane platinum complex as a main component (the average diameter of the emulsion = 〇_〇5 μιη; Metal concentration = 0_05 mass% by weight) with the water-based emulsion of the crosslinkable composition such that it is uniformly mixed in mass (by weight) relative to the crosslinkable composition comprising 20 ppm of platinum metal, and at 6 〇 t mixed minutes. Thereafter, the solidified product particles having an average diameter of 丨(4) to 5 are prepared by removing water. 161877.doc -53- 201235296 Preparation of composite material containing ruthenium carbon group As in Practical Example 1, the solidified product particles were placed in an MSSA_S grade alumina crucible and baked. After cooling, black particles having a yield of 62% were obtained. The SEM and EDX observations of the obtained black particles revealed that the black particles were spherical particles having an average diameter of about 1.0 μm to 5.0 μm and mainly composed of Si0C components. Electrode fabrication 107.58 parts by mass of the obtained ruthenium-containing carbon-containing composite material was mixed with 6.94 parts by mass of acetylene black in a mortar for 15 minutes. Thereafter, 12.00 mass parts by weight of polyvinylidene fluoride was added and 15 parts of each component were further mixed. Subsequently, a solvent N-methyl-2-pyrrolidone was mixed to obtain a slurry-like mixture, which was then applied to a copper foil roll by a doctor blade method at a thickness of about 25 Å μη. Thereafter, the coated foil roll was dried under vacuum at 851 for not less than 12 hours' and an electrode having a thickness of about 4 Å was obtained. Manufacturing and Evaluation of Secondary Battery The manufacture and evaluation of the secondary battery were carried out in the same manner as in Practical Example 1. Battery characteristics are shown in Table 2. Comparative Example 2 99.40 parts by weight of the dream carbon-based composite material obtained in Comparative Example 1 was mixed with 14.58 parts by weight of acetylene black in a mortar for 15 minutes. Thereafter, 12.00 parts by mass of polyvinylidene fluoride was added and the respective sets of knives were further mixed for 15 minutes. Then, the solvent N-methyl·2 pirodione was mixed to obtain a slurry-like mixture, followed by a doctor blade method. It was applied to a copper foil roll with a thickness of about 25 cm. Thereafter, at 85. The coated foil roll was dried under vacuum for not less than 12 hours&apos; and an electrode having a thickness of about 4 μm was obtained. Electrode and 161877.doc -54- 201235296 The manufacture and evaluation of the secondary battery were carried out in the same manner as in Practical Example 1. The battery characteristics are shown in Table 2. Table 1 Actual example 1 Actual example 2 Actual example 3 Actual example 4 Actual example 5 Actual example 6 Initial discharge capacity (mAh/g) 812 842 700 759 743 603 CE% 68 66 67 70 69 68 Capacity retention after 10 cycles (%) 95 90 96 98 90 95 Table 2 Practical example 7 Practical example 8 Practical example 9 Practical example 10 Comparative example 1 Comparative example 2 Initial discharge capacity (mAh/g) 603 810 812 830 820 750 CE% 63 68 68 70 60 55 Capacity retention rate after 10 cycles (%) 97 95 90 98 65 60 BRIEF DESCRIPTION OF THE DRAWINGS Fig. 1 illustrates a lithium ion secondary battery as an example of the electric storage device of the present invention. Fig. 2 illustrates a lithium secondary battery as an example of the electrical storage device of the present invention. Fig. 3 is an electron micrograph of spherical ruthenium-containing crosslinked particles prepared in Practical Example 1. Figure 4 is an electron micrograph of a carbon-coated ruthenium-containing carbon-based composite prepared in Practical Example 1. Figure 5 is a transmission electron micrograph of a cross section of a carbon-coated carbon-containing composite 161877.doc -55 - 201235296 material prepared in Practical Example 1. [Main component symbol description] 1 Enclosure 2 Gasket 3 Washer 4 SUS plate 5 Current collector 6 Negative electrode 7 Isolator 8 Positive electrode 9 ' 9, Current collector 10 Sealing plate 161877.doc -56-

Claims (1)

201235296 VII. Patent application scope: 1. A method for producing a carbon-coated ruthenium-containing carbon-containing composite material, characterized by: (A) an organic compound having a crosslinkable group (hereinafter referred to as "Component (A)") and (B) are obtained by crosslinking a ruthenium-containing compound (hereinafter referred to as "component (B)") which crosslinks the organic compound having a crosslinkable group to obtain a cured product. And baking a mixture of the cured product and (C) a carbonaceous material (hereinafter referred to as "component (C)"). The manufacturing method of the invention, wherein the baking is in the range of 3〇〇1 to 15〇〇. The temperature is 在 in an inert gas or in a vacuum. 3. The method of producing the item 1 or 2, wherein the crosslinkable group is selected from the group consisting of aliphatic unsaturated groups, epoxy groups, acryl groups, methacryl groups, amines Base, hydroxyl, thiol and functional alkyl. 4. The method of producing any one of clauses 1 to 3, wherein the component (4) has an aromatic group. 201235296 wherein R7 each independently represents a monovalent hydrocarbon group, a hydrogen atom, an organic group containing an epoxy group of a halogen atom, an organic group containing an acryloyl group or a mercaptopropenyl group, an organic group containing an amine group, a mercapto group-containing group Organic group, alkoxy group or via group; "a", "b", "c" and "d" are greater than or equal to 〇 and less than or equal to 1 and satisfy "a" + "b" + "c" The value of + rd" = 1, however; "a", "b" and "c" cannot be simultaneously 8. The manufacturing method of any one of claims 1 to 7, wherein the component (c) is carbon black , carbon fiber, carbon nanofiber, carbon nanotube or a mixture thereof. The production method according to any one of claims 1 to 8, wherein the crosslinking is carried out via an addition reaction, a condensation reaction, a ring opening reaction or a radical reaction. The production method according to any one of claims 1 to 9, wherein the cured product is obtained by the component (A) having an aliphatic unsaturated group and the component having a hydrazine-bonded hydrogen atom ( Obtained by the argon argonization reaction of B). The method of any one of the preceding claims, wherein the cured product is obtained by the component (A) having an aliphatic unsaturated group and having an aliphatic unsaturated group, an acrylonitrile group, It is obtained by a radical reaction of the component (B) of a methacrylinyl group or a hydrazine-bonded hydrogen atom. The manufacturing method according to any one of the preceding claims, wherein the surface of the cured product is covered by the component (C). A carbon-coated carbon-containing composite material having a surface, which is obtained by the production method according to any one of claims 1 to 12. 14. The composite of claim 13 wherein the ruthenium-containing composite material is comprised of particles having an average diameter of from 5 nm to 50 μm. 15. The composite of claim 13 or 14, wherein the amount of carbon included in the composite 161877.doc 201235296 is from 1 mass% by weight to 5 mass% by weight. 16. 17. 18. 19. 20. 21. In the case of any of the items 13 to 15 of the ninth, the composite of τ, which comprises a carbon coating having a thickness of 5 nm to 2 μηη. An electrode active material, a potting technique + l + n , consisting of a composite material according to any one of the items 13 to 16. The electrode active ingredient of claim 17 is composed of particles having an average diameter of 1 _ to 50 μηη. μ An electrode 'which contains an electrode storage device as claimed in claim 17 or 18, an electric storage device, and the electrode of claim 19 contains an electrode as claimed in claim 19. It is a meridian or secondary ion secondary battery. 161877.doc