WO2012105671A1 - Silicon-containing carbon-based composite material - Google Patents

Abstract

A silicon-containing carbon-based composite material represented by the compositional formula SiO_xC_y (in the formula, x is 0.8 to 1.7 and y is 1.4 to 7.5), and for which the ratio of (peak area attributed to sp2 carbon atom/ peak area attributed to sp3 carbon atom) in the ¹³C NAS NMR spectrum is 1.6 to 46.0 is used. The composite material is preferably obtained by heat treatment of a cured product obtained by a crosslinking reaction of (A) an organic compound containing a crosslinking group, and (B) a silicon-containing compound crosslinkable with the organic compound containing a crosslinking group. The composite material has high reversible capacitance and stable charge-discharge cycle characteristics, and moreover high initial charge-discharge efficiency, and is suitable for an electrode of an electric storage device, particularly a lithium or lithium ion secondary battery.

Description

Silicon-containing carbon-based composite material

The present invention relates to a silicon-containing carbon-based composite material, an electrode active material made of the composite material, an electrode including the active material, and an electricity storage device including the electrode.

An electricity storage device, in particular, a lithium or lithium ion secondary battery has been studied as a kind of high energy density type secondary battery. And as a negative electrode material of a lithium ion secondary battery, a high charge / discharge capacity far exceeding the theoretical capacity of graphite can be obtained by firing various carbon sources at a temperature around 1000 ° C. in an inert gas or in vacuum. It is known. For example, J. et al. Electrochem. Soc. , 142, 2581 (1995), it is reported that a reversible capacity exceeding 800 mAh / g can be obtained by firing various carbon sources in an argon atmosphere and using the obtained carbon material as a negative electrode material. . However, the carbon material obtained by firing in such a temperature region has drawbacks such as low initial charge / discharge efficiency and charge / discharge cycle characteristics.

On the other hand, as a negative electrode material for a lithium ion secondary battery, it has been reported that a silicon-containing carbon material obtained by thermally decomposing a silicon polymer is used. For example, in Japanese Patent Laid-Open No. 10-97853 and Solid State Ionics, 122, 71 (1999), materials that can be used for manufacturing a large-capacity battery by using polysilane and coal tar pitch as precursors are disclosed. The production is described. JP-A-10-74506, JP-A-10-275617, JP-A-2004-273377, and J. Org. Electrochem. Soc. , 144, 2410 (1997) describes that a high-capacity battery is obtained by thermally decomposing a siloxane polymer and then introducing lithium into an electrode for a lithium or lithium ion secondary battery. . However, a lithium ion secondary battery including such an electrode containing a silicon-containing carbon material has a high reversible capacity, but has a low initial charge / discharge efficiency and lacks practical performance in terms of charge / discharge cycle characteristics and the like. Yes.

In addition, JP 2006-062949 A describes a silicon-containing carbon material obtained by curing and sintering a siloxane polymer containing a graphene-based material such as graphite. However, a lithium or lithium ion secondary battery including an electrode including such a silicon-containing carbon material has a limited reversible capacity due to a crystal structure such as graphite.

JP 10-97853 A JP-A-10-74506 Japanese Patent Laid-Open No. 10-275617 JP 2004-273377 A JP 2006-062949 A

An object of the present invention is to provide an electricity storage device, in particular, a composite material suitable for an electrode of a lithium or lithium ion secondary battery, an electrode active material made of the composite material, an electrode using the active material, and an electricity storage device including the electrode Is to provide.

The object of the present invention is represented by the composition formula: SiO _x C _y (wherein x is 0.8 to 1.7, y is 1.4 to 7.5), and (sp2 carbon of ¹³ C MAS NMR spectrum) This is achieved by a silicon-containing carbon-based composite material having a ratio of atomic origin peak area / sp3 carbon atom origin peak area of 1.6 to 46.0.

The composite material is obtained by heat-treating a cured product obtained by crosslinking reaction of (A) a crosslinkable group-containing organic compound and (B) a silicon-containing compound capable of crosslinking the crosslinkable group-containing organic compound. Can do. Therefore, the present invention relates to (A) a crosslinkable group-containing organic compound (hereinafter also referred to as “component (A)”) and (B) the crosslinkable group-containing organic compound (hereinafter referred to as “component (B)”). A composition obtained by heat-treating a cured product obtained by cross-linking a silicon-containing compound capable of cross-linking: SiO _x C _y (wherein x is 0.8 to 1.7, y is 1.4 to 7.5) and a side surface as a method for producing a silicon-containing carbon-based composite material.

The heat treatment is preferably performed at 300 to 1500 ° C. in an inert gas or in vacuum.

The crosslinkable group can be selected from the group consisting of aliphatic unsaturated groups, epoxy groups, acrylic groups, methacrylic groups, amino groups, hydroxyl groups, mercapto groups, and halogenated alkyl groups.

The component (A) may have an aromatic group.

The component (A) has the general formula:

(In the formula, R ¹ is a crosslinkable group, x is an integer of 1 or more, and R ² is an x-valent aromatic group).

The component (A) preferably contains a silicon atom.

The component (A) is preferably siloxane, silane, silazane, carbosilane, or a mixture thereof.

The siloxane has an average unit formula:

(In the formula, each R ³ independently represents a crosslinkable group, a monovalent substituted or unsubstituted saturated aliphatic hydrocarbon group or aromatic hydrocarbon group having 1 to 20 carbon atoms, an alkoxy group, a hydrogen atom, or A, b, c and d are each a number satisfying 0 or more and 1 or less and satisfying a + b + c + d = 1, provided that a, b and c are not all 0; It is preferable that at least one of R ^{3 in} the molecule is a crosslinkable group.

The component (B) is preferably siloxane, silane, silazane, carbosilane, or a mixture thereof.

The siloxane has an average unit formula:

(In the formula, each R ³ independently represents a monovalent hydrocarbon group, hydrogen atom, halogen atom, epoxy group-containing organic group, acrylic group-containing organic group, methacryl group-containing organic group, amino group-containing organic group, mercapto. A group-containing organic group, an alkoxy group or a hydroxy group; a, b, c and d are each a number satisfying 0 or more and 1 or less and satisfying a + b + c + d = 1, provided that a, b and c are Neither of them can be 0).

The crosslinking reaction may be any of an addition reaction, a condensation reaction, a ring-opening reaction, or a radical reaction.

The cured product may be obtained by a hydrosilylation reaction between the component (A) having an aliphatic unsaturated group and the component (B) having a silicon atom-bonded hydrogen atom.

The cured product may be obtained by a hydrosilylation reaction between the component (A) having a silicon atom-bonded hydrogen atom and the component (B) having an aliphatic unsaturated group.

The cured product is obtained by radical reaction between the component (A) having an aliphatic unsaturated group and the component (B) having an aliphatic unsaturated group, an acrylic group, a methacryl group or a silicon-bonded hydrogen atom. It may be.

The said hardened | cured material was obtained by the radical reaction of (A) component which has an aliphatic unsaturated group, an acryl group, a methacryl group, or a silicon atom bond hydrogen atom, and (B) component which has an aliphatic unsaturated group. It may be a thing.

The silicon-containing carbon-based composite material of the present invention is preferably in an amorphous form. The composite material is preferably in the form of particles having an average particle diameter of 5 nm to 50 μm.

The electrode active material of the present invention is composed of the above composite material. The electrode active material is preferably particles having an average particle diameter of 1 to 50 μm.

The electrode of the present invention contains the above electrode active material. The said electrode can be used conveniently for an electrical storage device, especially a lithium or lithium ion secondary battery.

The composite material of the present invention has high reversible capacity and stable charge / discharge cycle characteristics, and has high initial charge / discharge efficiency, and is suitable for an electrode of an electricity storage device, particularly lithium or lithium ion secondary battery. Further, the composite material of the present invention can be manufactured by a simple manufacturing process using inexpensive raw materials.

The electrode active material of the present invention is suitable for an electricity storage device, particularly an electrode of a lithium or lithium ion secondary battery. The electrode of the present invention can impart high reversible capacity, stable charge / discharge cycle characteristics, and high initial charge / discharge efficiency to the battery. Thereby, the electrical storage device of the present invention can have high reversible capacity, stable charge / discharge cycle characteristics, and high initial charge / discharge efficiency.

The lithium ion secondary battery which is an example of the electrical storage device of this invention is shown. The lithium secondary battery which is an example of the electrical storage device of this invention is shown.

(Composite material)
The composite material of the present invention includes a step of heat treating a cured product obtained by crosslinking reaction of (A) a crosslinkable group-containing organic compound and (B) a silicon-containing compound capable of crosslinking the crosslinkable group-containing organic compound. It can obtain by the manufacturing method containing.

The crosslinkable group in the component (A) is not particularly limited as long as it is a crosslinkable group. For example, an aliphatic unsaturated group, an epoxy group, an acrylic group, a methacryl group, an amino group, a hydroxyl group, A mercapto group or a halogenated alkyl group may be mentioned. Specific examples of the aliphatic unsaturated group include alkenyl groups such as vinyl group, propenyl group, butenyl group, pentenyl group and hexenyl group; and alkynyl groups such as acetyl group, propynyl group and pentynyl group. Specific examples of the epoxy group include a glycidyl group, a glycidoxy group, an epoxycyclohexyl group, a 3-glycidoxypropyl group, and a 2- (3,4-epoxycyclohexyl) ethyl group. Specific examples of the acryl group include a 3-acryloxypropyl group. Specific examples of the methacryl group include a 3-methacryloxypropyl group. Specific examples of the amino group include a 3-aminopropyl group and an N- (2-aminoethyl) -3-aminopropyl group. Specific examples of the hydroxyl group include hydroxyalkyl groups such as hydroxyethyl group and hydroxypropyl group; and hydroxyaryl groups such as hydroxyphenyl group. Specific examples of the mercapto group include a 3-mercaptopropyl group. Specific examples of the halogenated alkyl group include a 3-chloropropyl group.

The component (A) may be a mixture of an organic compound having one crosslinkable group in one molecule and an organic compound having at least two crosslinkable groups in one molecule. In this case, the content of the latter in the mixture is not particularly limited, but is preferably at least 15 mass (weight)%, and more preferably at least 30 mass (weight)% because of its excellent crosslinkability. preferable.

The component (A) may not contain a silicon atom or may contain a silicon atom.

The component (A) that does not contain a silicon atom is preferably an organic compound having at least one aromatic ring in the molecule from the viewpoint of good carbonization efficiency by heat, such as easy formation of a graphene structure.

As such component (A), specifically, an aliphatic hydrocarbon compound containing no silicon atom having a crosslinkable group at the molecular chain terminal and / or molecular chain side chain, the molecular chain terminal and / or molecular chain side An aliphatic hydrocarbon compound having a crosslinkable group in the chain and not containing a silicon atom having a heteroatom other than a carbon atom such as a nitrogen atom, oxygen atom or boron atom in the molecular chain, or having a crosslinkable group in the molecule Examples include aromatic hydrocarbon compounds that do not contain silicon atoms, and alicyclic compounds that contain a crosslinkable group in the molecule and that do not contain silicon atoms that have hetero atoms other than carbon atoms such as nitrogen atoms, oxygen atoms, and boron atoms. Is done.

Specific examples of the aliphatic hydrocarbon compound include compounds represented by the following general formula.
R ¹ — (CH ₂ ) _m —R ¹
_{CH 3 - (CH 2) m} - (CHR 1) n -CH 3
_{CH 3 - (CH 2) m} - (CH = CH) n -CH 3
_{CH 3 - (CH 2) m} - (C≡C) n -CH 3
_{^{R 1 -O (CH 2 CH 2}} O) m (CH 2 CH 2 CH 2 O) n -R 1

(In the formula, R ¹ is a crosslinkable group, and examples thereof include an aliphatic unsaturated group, an epoxy group, an acrylic group, a methacryl group, an amino group, a hydroxyl group, a mercapto group, and a halogenated alkyl group. Is exemplified by the same groups as described above, wherein m and n are each an integer of 1 or more, and x is an integer of 1 or more.

As the aromatic hydrocarbon compound, specifically, a general formula:

Is mentioned. In the formula, R ¹ is a crosslinkable group, and examples thereof are the same groups as described above. In the formula, x is an integer of 1 or more. In the formula, R ² represents an x-valent aromatic group. That is, in the formula, when x is 1, R ² represents a monovalent aromatic group, and specific examples thereof include the following groups.

Specific examples of such aromatic hydrocarbon compounds include α- or β-methylstyrene, α- or β-ethylstyrene, methoxystyrene, phenylstyrene, chlorostyrene, o-, m- or p-methylstyrene. , Ethyl styrene, methyl silyl styrene, hydroxy styrene, cyano styrene, nitro styrene, amino styrene, carboxy styrene, sulfoxy styrene, sodium styrene sulfonate, vinyl pyridine, vinyl thiophene, vinyl pyrrolidone, vinyl naphthalene, vinyl anthracene, vinyl biphenyl Is exemplified.

In the formula, when x is 2, R ² represents a divalent aromatic group, and specific examples thereof include the following groups.

Specific examples of such aromatic hydrocarbon compounds include divinylbenzene, divinylbiphenyl, vinylbenzyl chloride, divinylpyridine, divinylthiophene, divinylpyrrolidone, divinylnaphthalene, divinylxylene, divinylethylbenzene, and divinylanthracene. . The aromatic hydrocarbon compound is preferably divinylbenzene because the resulting cured product has excellent thermal decomposition characteristics.

In the formula, when x is 3, R ² represents a trivalent aromatic group, and specific examples thereof include the following groups.

Specific examples of such aromatic hydrocarbon compounds include trivinylbenzene and trivinylnaphthalene.

Further, as an aromatic compound having a hetero atom, specifically, the following general formula:

The aromatic compound represented by these is illustrated. In the formula, R ¹ is a crosslinkable group, and examples thereof are the same groups as described above.

Furthermore, as a cyclic compound having a hetero atom, specifically, the following general formula:

The cyclic compound represented by these is illustrated. In the formula, R ¹ is a crosslinkable group, and examples thereof are the same groups as described above.

The component (A) containing a silicon atom is not particularly limited as long as it has a crosslinkable group, and examples thereof include a monomer, oligomer or polymer containing a silicon atom. For example, a silane composed of a structural unit characterized by having a silicon-silicon bond, a silazane composed of a structural unit characterized by having a silicon-nitrogen-silicon bond, and a silicon-oxygen-silicon bond Examples thereof include siloxanes composed of structural units, carbosilanes composed of structural units characterized by having a silicon-carbon-silicon bond, and mixtures thereof.

Examples of the silane of the component (A) include an average unit formula:

Or average unit formula:

(In the formula, each R ³ independently represents a crosslinkable group, a monovalent substituted or unsubstituted saturated aliphatic hydrocarbon group or aromatic hydrocarbon group having 1 to 20 carbon atoms, an alkoxy group, or a hydrogen atom. Or a, b, c and d are 0 or a positive number, provided that a + b + c + d = 1, and at least one, preferably at least two of R ^{3 in} one molecule is the above-mentioned crosslinkable Which is a group) can be used.

The saturated aliphatic hydrocarbon group is preferably an alkyl group, and the aromatic hydrocarbon group is preferably an aryl group or an aralkyl group.

The alkyl group _is preferably a C 1 _{-C 12} alkyl _group, C 1 -C ₆ alkyl is more preferable. The alkyl group is a linear or branched alkyl group, a cycloalkyl group, or a cycloalkylene group (a linear or branched alkylene group (preferably a C ₁ -C ₆ alkylene group such as a methylene group or an ethylene group). ) And a carbon ring (preferably an alkyl group composed of a C ₃ -C ₈ ring).

As the linear or branched alkyl group, a linear or branched C ₁ -C ₆ alkyl group is preferable. For example, a methyl group, an ethyl group, an n-propyl group, an isopropyl group, a butyl group, t- Examples thereof include a butyl group, a pentyl group, and a hexyl group, and a methyl group is particularly preferable.

The cycloalkyl group is preferably a C ₄ -C ₆ cycloalkyl group, for example, a cyclobutyl group, a cyclopentyl group, cyclohexyl group, etc., a cyclopentyl group and cyclohexyl group are preferable.

The aryl group _is preferably C 6 _{-C 12} aryl, phenyl group, naphthyl group, tolyl group.

As the aralkyl group, a C ₇ -C ₁₂ aralkyl group is preferable. Examples of the C ₇ -C ₁₂ aralkyl group include a benzyl group, a phenethyl group, and phenylpropyl.

The hydrocarbon group may have a substituent. Examples of the substituent include halogens such as fluorine atom, chlorine atom, bromine atom and iodine atom; hydroxyl group; methoxy group, ethoxy group, n-propoxy group, iso C ₁ -C ₆ alkoxy groups such as propoxy group; amino group; amide group; nitro group; epoxy group and the like. The substituent can be bonded to any part of the hydrocarbon chain, saturated ring or aromatic ring.

Examples of the alkoxy group include a methoxy group, an ethoxy group, an n-propoxy group, and an isopropoxy group.

Examples of the halogen atom include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom.

The silane can be prepared using various known methods. For example, a method of dehalogenating a halosilane in the presence of an alkali metal (Macromolecules, 23, 3423 (1990), etc.), a method of anionic polymerization of disilene (Macromolecules, 23, 4494 (1990), etc.), electrode reduction, etc. (J. Chem. Soc., Chem. Commun., 1161 (1990), J. Chem. Soc., Chem. Commun., 897 (1992), etc.), magnesium, etc. A method of performing a dehalogenation reaction of halosilanes in the presence of hydrogen (WO98 / 29476, etc.), a method of performing a dehydrogenation reaction of hydrosilanes in the presence of a metal catalyst (JP-A-4-334551, etc.), etc. Is mentioned.

Examples of the silazane of the component (A) include an average unit formula:

(In the formula, each R ³ independently represents a crosslinkable group, a monovalent substituted or unsubstituted saturated aliphatic hydrocarbon group or aromatic hydrocarbon group having 1 to 20 carbon atoms, an alkoxy group, or a hydrogen atom. Or a halogen atom, R ⁴ represents a hydrogen atom or a monovalent substituted or unsubstituted saturated aliphatic hydrocarbon group or aromatic hydrocarbon group having 1 to 20 carbon atoms, and a, b, c and d are 0 or a positive number, provided that a + b + c + d = 1, and at least one, preferably at least two of R ^{3 in} one molecule is the crosslinkable group). it can. Here, the saturated aliphatic hydrocarbon group, aromatic hydrocarbon group, alkoxy group and halogen atom have the same meaning as defined for the silane.

The silazane can be prepared by methods well known in the art. For example, U.S. Pat.Nos. 4,321,970, 4,340,619, 4,395,460, 4,404,153, 4,482,689, 4,398,828, 4,540,803, 4,543,344, 4,835,312, No. 4,929,742 and No. 4,916,200. Furthermore, J. et al. Mater. Sci. 22, 2609 (1987).

Examples of the siloxane of the component (A) include an average unit formula:

(In the formula, each R ³ independently represents a crosslinkable group, a monovalent substituted or unsubstituted saturated aliphatic hydrocarbon group or aromatic hydrocarbon group having 1 to 20 carbon atoms, an alkoxy group, or a hydrogen atom. Each of a, b, c and d is a number satisfying 0 or more and 1 or less and satisfying a + b + c + d = 1, provided that a, b and c are not all 0; It is possible to use at least one of R ^{3 in} one molecule, preferably at least two of the above-mentioned crosslinkable groups. Here, the saturated aliphatic hydrocarbon group, aromatic hydrocarbon group, alkoxy group and halogen atom have the same meaning as defined for the silane.

The siloxane can be prepared by methods well known in the art. The method for preparing siloxane is not particularly limited. Most commonly, siloxanes are prepared by hydrolysis of organochlorosilanes. Such and other methods are described in Noll, Chemistry and Technology of Silicones, Chapter 5 (translated 2nd German version, Academic Press, 1968).

Examples of the carbosilane of the component (A) include an average unit formula:

(In the formula, each R ³ independently represents a crosslinkable group, a monovalent substituted or unsubstituted saturated aliphatic hydrocarbon group having 1 to 20 carbon atoms, an aromatic hydrocarbon group, an alkoxy group, or a hydrogen atom. Each of R ⁵ and R ⁶ independently represents a hydrogen atom or a monovalent substituted or unsubstituted saturated aliphatic hydrocarbon group or aromatic hydrocarbon group having 1 to 20 carbon atoms; a, b, c and d represent 0 or a positive number, provided that a + b + c + d = 1, and at least one, preferably at least two of R ^{3 in} one molecule is the above-mentioned crosslinkable group). Can be used. Here, the saturated aliphatic hydrocarbon group, aromatic hydrocarbon group, alkoxy group and halogen atom have the same meaning as defined for the silane.

The carbosilane can be prepared by a method well known in the art. The preparation method of carbosilane is described in, for example, Macromolecules, 21, 30 (1988), US Pat. No. 3,293,194.

The shape of silane, silazane, siloxane, and carbosilane is not particularly limited, and may be solid, liquid, paste, or the like, but is preferably solid in terms of handleability.

Of these silicon-based polymer compounds, the silicon content is not extremely low, it has sufficient chemical stability, it is easy to handle at room temperature and in air, and the raw material price and manufacturing process cost are low enough. Considering industrial advantages such as having good economic efficiency, a siloxane composed of units having a silicon-oxygen-silicon bond is preferred, and a polysiloxane is more preferred.

The component (A) may be one type of organic compound or a mixture of two or more types, and may further contain a nitrogen-containing monomer such as acrylonitrile as another component. In this case, the content of the nitrogen-containing monomer is preferably 50% by mass or less, and particularly preferably in the range of 10 to 50% by mass.

The component (B) is a silicon-containing compound capable of crosslinking the component (A). Examples of such component (B) include siloxane, silane, silazane, carbosilane, and mixtures thereof. Specifically, siloxanes such as monomers, oligomers, or polymers having a Si—O—Si bond; , Silanes such as monomers, oligomers or polymers having a Si—Si bond; silalkylenes such as monomers, oligomers or polymers having a Si— (CH ₂ ) _n —Si bond; Si— (C ₆ H ₄ ) _n − Si or _{Si- (CH 2 CH 2 C 6} H 4 CH 2 CH 2) silarylene of monomers having n -Si bonds, oligomers or polymers; Si-n-Si monomer having a binding, such as oligomers or polymers Silazanes; Si—O—Si bond, Si—Si bond, Si— (CH ₂ ) _n —Si bond , Si- (C ₆ H ₄ ) _n —Si bond, and silicon-containing copolymer compound having at least two types of bonds consisting of Si—N—Si bond; and a mixture thereof. In the formula, n is an integer of 1 or more. The component (B) preferably has a silicon atom-bonded hydrogen atom.

Examples of the siloxanes of the component (B) include an average unit formula:

(In the formula, each R ⁷ independently represents a monovalent hydrocarbon group, a hydrogen atom, a halogen atom, an epoxy group-containing organic group, an acrylic group-containing organic group, a methacryl group-containing organic group, an amino group-containing organic group, or a mercapto group. A group-containing organic group, an alkoxy group or a hydroxy group; a, b, c and d are each a number satisfying 0 or more and 1 or less and satisfying a + b + c + d = 1, provided that both a, b and c are It is not 0).

Specific examples of the monovalent hydrocarbon group for R ⁷ include an alkyl group, an alkenyl group, an aralkyl group, and an aryl group. The alkyl group is preferably a C ₁ to C ₁₂ alkyl group, and particularly preferably a C ₁ to C ₆ alkyl group. The alkyl group is a linear or branched alkyl group, a cycloalkyl group, or a cycloalkylene group (a linear or branched alkylene group (preferably a C ₁ -C ₆ alkylene group such as a methylene group or an ethylene group). ) And a carbon ring (preferably an alkyl group composed of a C ₃ to C ₈ ring). The linear or branched alkyl group is preferably a linear or branched C ₁ -C ₆ alkyl group, specifically, a methyl group, an ethyl group, an n-propyl group, an isopropyl group, a butyl group, Examples are t-butyl group, pentyl group, and hexyl group. The cycloalkyl group is preferably a C ₄ to C ₆ cycloalkyl group, and specific examples include a cyclobutyl group, a cyclopentyl group, and a cyclohexyl group. The alkenyl group is preferably a C ₂ to C ₁₂ alkenyl group, and particularly preferably a C ₂ to C ₆ alkenyl group. Specific examples of the C ₂ -C ₆ alkenyl group include a vinyl group, a propenyl group, a butenyl group, a pentenyl group, and a hexenyl group, and a vinyl group is preferable. The aralkyl group is preferably a C ₇ to C ₁₂ aralkyl group. Specific examples of the C ₇ to C ₁₂ aralkyl group include a benzyl group, a phenethyl group, and phenylpropyl. The aryl group is preferably a C ₆ -C ₁₂ aryl group, and specific examples thereof include a phenyl group, a naphthyl group, and a tolyl group. These monovalent hydrocarbon groups may have a substituent. Specific examples of the substituent include halogen such as fluorine atom, chlorine atom, bromine atom and iodine atom; hydroxyl group; alkoxy group such as methoxy group, ethoxy group, n-propoxy group and isopropoxy group. Specific examples of such a substituted monovalent hydrocarbon group include a 3-chloropropyl group, a 3,3,3-trifluoropropyl group, a perfluorobutylethyl group, and a perfluorooctylethyl group.

Specific examples of the halogen atom for R ⁷ include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom, and a chlorine atom is preferable.

Specific examples of the epoxy group-containing organic group represented by R ⁷ include glycidoxyalkyl groups such as 3-glycidoxypropyl group and 4-glycidoxybutyl group; 2- (3,4-epoxycyclohexyl). -An epoxy cyclohexyl alkyl group such as an ethyl group or a 3- (3,4-epoxycyclohexyl) -propyl group; an oxiranyl alkyl group such as a 4-oxiranylbutyl group or an 8-oxiranyloctyl group; A glycidoxyalkyl group is preferable, and a 3-glycidoxypropyl group is particularly preferable.

Specific examples of the acrylic group-containing organic group or the methacrylic group-containing organic group represented by R ⁷ include a 3-acryloxypropyl group, a 3-methacryloxypropyl group, a 4-acryloxybutyl group, and a 4-methacryloxybutyl group. And is preferably a 3-methacryloxypropyl group.

Specific examples of the amino group-containing organic group for R ⁷ include a 3-aminopropyl group, a 4-aminobutyl group, and an N- (2-aminoethyl) -3-aminopropyl group. 3-aminopropyl group and N- (2-aminoethyl) -3-aminopropyl group.

Specific examples of the mercapto group-containing organic group for R ⁷ include a 3-mercaptopropyl group and a 4-mercaptobutyl group.

Specific examples of the alkoxy group for R ⁷ include a methoxy group, an ethoxy group, an n-propoxy group, and an isopropoxy group, and a methoxy group and an ethoxy group are preferable.

In addition, at least 1, preferably at least 2, R ⁷ in one molecule is an alkenyl group, a hydrogen atom, a halogen atom, an epoxy group-containing organic group, an acrylic group-containing organic group, a methacryl group-containing organic group, or an amino group. A containing organic group, a mercapto group-containing organic group, an alkoxy group, or a hydroxy group.

Further, a, b, c and d are numbers which are 0 or more and 1 or less and satisfy a + b + c + d = 1, respectively. However, a, b and c are not all 0.

Such siloxanes are structural units represented by (R ⁷ ₃ SiO _1/2 ), (R ⁷ ₂ SiO _2/2 ), (R ⁷ SiO _3/2 ), and (SiO _4/2 ). And, specifically, a linear polysiloxane comprising units of (R ⁷ ₃ SiO _1/2 ) and (R ⁷ 2SiO _2/2 ); (R ⁷ 2SiO cyclic polysiloxane comprising units of _{^{2/2); (R 7 SiO 3/2}} ) or (consisting _{SiO 4/2)} units of branched ^{polysiloxane;} _(R 7 _{3 SiO 1/2)} and ^{(R 7} Polysiloxane composed of units of (SiO _3/2 ); polysiloxane composed of units of (R ⁷ 3SiO _1/2 ) and (SiO _4/2 ); of (R ⁷ SiO _3/2 ) and (SiO _4/2 ) Polysiloxane consisting of units ^(R ₇ 2 _{SiO 2/2)} and polysiloxane comprising units of _{^{(R 7 SiO 3/2); (}} R 7 2 SiO 2/2) and polysiloxane comprising units of _{(SiO 4/2); (R} ⁷ ₃ SiO _1/2 ), (R ⁷ ₂ SiO _2/2 ) and (R ⁷ SiO _3/2) units of polysiloxane; (R ⁷ ₃ SiO _1/2 ), (R ⁷ ₂ SiO _{2 / 2} ) and (SiO _4/2 ) units of polysiloxane; (R ⁷ ₃ SiO _1/2 ), (R ⁷ SiO _3/2 ) and (SiO _4/2 ) units of polysiloxane; (R ⁷ ₂ SiO _2/2 ), (R ⁷ SiO _3/2 ) and (SiO _4/2 ) units of polysiloxane; (R ⁷ 3SiO _1/2 ), (R ⁷ ₂ SiO _2/2 ), ( R ⁷ SiO _3/2) and (SiO ₄ Polysiloxanes and the like comprising units of _2). The preferred number of repeating structural units represented by (R ⁷ ₃ SiO _1/2 ), (R ⁷ ₂ SiO _2/2 ), (R ⁷ Si ○ _3/2 ), and (SiO _4/2 ) is Each is preferably within the range of 1 to 10,000, more preferably within the range of 1 to 1,000, and particularly preferably within the range of 3 to 500.

These siloxanes can be prepared by methods well known in the art. The method for preparing the siloxanes is not particularly limited, and is most commonly prepared by hydrolysis of organochlorosilanes. Such and other methods are those described in Noll, Chemistry and Technology of Silicones, Chapter 5 (translated 2nd German version, Academic Press, 1968).

These siloxanes may be silicon-containing copolymer compounds with polymers. For example, silicon-containing copolymer compound having Si—O—Si bond and Si—Si bond; silicon-containing copolymer compound having Si—O—Si bond and Si—N—Si bond; Si—O—Si bond And Si- (CH ₂ ) _n —Si bond-containing copolymer compound; Si—O—Si bond and Si— (C ₆ H ₄ ) _n —Si bond or Si— (CH ₂ CH ₂ C ₆ H) _A silicon-containing copolymer compound having a ₄ CH ₂ CH ₂ ) _n —Si bond or the like can be used as the siloxane. In the formula, n is the same as described above.

Silanes are, for example, general formulas:

Or average unit formula:

(In the formula, each R ⁷ independently represents a monovalent hydrocarbon group, a hydrogen atom, a halogen atom, an epoxy group-containing organic group, an acrylic group-containing organic group, a methacryl group-containing organic group, an amino group-containing organic group, or a mercapto group. A group-containing organic group, an alkoxy group or a hydroxy group, provided that at least one, preferably at least 2, R ⁷ in one molecule is an alkenyl group, a hydrogen atom, a halogen atom, an epoxy group-containing organic group, an acrylic group A group-containing organic group, a methacryl group-containing organic group, an amino group-containing organic group, a mercapto group-containing organic group, an alkoxy group or a hydroxy group; a, b, c and d are each 0 or more, 1 or less, and a + b + c + d = 1, provided that a, b, and c are not all 0).

These silanes are represented by a general formula: R ⁷ ₄ Si or a structure represented by (R ⁷ ₃ Si), (R ⁷ ₂ Si), (R ⁷ Si), and (Si). It is composed of at least one unit among the units, specifically, a linear polysilane composed of units of (R ⁷ ₃ Si) and (R ⁷ ₂ Si); composed of units of (R ⁷ ₂ Si) Cyclic polysilane; Branched polysilane (polysilin) consisting of units of (R ⁷ Si) or (Si); Polysilane consisting of units of (R ⁷ ₃ Si) and (R ⁷ Si); (R ⁷ ₃ Si) and ( (Si) unit polysilane; (R ⁷ Si) and (Si) unit polysilane; (R ⁷ ₂ Si) and (R ⁷ Si) unit polysilane; (R ⁷ ₂ Si) and (Si) (R; polysilane consisting of units) ^{_{3 Si), (R 7 2Si}} ) and ^(polysilane comprising units of _{^{R 7 Si); (R 7}} 3 Si), (R 7 2 Si) and (polysilane comprising units of _{^{Si); (R 7 3 Si}} ) , (R ⁷ Si) and (Si) units; polysilanes; (R ⁷ ₂ Si), (R ⁷ Si) and (Si) units; (R ⁷ ₃ Si), (R ⁷ ₂ Si ), (R ⁷ Si) and polysilanes composed of (Si) units. The preferable number of repeating structural units represented by (R ⁷ ₃ Si), (R ⁷ ₂ Si), (R ⁷ Si) and (Si) is preferably in the range of 2 to 10,000, Is preferably within the range of 3 to 1,000, and particularly preferably within the range of 3 to 500.

These silanes can be prepared using various known methods. For example, a method of dehalogenating a halosilane in the presence of an alkali metal (Macromolecules, 23, 3423 (1990), etc.), a method of anionic polymerization of disilene (Macromolecules, 23, 4494 (1990), etc.), electrode reduction, etc. (J. Chem. Soc., Chem. Commun., 1161 (1990), J. Chem. Soc., Chem. Commun., 897 (1992), etc.), presence of magnesium Examples thereof include a method for dehalogenating halosilanes (WO98 / 29476 etc.), a method for dehydrogenating hydrosilanes in the presence of a metal catalyst (JP-A-4-334551 etc.), and the like. It is done.

These silanes may be silicon-containing copolymer compounds with other polymers. For example, a silicon-containing copolymer compound having a Si-Si bond and a Si-O-Si bond; a silicon-containing copolymer compound having a Si-Si bond and a Si-N-Si bond; a Si-Si bond and a Si- ( CH ₂₎ containing copolymer compounds having _n -Si bonds; Si-Si bonds and _{Si- (C 6 H 4) n} -Si bonds or _{Si- (CH 2 CH 2 C 6} H 4 CH 2 CH 2) Silicon-containing copolymer compounds having an _n- Si bond can be used as silanes.

Other silanes have the general formula:

Wherein R ⁸ is each independently a substituted or unsubstituted monovalent hydrocarbon group; e is an integer of 2 or more; and R ⁹ is an e-valent organic group. Silicon compounds are exemplified. In the formula, examples of the monovalent hydrocarbon group for R ⁸ include the same groups as the monovalent hydrocarbon group for R ⁷ . e is an integer of 2 or more, preferably an integer of 2 to 6. R ⁹ is an e-valent organic group, and when e is 2, R ⁹ is a divalent organic group. Specifically, an alkylene group, an alkenylene group, an alkyleneoxyalkylene group, an arylene group, an arylene An oxyarylene group and an arylenealkylenearylene group are exemplified, and more specifically, the following groups are exemplified.
_{, - - -CH 2 CH 2 CH} 2 CH 2 CH 2 -, - CH 2 CH (CH 3) -, - CH = CH -, - C≡C -, - CH 2 CH 2 OCH 2 CH 2 -, - CH ₂ CH ₂ CH ₂ OCH ₂ CH _2- ,

When e is 3, R ⁹ is a trivalent organic group, and specific examples thereof include the following groups.

Examples of silazanes include, for example, an average unit formula:

(In the formula, each R ⁷ independently represents a monovalent hydrocarbon group, a hydrogen atom, a halogen atom, an epoxy group-containing organic group, an acrylic group-containing organic group, a methacryl group-containing organic group, an amino group-containing organic group, or a mercapto group. A group-containing organic group, an alkoxy group or a hydroxy group, provided that at least one, preferably at least 2, R ⁷ in one molecule is an alkenyl group, a hydrogen atom, a halogen atom, an epoxy group-containing organic group, an acrylic group A group-containing organic group, a methacryl group-containing organic group, an amino group-containing organic group, a mercapto group-containing organic group, an alkoxy group or a hydroxy group; R ¹⁰ is a hydrogen atom or a substituted or unsubstituted monovalent hydrocarbon group; a, b, c and d are numbers which are 0 or more and 1 or less and satisfy a + b + c + d = 1, respectively, provided that a, b and c are both 0. Represented in the stomach). Examples of the monovalent hydrocarbon group for R ¹⁰ include the same groups as the monovalent hydrocarbon group for R ⁷ . R ¹⁰ is preferably a hydrogen atom or an alkyl group, particularly preferably a hydrogen atom or a methyl group.

This silazane is composed of at least one unit among structural units represented by (R ⁷ ₃ SiNR ¹⁰ ), (R ⁷ ₂ SiNR ¹⁰ ), (R ⁷ SiNR ¹⁰ ), and (SiNR ¹⁰ ). Specifically, a linear polysilazane composed of units of (R ⁷ ₃ SiNR ¹⁰ ) and (R ⁷ ₂ SiNR ¹⁰ ); a cyclic polysilazane composed of units of (R ⁷ ₂ SiNR ¹⁰ ); (R ⁷ SiNR ¹⁰ ) Or (SiNR ¹⁰ ) units of branched polysilazane; (R ⁷ ₃ SiNR ¹⁰ ) and (R ⁷ SiNR ¹⁰ ) units of polysilazane; (R ⁷ ₃ SiNR ¹⁰ ) and (SiNR ¹⁰ ) units of comprising ^{polysilazane;} (R 7 SiNR ¹⁰⁾ and polysilazane comprising units of _{^{(SiNR 10); (R 7}} 2 SiNR ⁰⁾ and ^{(polysilazane} comprising units of _{^{R 7 SiNR 10); (R}} 7 2 SiNR 10) and (polysilazane comprising units of _{^{SiNR 10); (R 7 3}} SiNR 10), (R 7 2 SiNR 10) and ( Polysilazane composed of units of R ⁷ SiNR ¹⁰ ); Polysilazane composed of units of (R ⁷ ₃ SiNR ¹⁰ ), (R ⁷ ₂ SiNR ¹⁰ ) and (SiNR ¹⁰ ); (R ⁷ ₃ SiNR ¹⁰ ), (R ⁷ SiNR ¹⁰ ) And (SiNR ¹⁰ ) units; polysilazanes composed of units (R ⁷ ₂ SiNR ¹⁰ ), (R ⁷ SiNR ¹⁰ ) and (SiNR ¹⁰ ); (R ⁷ ₃ SiNR ¹⁰ ), (R ⁷ ₂ SiNR ^10), Porishiraza composed of units of (R 7 SiNR ¹⁰⁾ and (SiNR ¹⁰⁾ Etc. The. The preferred number of repeating structural units represented by (R ⁷ ₃ SiNR ¹⁰ ), (R ⁷ ₂ SiNR ¹⁰ ), (R ⁷ SiNR ¹⁰ ), and (SiNR ¹⁰ ) is in the range of 2 to 10,000, respectively. More preferably, it is preferably within the range of 3 to 1,000, and particularly preferably within the range of 3 to 500.

These silazanes can be prepared by methods well known in the art. For example, U.S. Pat. Nos. 4,321,970, 4,340,619, 4,395,460, 4,404,153, 4,482,689, 4,398,828, 4,540,343, 4,543,344, 4,835,238 can be used for preparing such silazanes. Nos. 4,774,312, 4,929,742 and 4,916,200. Furthermore, J. et al. Mater. Sci. 22, 2609 (1987).

These silazanes may be silicon-containing copolymer compounds with other polymers. For example, silicon-containing copolymer compound having Si—N—Si bond and Si—O—Si bond; silicon-containing copolymer compound having Si—N—Si bond and Si—Si bond; Si—N—Si bond and Si- _{(CH 2)} containing copolymer compounds having n -Si bonds; Si-n-Si bonds and _{Si- (C 6 H 4) n} -Si bonds or _{Si- (CH 2 CH 2 C 6} H ₄ CH ₂ CH _{2) n} containing copolymer compounds having -Si bond or the like may be used as a polysilazane. In the formula, n is the same as described above.

Examples of carbosilanes include an average unit formula:

(In the formula, each R ⁷ independently represents a monovalent hydrocarbon group, a hydrogen atom, a halogen atom, an epoxy group-containing organic group, an acrylic group-containing organic group, a methacryl group-containing organic group, an amino group-containing organic group, or a mercapto group. A group-containing organic group, an alkoxy group or a hydroxy group, provided that at least one, preferably at least 2, R ⁷ in one molecule is an alkenyl group, a hydrogen atom, a halogen atom, an epoxy group-containing organic group, an acrylic group A group-containing organic group, a methacryl group-containing organic group, an amino group-containing organic group, a mercapto group-containing organic group, an alkoxy group, or a hydroxy group; R ¹¹ is an alkylene group or an arylene group; a, b, c, and d Is a number satisfying 0 or more and 1 or less and satisfying a + b + c + d = 1, provided that a, b and c are not 0). The alkylene group of R ¹¹ is represented by, for example, the formula: — (CH ₂ ) _n —, and the arylene group of R ¹¹ is represented, for example, by the formula: — (C ₆ H ₄ ) _n —. In the formula, n is the same as described above.

The carbosilanes are composed of at least one of structural units represented by (R ⁷ ₃ SiR ¹¹ ), (R ⁷ ₂ SiR ¹¹ ), (R ⁷ SiR ¹¹ ), and (SiR ¹¹ ), Specifically, for example, a linear polycarbosilane composed of units of (R ⁷ ₃ SiR ¹¹ ) and (R ⁷ ₂ SiR ¹¹ ); a cyclic polycarbosilane composed of units of (R ⁷ ₂ SiR ¹¹ ); R ⁷ SiR ¹¹ ) or branched polycarbosilane composed of (SiR ¹¹ ) units; (R ⁷ ₃ SiR ¹¹ ) and (R ⁷ SiR ¹¹ ) units composed of units; (R ⁷ ₃ SiR ¹¹ ) and polycarbosilane comprising units of ^{(SiR 11); (R 7} SiR 11) and polycarbosilane comprising units of _{^{(SiR 11); (R 7}} 2 SiR ¹⁾ and ^{(polycarbosilane} consisting R 7 ^{SiR 11) units;} _(R 7 2 ^{SiR 11)} and (polycarbosilane comprising units of _{^{SiR 11); (R 7 3}} SiR 11), (R 7 2 SiR ¹¹ ) and (R ⁷ SiR ¹¹ ) units of polycarbosilane; (R ⁷ ₃ SiR ¹¹ ), (R ⁷ ₂ SiR ¹¹ ) and (SiR ¹¹ ) units of polycarbosilane; (R ⁷ ₃ SiR ¹¹ ), a polycarbosilane composed of units of (R ⁷ SiR ¹¹ ) and (SiR ¹¹ ); a polycarbosilane composed of units of (R ⁷ ₂ SiR ¹¹ ), (R ⁷ SiR ¹¹ ) and (SiR ¹¹ ); _{^{R 7 3 SiR 11), (}} R 7 2 SiR 11), include polycarbosilane like comprising units of (R 7 ^{SiR 11)} and ^{(SiR 11)} It is. The preferable number of repeating structural units represented by (R ⁷ ₃ SiR ¹¹ ), (R ⁷ ₂ SiR ¹¹ ), (R ⁷ SiR ¹¹ ) and (SiR ¹¹ ) is within the range of 2 to 10,000, respectively. More preferably, it is preferably within the range of 3 to 1,000, and particularly preferably within the range of 3 to 500.

These carbosilanes can be prepared by methods well known in the art. The preparation method of carbosilanes is described in, for example, Macromolecules, 21, 30 (1988), US Pat. No. 3,293,194.

These carbosilanes may be silicon-containing copolymer compounds with other polymers. For example, a silicon-containing copolymer compound having a Si— (CH ₂ ) _n —Si bond and a Si—O—Si bond; a silicon-containing copolymer having a Si— (CH ₂ ) _n —Si bond and a Si—Si bond Compound; silicon-containing copolymer compound having Si— (CH ₂ ) _n —Si bond and Si—N—Si bond; Si— (CH ₂ ) _n —Si bond and Si— (C ₆ H ₄ ) _n —Si Silicon-containing copolymer compound having a bond; silicon-containing copolymer compound having a Si— (C ₆ H ₄ ) _n —Si bond and a Si—O—Si bond; Si— (C ₆ H ₄ ) _n —Si bond And a silicon-containing copolymer compound having a Si—Si bond; Si— (C ₆ H ₄ ) _n —Si bond or Si— (CH ₂ CH ₂ C ₆ H ₄ CH ₂ CH ₂ ) _n —Si bond and Si— Containing N-Si bond Lee Mototomo polymer compound or the like can be used as carbosilanes acids. In the formula, n is the same as described above.

As the component (B), in particular, the average unit formula:

(In the formula, each R ⁷ independently represents a monovalent hydrocarbon group, a hydrogen atom, a halogen atom, an epoxy group-containing organic group, an acrylic group-containing organic group, a methacryl group-containing organic group, an amino group-containing organic group, or a mercapto group. A group-containing organic group, an alkoxy group or a hydroxy group; a, b, c and d are each a number satisfying 0 or more and 1 or less and satisfying a + b + c + d = 1, provided that both a, b and c are (In particular, polysiloxane is preferred).

Specific examples of crosslinking reactions include hydrosilylation reactions, Michael addition reactions, Diels-Alder reactions, and the like; condensation reactions such as dealcoholization, dehydrogenation, dehydration, and deamination; epoxy ring opening, ester ring opening, etc. Ring-opening reaction; radical reactions such as peroxide and UV are exemplified. In particular, when the component (A) has an aliphatic unsaturated group and the component (B) has a silicon atom-bonded hydrogen atom, the hydrosilylation reaction can be performed in the presence of a hydrosilylation reaction catalyst.

Specific examples of the hydrosilylation reaction catalyst include platinum fine powder, platinum black, platinum-supported silica fine powder, platinum-supported activated carbon, chloroplatinic acid, platinum tetrachloride, chloroplatinic acid alcohol solution, platinum and olefins. Complexes, platinum and alkenylsiloxane complexes are exemplified. The content is not particularly limited, but the metal atoms in the catalyst are within the range of 0.1 to 1,000 ppm in terms of mass (weight) with respect to the total amount of the components (A) and (B). It is preferable that the amount be in the range of 1 to 500 ppm.

In addition, when the component (A) has an aliphatic unsaturated group and the component (B) has a silicon-bonded hydrogen atom, the component (A) has a silicon-bonded hydrogen atom, and the component (B) When A has an aliphatic unsaturated group, the amount of each component used is not particularly limited, but the component (B) or (A) is used with respect to 1 mol of the aliphatic unsaturated group in the component (A) or (B). ) The amount of silicon-bonded hydrogen atoms in the component is in the range of 0.1 to 50 mol, preferably in the range of 0.1 to 30 mol, particularly preferably 0.1 The amount is in the range of ~ 10 mol. This is because when the amount of silicon atom-bonded hydrogen atoms is less than the lower limit of the range, the yield of carbonization when the resulting cured product is fired tends to be reduced, whereas when the amount exceeds the range, it is obtained. This is because the performance as an electrode active material of the silicon-containing carbon-based composite material obtained by firing the cured product tends to decrease.

In addition, when the component (A) has an aliphatic unsaturated group, the component (B) has an aliphatic unsaturated group, an acrylic group, a methacryl group, or a silicon-bonded hydrogen atom, and the component (B) In the case where the component (A) has an aliphatic unsaturated group, an acrylic group, a methacryl group, or a silicon atom-bonded hydrogen atom, it undergoes a radical reaction by heat and / or light with a radical initiator. You can also.

Specific examples of the radical initiator include organic peroxides such as dialkyl peroxide, diacyl peroxide, peroxyester, peroxydicarbonate, and organic azo compounds. Specifically, as this organic peroxide, dibenzoyl peroxide, bis-p-chlorobenzoyl peroxide, bis-2,4-dichlorobenzoyl peroxide, di-t-butyl peroxide, dicumyl peroxide, t-butyl perbenzoate, 2,5-bis (t-butylperoxy) -2,3-dimethylhexane, t-butyl peracetate, bis (o-methylbenzoyl peroxide), bis (m-methylbenzoyl peroxide) ), Bis (p-methylbenzoyl peroxide), 2,3-dimethylbenzoyl peroxide, 2,4-dimethylbenzoyl peroxide, 2,6-dimethylbenzoyl peroxide, 2,3,4-trimethylbenzoyl peroxide, 2,4,6-trimethylbenzoylpa Methyl group-substituted benzoyl peroxide such as oxide; t-butyl perbenzoate, dicumyl peroxide, 2,5-dimethyl-2,5-di (t-butylperoxy) hexane, t-butylperoxyisopropyl monocarbonate, Examples thereof include t-butyl peroxyacetate and a mixture thereof. Specific examples of the organic azo compound include 2,2′-azobisisobutyronitrile, 2,2′-azobis (4-methoxy-2,4-dimethylvaleronitrile, 2,2′-azobis). Examples include (2,4-dimethylvaleronitrile), 2,2′-azobis-isobutylvaleronitrile, and 1,1′-azobis (1-cyclohexanecarbonitrile).

The content of the radical initiator is not particularly limited, but is preferably an amount that falls within a range of 0.1 to 10 mass (weight)% with respect to the total amount of the component (A) and the component (B). In particular, the amount is preferably in the range of 0.5 to 5 mass (weight)%.

In addition, when the component (A) has an aliphatic unsaturated group, the component (B) has an aliphatic unsaturated group, an acrylic group, a methacryl group, or a silicon atom-bonded hydrogen atom, and the component (B) When it has an aliphatic unsaturated group and the component (A) has an aliphatic unsaturated group, an acrylic group, a methacryl group or a silicon atom-bonded hydrogen atom, the amount of each component used is not particularly limited, The amount of the aliphatic unsaturated group, acrylic group, methacrylic group or silicon atom-bonded hydrogen atom in the other component in the range of 0.1 to 50 moles per mole of the aliphatic unsaturated group of The amount is preferably in the range of 0.1 to 30 mol, and particularly preferably in the range of 0.1 to 10 mol. This is because the amount of aliphatic unsaturated group, acrylic group, methacryl group or silicon-bonded hydrogen atom is less than the lower limit of the above range, the carbonization yield when the obtained cured product is fired tends to decrease. On the other hand, if the above range is exceeded, the performance as an electrode active material of the silicon-containing carbon-based composite material obtained by firing the obtained cured product tends to be reduced.

When forming the hardened | cured material formed by carrying out the crosslinking reaction of (A) component and (B) component, it can manufacture by the method of following I or II, for example, Then, it can transfer to the process of heat processing (baking).
I: After mixing the component (A) and the component (B), precure at a temperature of 300 ° C. or less, particularly 60 to 300 ° C. The obtained cured product may be used as it is in the next baking step, or may be used in the next baking step after being pulverized to a particle size of 0.1 to 30 μm, more preferably 1 to 20 μm.
II: When the cured product is formed as spherical particles, for example, a crosslinkable composition comprising the component (A) and the component (B) is sprayed into hot air to cause a crosslink reaction, or the crosslinkable composition and the noncrosslinkable composition It is preferable to carry out a crosslinking reaction by emulsifying or dispersing in a compatible medium.

When one of the component (A) or the component (B) has an aliphatic unsaturated group and the other has a silicon atom-bonded hydrogen atom, the component (A), the component (B) and the hydrosilylation reaction catalyst are mixed. The resulting crosslinkable composition is sprayed into hot air in the form of fine particles and crosslinked by a hydrosilylation reaction to obtain a fine particle cured product powder.

On the other hand, the crosslinkable composition obtained by mixing the component (A), the component (B) and the hydrosilylation reaction catalyst is added to an aqueous solution of an emulsifier, and emulsified by stirring to form fine particles of the crosslinkable composition. Subsequently, it can also be crosslinked by a hydrosilylation reaction to form a fine particle cured product powder.

This emulsifier is not particularly limited, and specific examples include ionic surfactants, nonionic surfactants, and mixtures of ionic surfactants and nonionic surfactants. In particular, since the uniform dispersibility and stability of the oil-in-water emulsion produced by mixing the crosslinkable composition and water are good, one or more ionic surfactants and one or more nonionics are used. It is preferred to use a mixture of surfactants.

In addition, by using a metal oxide such as silica (colloidal silica) or titanium oxide in combination with an emulsifier, carbonization is performed while holding the silica on the surface of the cured powder, thereby forming a stable film on the carbon surface. Further, it is possible to increase the carbonization yield or to suppress surface oxidation that occurs when the carbon material is left standing.

The particle size of the cured product powder is not particularly limited, but since a silicon-containing carbon-based composite material having an average particle size of 1 to 20 μm suitable as an electrode active material is formed by firing, the preferable average particle size is 5 to 30 μm. It is preferably within the range, and particularly preferably within the range of 5 to 20 μm.

It is preferable to further heat-treat at 150 to 300 ° C. in the air, since crosslinking of the cured powder thus obtained can be further promoted and the carbonization yield by firing can be improved.

The silicon-containing carbon-based composite material of the present invention can be obtained through a step of heat-treating (baking) the cured product of the component (A) and the component (B).

The firing conditions are not particularly limited, but firing at 300 to 1500 ° C. in an inert gas or vacuum is preferable. Nitrogen, helium, and argon are illustrated as an inert gas. The inert gas may contain a reducing gas such as hydrogen gas. The firing temperature is more preferably in the range of 500 ° C to 1000 ° C. The firing time is not particularly limited, but can be, for example, in the range of 10 minutes to 10 hours, preferably 30 minutes to 3 hours.

Calcination can be performed in a fixed bed or fluidized bed type carbonization furnace, and the heating method and type of the carbonization furnace are not particularly limited as long as the furnace has a function of raising the temperature to a predetermined temperature. Specific examples of the carbonization furnace include a lead hammer furnace, a tunnel furnace, a single furnace, an oxynon furnace, a roller hearth kiln, a pusher kiln, a batch rotary kiln, and a continuous rotary kiln.

When a continuous furnace such as a roller hearth kiln, pusher kiln, or continuous rotary kiln is used, a process of forming a cured product obtained by cross-linking the components (A) and (B) and a baking process of the cured product are continuously performed. Can be done automatically. In addition, the step of forming a cured product obtained by crosslinking the component (A) and the component (B), the firing step, and the surface coating treatment step such as sputtering and thermal chemical vapor deposition treatment may be continuously performed in a continuous furnace. it can. When a continuous furnace such as a roller hearth kiln, pusher kiln, or continuous rotary kiln is used, the oxygen concentration in each process atmosphere can be strictly controlled, so the amount of oxygen atoms in the resulting silicon-containing carbon composite material can be controlled and adjusted. There is an advantage that becomes easy.

The silicon-containing carbon composite material of the present invention thus obtained has a chemical composition represented by the formula: SiO _x C _y . In the formula, x is 0.8 to 1.5, preferably 0.8 to 1.4, more preferably 0.8 to 1.3, and still more preferably 0.9 to 1.2. y is 1.4 to 7.5, preferably 1.7 to 7.0, more preferably 2.0 to 7.0, and still more preferably 2.5 to 4.5. In the silicon-containing carbon composite material of the present invention, the peak area derived from sp2 carbon atom / the peak area derived from sp3 carbon atom in the ¹³ C MAS NMR spectrum is 1.6 to 46, preferably 2.0 to 40, more preferably 3. It is 0 to 30, and most preferably 4.0 to 25. Within the above range, reversible capacity and charge / discharge cycle characteristics are improved, and in particular, initial charge / discharge efficiency is improved. In addition, the measurement conditions of ¹³ C MAS NMR are not particularly limited, and can be appropriately changed according to the measurement apparatus.

The peak derived from the sp2 carbon atom in the ¹³ C MAS NMR spectrum can be attributed to carbon in a condensed ring condensed with an aromatic ring such as a graphene structure, and its chemical shift is 99 to 160 ppm. The peak derived from the sp3 carbon atom in the ¹³ C MAS NMR spectrum can be attributed to aliphatic carbon and refers to a peak with a chemical shift of 11-49 ppm when TMS is 0 ppm. Although the calculation method of each peak area is arbitrary, it can obtain | require by the approximation method using a Gaussian waveform, for example.

The chemical composition of the silicon-containing carbon composite material and the sp2 carbon atom-derived peak area / sp3 carbon atom-derived peak area of the ¹³ C MAS NMR spectrum are, for example, (A) component type, (B) component type, and (A It is possible to control by adjusting in advance the ratio of oxygen atom and carbon atom per silicon atom in the cured product by changing the quantitative ratio of component (B) and component (B) during the curing reaction. In particular, if there is an aromatic hydrocarbon group bonded to a silicon atom, it becomes easy to control the value of “y” after firing and the ratio of the peak area derived from sp2 carbon atom / sp3 carbon atom derived from ¹³ C MAS NMR spectrum. Therefore, it is preferable that the component (A) contains a silicon atom, and either the component (A) or the component (B) or both contain a silicon atom-bonded aromatic hydrocarbon group. It can also be controlled by the heat treatment atmosphere during firing, the flow rate of the inert gas, the heating rate, and the heat treatment time.

The silicon-containing carbon-based composite material preferably has an amorphous structure in which silicon atoms are bonded to oxygen atoms and carbon atoms. Such a structure can be confirmed by ²⁹ Si MAS NMR or X-ray diffraction analysis. If the silicon-containing carbon-based composite material is crystallized, the charge / discharge cycle characteristics and the initial charge / discharge efficiency may be reduced.

The surface of the silicon-containing carbon-based composite material of the present invention may be further subjected to a surface coating treatment with metal or carbon. However, “y”, “sp2 carbon atom”, and “sp3 carbon atom” in the above composition formula do not include carbon atoms in the surface-coated carbon phase.

The carbon surface coating method of the silicon-containing carbon-based composite material is arbitrary. For example, the carbon film derived from the vapor deposition carbon source (D1) may be subjected to thermal chemical vapor deposition on the surface of the silicon-containing carbon-based composite material at a temperature of 800 ° C. or higher in a non-oxidizing atmosphere. In addition, (D2) a silicon-containing carbon-based composite material covered with a carbon phase derived from an organic material that is carbonized by heat by mixing an organic material that is carbonized by heat and a silicon-containing carbon-based composite material and further firing the mixture. It can also be obtained.

The apparatus used for the thermal chemical vapor deposition is not particularly limited as long as it has an apparatus for heating to 800 ° C. or higher in a non-oxidizing atmosphere, and can be appropriately selected according to the purpose. A continuous method, a batch method, and an apparatus using both of these can be used. Specific examples include a fluidized bed reactor, a rotary furnace, a vertical moving bed reactor, a tunnel furnace, a batch furnace, a batch rotary kiln, and a continuous rotary kiln. The

Specifically, (D1) vapor deposition carbon source used in the thermal chemical vapor deposition treatment is an aliphatic hydrocarbon such as methane, ethane, ethylene, acetylene, propane, butane, butene, pentane, isobutane, hexane, or a mixture thereof. ; Aromatic hydrocarbons such as benzene, divinylbenzene, monovinylbenzene, ethyl vinylbenzene, toluene, xylene, styrene, ethylbenzene, diphenylmethane, naphthalene, phenol, cresol, nitrobenzene, chlorobenzene, indene, coumarone, pyridine, anthracene, phenanthrene Gas gas oil, creosote oil, anthracene oil, naphtha cracked tar oil obtained in the tar distillation process; exhaust gas generated in the calcination process, or a mixture thereof. It is common to be methane or acetylene.

The non-oxidizing atmosphere includes the vapor deposition carbon source gas or a vaporized gas thereof; a non-oxidizing gas such as argon gas, helium gas, hydrogen gas, nitrogen gas; Can be obtained.

(D2) When the organic material carbonized by heat and the silicon-containing carbon composite material are mixed and further baked to obtain a silicon-containing carbon-based composite material covered with the carbon phase derived from the organic material carbonized by heat. Can be performed in the same manner as described above. (D2) Specific examples of organic materials that are carbonized by heat include paraffin, polyethylene, polypropylene, polystyrene, polymethyl methacrylate, urethane resin, AS resin, ABS resin, polyvinyl chloride, and polyacetal that are liquid or waxy at room temperature. And aromatic polycarbonate resins, aromatic polyester resins, coal tar, phenol resins, epoxy resins, urea resins, melamine resins, fluororesins, imide resins, urethane resins, furan resins, and mixtures thereof. Among these, high molecular weight aromatic compounds such as aromatic polycarbonates, aromatic polyesters, coal tars, phenol resins, fluororesins, imide resins, furan resins, and melamine resins are preferable. This is because the carbonization efficiency by heat is good, for example, the formation of the graphene structure is easy.

When the surface of the silicon-containing carbon composite material is coated with carbon, the coating amount of carbon is preferably 0.5 to 50 mass (weight)% in the silicon-containing carbon-based composite material, and 1 to 30 mass (weight). %, More preferably 1 to 20% by mass (weight). This is because even when only a silicon-containing carbon-based composite material is used as the electrode active material, it has suitable conductivity and can suppress a decrease in charge / discharge capacity of the electrode.

The metal surface coating method of the silicon-containing carbon-based composite material is arbitrary. For example, the surface of a silicon-containing carbon-based composite material with a metal coating such as gold, silver, copper, iron, zinc, platinum, aluminum, cobalt, nickel, titanium, palladium, stainless steel, etc. by vacuum deposition, sputtering, electrolytic plating or electroless plating Can be formed. Among these, nickel and copper are suitable as the surface coating metal.

The silicon-containing carbon-based composite material of the present invention can be in the form of particles having an average particle diameter of 5 nm to 50 μm. The average particle size is preferably 10 nm to 40 μm, more preferably 100 nm to 30 μm, and even more preferably 1 μm to 20 μm.

The silicon-containing carbon-based composite material of the present invention can be used as an electrode active material. The electrode active material of the present invention can be in the form of particles, in which case the average particle size is preferably 1 to 50 μm, more preferably 1 to 40 μm, and further preferably 1 to 30 μm. Is more preferable.

The electrode active material comprising the silicon-containing carbon-based composite material of the present invention has a high reversible capacity, stable charge / discharge cycle characteristics, and can produce an electrode with a small potential loss when lithium is released by a simple manufacturing process. It can be. Therefore, this electrode active material can be suitably used as an active material for an electrode of a nonaqueous electrolyte secondary battery. In particular, this electrode active material is suitable as an active material for electrodes of lithium or lithium ion secondary batteries.

(electrode)
The electrode of the present invention is characterized by containing the above electrode active material, and the shape and preparation method of the electrode are not particularly limited. Specifically, the electrode of the present invention was prepared by mixing a silicon-containing carbon-based composite material with a binder to produce an electrode; obtained by mixing the silicon-containing carbon-based composite material with a binder and a solvent. Examples of the method of producing the electrode include a method in which the paste is pressure-bonded on the current collector or coated on the current collector and then dried to form an electrode. The thickness of the paste applied to the current collector is, for example, about 30 to 500 μm, preferably about 50 to 300 μm. The means for drying after coating is not particularly limited, but a heat vacuum drying treatment is preferable. The film thickness of the electrode material on the current collector after the drying treatment is, for example, about 10 to 300 μm, preferably about 20 to 200 μm. In addition, when the silicon-containing carbon-based composite material is in a fibrous form, it is arranged in a uniaxial direction, or in the form of a structure such as a woven fabric, and bundled or braided with conductive fibers such as metal or conductive polymer, An electrode can be produced. In forming the electrodes, terminals may be combined as necessary.

The current collector is not particularly limited, and specifically, a metal mesh or foil such as copper, nickel, or an alloy thereof is exemplified.

Specific examples of the binder include fluorine resins (polyvinylidene fluoride, polytetrafluoroethylene, etc.) and styrene-butadiene resins. The amount of the binder used is not particularly limited, and the lower limit thereof is preferably in the range of 5 to 30 mass (weight) parts with respect to 100 mass (weight) parts of the silicon-containing carbon-based composite material, preferably Is in the range of 5 to 20 parts by mass (weight). When the amount of the binder used is outside the above range, for example, the adhesion strength of the silicon-containing carbon-based composite material on the current collector surface becomes insufficient, and an insulating layer that causes an increase in electrode internal resistance is formed. There is a risk. The method for preparing the paste is not particularly limited, and examples thereof include a method of mixing a silicon-containing carbon-based composite material in a mixed liquid (or dispersion liquid) of a binder and an organic solvent.

As the solvent, a solvent capable of dissolving or dispersing the binder is usually used, and specific examples thereof include organic solvents such as N-methylpyrrolidone and N, N-dimethylformamide. The amount of the solvent used is not particularly limited as long as it is in a paste form, and is usually within a range of 0.01 to 500 mass (weight) parts with respect to 100 mass (weight) parts of the silicon-containing carbon-based composite material, Preferably it is in the range of 0.01 to 400 parts by weight (weight), more preferably in the range of 0.01 to 300 parts by weight (weight).

In addition, you may mix | blend arbitrary additives with the electrode of this invention. For example, you may manufacture an electrode by adding a conductive support agent. The use ratio of the conductive auxiliary agent is not particularly limited, but is within the range of 2 to 60 mass (weight) parts, preferably 5 to 40 mass (weight) with respect to 100 mass (weight) parts of the silicon-containing carbon-based composite material. ) Parts, and more preferably in the range of 5 to 20 parts by weight (weight). It is because it is excellent in electroconductivity and can suppress the fall of the charge / discharge capacity of an electrode.

Examples of the conductive aid include carbon black (Ketjen black, acetylene black, etc.), carbon fiber, carbon nanotube, and the like. A conductive support agent can be used individually or in combination of 2 or more types. In addition, a conductive support agent can be mixed with the paste containing a silicon containing carbon type composite material, a binder, and a solvent, for example.

Moreover, an electrode active material such as graphite may be blended in the electrode of the present invention as any other additive.

(Electric storage device)
An electricity storage device according to the present invention includes the electrode. Examples of such electricity storage devices include lithium primary batteries, lithium secondary batteries, lithium ion secondary batteries, capacitors, hybrid capacitors (redox capacitors), organic radical batteries, and dual carbon batteries, particularly lithium or lithium ion secondary batteries. A battery is preferred. Lithium ion secondary batteries use, for example, battery components such as a negative electrode comprising the above electrodes, a positive electrode capable of inserting and extracting lithium, an electrolyte solution, a separator, a current collector, a gasket, a sealing plate, a case, and the like. Can be manufactured. The lithium secondary battery can be produced by a conventional method using battery components such as a positive electrode made of the electrode, a negative electrode made of metallic lithium, an electrolyte, a separator, a current collector, a gasket sealing plate, and a case. .

The lithium or lithium ion secondary battery, which is a preferred embodiment of the battery of the present invention, will be described in detail with reference to FIGS.

FIG. 1 is a schematic exploded sectional view of a button-type battery which is a lithium ion secondary battery which is an example of the battery of the present invention.

A lithium ion secondary battery shown in FIG. 1 includes a cylindrical case 1 having a bottom surface with a top opening, a cylindrical gasket 2 having an inner periphery that is substantially the same size as the outer periphery of the case 1, a washer 3, a SUS plate 4, It consists of a current collector 5, a negative electrode 6 containing the silicon-containing carbon-based composite material of the present invention as an electrode active material, a separator 7, a positive electrode 8, a current collector 9, and a sealing plate 10.

In the case 1 of the lithium ion secondary battery shown in FIG. 1, a washer 3 having a substantially ring shape slightly smaller than the inner periphery of the case 1 is accommodated, and the inner periphery of the case 1 is placed on the washer 3. A SUS plate 4 having a substantially disk shape slightly smaller than that is placed. On the SUS plate 4, a current collector 5 and a negative electrode 6 that are both substantially disk-shaped and slightly smaller than the inner circumference of the case 1 are disposed. On the negative electrode 6, a separator 7 as a disk-shaped member having a size substantially the same as the inner periphery of the case 1 is placed, and the separator 7 is impregnated with an electrolytic solution. The separator 7 may be composed of two or more disk-shaped members. On the separator 7, a positive electrode 8 having a size substantially equal to that of the negative electrode 6 and a current collector 9 having a size substantially equal to that of the current collector 5 are disposed. The current collector 5 is made of foil, mesh, or the like made of metal such as copper or nickel, and the current collector 9 is made of foil, mesh, or the like made of metal such as aluminum, and the negative electrode 6 and the positive electrode, respectively. 8 is in close contact with and integrated.

In the lithium ion secondary battery shown in FIG. 1, the gasket 2 is fitted to the wall surface of the case 1, and the bottom-opening bottomed cylindrical sealing plate 10 having an inner peripheral surface slightly larger in size than the gasket 2. The inner peripheral surface is further fitted to the outer peripheral surface of the gasket 2. As a result, the case 1 and the sealing plate 10 are insulated by the gasket 2, and the case 1, the gasket 2, the washer 3, the SUS plate 4, the current collector 5, the negative electrode 6, the separator 7, the positive electrode 8, the current collector 9 and the sealing plate. A button-type battery in which 10 axes coincide with each other is formed.

The positive electrode 8 in the lithium ion secondary battery shown in FIG. 1 is not particularly limited, and can be composed of, for example, a positive electrode active material, a conductive additive, a binder, and the like. Examples of the positive electrode active material include metal oxides such as LiCoO ₂ , LiNiO ₂ , and LiMn ₂ O ₄ , polyanionic oxides such as LiFePO ₄ and Li ₂ FeSiO ₄ , and spinel-type LiMn ₂ O _4. . You may use a positive electrode active material individually or in combination of 2 or more types. Examples of the conductive aid and binder are the same as described above.

FIG. 2 is a schematic exploded cross-sectional view of a button-type battery that is a lithium secondary battery that is an example of the battery of the present invention manufactured in the examples.

The lithium secondary battery shown in FIG. 2 includes a cylindrical case 1 having a bottom surface with a top opening, a cylindrical gasket 2 having an inner periphery substantially the same size as the outer periphery of the case 1, a washer 3, a SUS plate 4, and a metal. It consists of a negative electrode 6 made of lithium, a separator 7, a positive electrode 8 containing the silicon-containing carbon-based composite material of the present invention as an electrode active material, a current collector 9 ′, and a sealing plate 10.

In the case 1 of the lithium secondary battery shown in FIG. 2, a washer 3 having a substantially ring shape that is slightly smaller than the inner periphery of the case 1 is accommodated. Also, a SUS plate 4 having a substantially disk shape with a slightly smaller size is placed. On the SUS plate 4, a negative electrode 6 having a substantially disk shape slightly smaller than the inner periphery of the case 1 is disposed. On the negative electrode 6, a separator 7 as a disk-shaped member having a size substantially the same as the inner periphery of the case 1 is placed, and the separator 7 is impregnated with an electrolytic solution. The separator 7 may be composed of two or more disk-shaped members. On the separator 7, a positive electrode 8 and a current collector 9 ′ having substantially the same size as the negative electrode 6 are disposed. The current collector 9 ′ is made of a foil, mesh, or the like made of a metal such as copper or nickel, and is in close contact with the positive electrode 8 so as to be integrated.

In the lithium secondary battery shown in FIG. 2, the gasket 2 is fitted to the wall surface of the case 1, and the inside of the bottom-opening bottomed cylindrical sealing plate 10 having an inner peripheral surface slightly larger in size than the gasket 2. The peripheral surface is further fitted to the outer peripheral surface of the gasket 2. Thereby, the case 1 and the sealing plate 10 are insulated by the gasket 2, and the axes of the case 1, the gasket 2, the washer 3, the SUS plate 4, the negative electrode 6, the separator 7, the positive electrode 8, the current collector 9 ', and the sealing plate 10 are aligned. A matched button cell is formed.

The electrolytic solution contained in the lithium or lithium ion secondary battery shown in FIGS. 1 and 2 is not particularly limited, and known ones can be used. For example, a non-aqueous lithium or lithium ion secondary battery can be manufactured by using a solution obtained by dissolving an electrolyte in an organic solvent as the electrolytic solution. As the electrolyte, for _example, can be exemplified _{LiPF 6, LiClO 4, LiBF 4} , LiClF 4, LiAsF 6, LiSbF 6, LiAlO 4, LiAlCl 4, LiCl, lithium salt such as LiI. Examples of the organic solvent include carbonates (propylene carbonate, ethylene carbonate, diethyl carbonate, etc.), lactones (γ-butyrolactone, etc.), chain ethers (1,2-dimethoxyethane, dimethyl ether, diethyl ether, etc.), cyclic Ethers (tetrahydrofuran, 2-methyltetrahydrofuran, dioxolane, 4-methyldioxolane, etc.), sulfolanes (sulfolane, etc.), sulfoxides (dimethylsulfoxide, etc.), nitriles (acetonitrile, propionitrile, benzonitrile, etc.), amides Aprotic solvents such as (N, N-dimethylformamide, N, N-dimethylacetamide and the like) and polyoxyalkylene glycols (diethylene glycol and the like) can be exemplified. An organic solvent may be used independently and may be used as a 2 or more types of mixed solvent. The electrolyte concentration is, for example, about 0.3 to 5 mol, preferably 0.5 to 3 mol, and more preferably about 0.8 to 1.5 mol with respect to 1 L of the electrolyte.

The separator 4 in the lithium or lithium ion secondary battery shown in FIGS. 1 and 2 is not particularly limited, and is a known separator, for example, a polyolefin-based porous material such as a porous polypropylene nonwoven fabric or a porous polyethylene nonwoven fabric. A membrane or the like can be used.

The electricity storage device of the present invention is not limited to the examples shown in FIGS. 1 and 2, and may be various forms such as a laminated shape, a pack shape, a button shape, a gum shape, an assembled battery shape, and a square shape. Applicable. The devices of the present invention, particularly lithium or lithium ion secondary batteries, are lightweight and have high capacity and high energy density, so that they can be used in small portable devices such as video cameras, personal computers, word processors, radio cassettes, and mobile phones. It is preferably used as a power source for electronic devices, a power source for hybrid vehicles and electric vehicles, and a power storage power source.

The electrode active material of the present invention has a high reversible capacity and stable charge / discharge cycle characteristics and high initial charge / discharge efficiency, and is suitable for an electrode of an electricity storage device, particularly lithium or lithium ion secondary battery. Moreover, the electrode active material of the present invention can be manufactured by a simple manufacturing process using inexpensive raw materials. The electrode of the present invention can impart high reversible capacity, stable charge / discharge cycle characteristics, and high initial charge / discharge efficiency to the battery. Therefore, the electricity storage device of the present invention can have high reversible capacity, stable charge / discharge cycle characteristics, and high initial charge / discharge efficiency.

EXAMPLES Hereinafter, although this invention is demonstrated in detail based on an Example and a comparative example, this invention is not limited to an Example. In addition, each elemental analysis in an Example and a comparative example, < ¹³ > C MAS NMR measurement, sp2 peak area / sp3 peak area determination, and evaluation of the battery characteristic were implemented as follows.

[Elemental analysis]
C, H, N analysis: The total amount of elements detected by the oxygen circulating combustion method / TCD detection method and the high frequency combustion method / infrared absorption detection method was used.
Apparatus: NCH-21 or NCH-22F type (manufactured by Sumika Chemical Analysis Service)
Device: CS-LS600 (manufactured by LECO)
O analysis: high temperature carbon reaction / NDIR detection system: EMGA-2800 (manufactured by Horiba, Ltd.)
Si analysis: Samples were incinerated, melted with alkali, dissolved in acid and decomposed, and then ICP detection was performed.
Device: iCAP6500 DuoView (manufactured by Thermo Fisher Scientific)

[ ¹³ C MAS NMR]
CMX-300 Infinity manufactured by Chemicals
Measuring method: DD MAS method was used to ensure quantitativeness.
Measurement nuclear frequency: 75.19 MHz
Sample rotation speed: 10.5 kHz
Reference substance: polydimethylsiloxane (1.56 ppm: chemical shift when TMS is 0 ppm)

[Ratio of sp2 peak area / sp3 peak area]
The peak area of 99-160 ppm in the ¹³ C MAS NMR spectrum is assumed to be derived from sp2 carbon, the peak area of 11-49 ppm is assumed to be derived from sp3 carbon, and the peak area is approximated using a Gaussian waveform for each peak. The ratio of the peak area derived from sp2 carbon atoms / the peak area derived from sp3 carbon atoms was determined.

[Battery characteristics]
The lithium insertion / extraction capacity of the silicon-containing carbon material of the present invention was measured as follows.
Using HJ1010mSM8A manufactured by Hokuto Denko, the lithium insertion / extraction capacity was measured at a constant current. At that time, the theoretical capacity per weight of the silicon-containing carbon material was set to 700 mAh, and the current value was set to 70 mA per weight of the silicon-containing carbon material. Lithium insertion was performed after the battery voltage reached 0.005 V until the current value was reduced to 1/10. Lithium release was the capacity until the battery voltage reached 1.5V. At the time of switching between each lithium insertion / extraction, it was left in an open circuit for 30 minutes. In addition, about cycling characteristics, it carried out on the same conditions except having set it as the electric current value of 140 mA per silicon-containing carbon material weight after the 2nd time. The calculation of the efficiency of the first cycle was performed based on the following formula.
Initial irreversible capacity loss (%) =
First cycle lithium desorption capacity / first cycle lithium insertion capacity x 100
The lithium desorption capacity at the second cycle was defined as a reversible capacity, and the capacity retention rate after the cycle test was expressed as the lithium desorption capacity after the cycle with respect to the lithium desorption capacity.

[Example 1]
(Preparation of silicon-containing cured product)
DVB570 (manufactured by Nippon Steel Chemical Co., Ltd., 57.0 mass (weight)% divinylbenzene and 38.9 mass (weight)% vinylethylbenzene are the main components, and the content of divinylbenzene in the main components is about 60 mass%) To 775 g, 531 g of vinyl group in the above-mentioned DVB570 (the content of silicon atom-bonded hydrogen atoms = 1.58 mass (weight)%) having a viscosity of 20 mPa · s and having a molecular chain at both ends trimethylsiloxy group-blocked methylhydrogenpolysiloxane The amount of silicon-bonded hydrogen atoms in this copolymer is about 1 mol) and platinum 1,3-divinyltetramethyldisiloxane complex platinum catalyst as platinum metal in an amount of 10 ppm mixed to form a crosslinkable composition Prepared. Thereafter, the composition was cured at 120 ° C. in the atmosphere to prepare a cured product.

(Preparation of silicon-containing carbon material)
969 g of the cured product was put into an SSA-S grade alumina boat, and the boat was placed in a degreasing furnace. Thereafter, the inside of the degreasing furnace was maintained at a reduced pressure for 10 minutes, and then returned to normal pressure with high-purity nitrogen (99.99%). This operation was repeated once in total. Thereafter, while supplying high-purity nitrogen at a flow rate of 2 L / min, the temperature was raised at a rate of 2 ° C./min and calcined at 600 ° C. for 2 hours. 591 g of the fired product obtained was put into an SSA-S grade alumina boat, and the boat was placed in a muffle furnace. The inside of the muffle furnace was maintained at a reduced pressure for 60 minutes, and then returned to normal pressure with high-purity nitrogen (99.99%). This operation was repeated once in total. Thereafter, while supplying high-purity argon at a flow rate of 100 mL / min, the temperature was raised at a rate of 5 ° C./min, and baked at 1000 ° C. for 1 hour to obtain a baked product. The obtained fired product was pulverized with an airflow pulverizer and then classified with a precision air classifier to obtain a silicon-containing carbon material. Table 1 shows the chemical composition of the obtained silicon-containing carbon material and the ratio of sp2 peak area / sp3 peak area.

(Production of electrodes)
85 mass (weight)% of the silicon-containing carbon material and 5 mass (weight)% of carbon black were added and mixed for 15 minutes. Then, 5 mass (weight)% polyvinylidene fluoride-containing N-methyl-2-pyrrolidone solution was added so that the polyvinylidene fluoride was 10 mass (weight)% as a solid content, and an appropriate amount of N-methyl-2-pyrrolidone was further added. The mixture was mixed for 15 minutes to form a slurry. Then, the slurry was apply | coated on the copper foil roll by the doctor blade method. The electrode thus obtained was stored under vacuum at 85 ° C. for 12 hours or more to produce an electrode having a thickness of about 40 μm.

(Production and evaluation of secondary battery)
Metallic lithium was used for the electrode, counter electrode, and a mixed solvent of ethylene carbonate and diethyl carbonate 1: 1 (volume ratio) in which lithium hexafluorophosphate was dissolved at a rate of 1 mol / L as an electrolyte, and a polypropylene nonwoven fabric was used as a separator. A coin-type lithium secondary battery was produced. Moreover, the constant current charge / discharge measurement was performed at a current value of 0.4 mA. Table 2 shows the characteristics of the battery of Example 1.

[Example 2]
(Preparation of silicon-containing cured product)
Diphenylbis (dimethylvinylsiloxy) silane (Toray Dow Corning, RMS 312) 3.0 g (containing 14.06 mass (weight)% vinyl group), viscosity 20 mPa · s molecular chain both ends trimethylsiloxy group blocked methyl Hydrogen polysiloxane (content of silicon atom-bonded hydrogen atom = 1.58 mass (weight)%) 0.98 g (in the copolymer with respect to 1 mol of vinyl group in the diphenylbis (dimethylvinylsiloxy) silane) The crosslinkable composition was prepared by mixing 10 ppm of platinum as a platinum metal with a platinum catalyst of 1,3-divinyltetramethyldisiloxane complex platinum of platinum). Thereafter, the composition was cured at 150 ° C. in nitrogen to prepare a cured product.

(Preparation of silicon-containing carbon material)
3.7 g of the cured product was put into an SSA-S grade alumina boat, and the boat was placed in a degreasing furnace. Thereafter, the inside of the degreasing furnace was maintained at a reduced pressure for 10 minutes, and then returned to normal pressure with high-purity nitrogen (99.99%). This operation was repeated once in total. Thereafter, while supplying high-purity nitrogen at a flow rate of 2 L / min, the temperature was raised at a rate of 2 ° C./min and calcined at 600 ° C. for 2 hours. The obtained fired product was pulverized with a ball mill and classified with 300 mesh. The SSA-S grade alumina boat was charged with 2.2 g of the fired product obtained after pulverization and classification, and the boat was placed in a muffle furnace. The inside of the muffle furnace was maintained at a reduced pressure for 60 minutes, and then returned to normal pressure with high-purity nitrogen (99.99%). This operation was repeated once in total. Thereafter, while supplying high-purity argon at a flow rate of 100 mL / min, the temperature was increased at a rate of 5 ° C./min, and baked at 1000 ° C. for 1 hour to obtain a silicon-containing carbon material. Table 1 shows the chemical composition of the obtained silicon-containing carbon material and the ratio of sp2 peak area / sp3 peak area.

(Production of electrodes)
An electrode having a thickness of about 40 μm was produced in the same manner as in Example 1.

(Production and evaluation of secondary battery)
The constant current charge / discharge measurement was performed in the same manner as in Example 1 except that the constant current charge / discharge measurement was performed at a current value of 0.3 mA. Table 2 shows the characteristics of the battery of Example 2.

[Example 3]
(Preparation of silicon-containing cured product)
Example 1 was performed except that the composition was cured at 120 ° C. in nitrogen.

(Preparation of silicon-containing carbon material)
The cured product 1200 g was put into an SSA-S grade alumina boat, and the boat was placed in a degreasing furnace. Thereafter, the inside of the degreasing furnace was maintained at a reduced pressure for 10 minutes, and then returned to normal pressure with high-purity nitrogen (99.99%). This operation was repeated once in total. Thereafter, while supplying high-purity nitrogen at a flow rate of 2 L / min, the temperature was raised at a rate of 2 ° C./min and calcined at 600 ° C. for 2 hours. The obtained fired product was pulverized with an airflow pulverizer and then classified with a precision air classifier. A carbon container was charged with 800 g of the fired product obtained after pulverization and classification, and the container was placed in an oxynon furnace. Thereafter, the silicon-containing carbon material was obtained by firing at 1000 ° C. for 1 hour while supplying 4% by volume of hydrogen-containing high-purity nitrogen at a flow rate of 10 L / min. Table 1 shows the chemical composition of the obtained silicon-containing carbon material and the ratio of sp2 peak area / sp3 peak area.

(Production of electrodes)
An electrode having a thickness of about 40 μm was produced in the same manner as in Example 1.

(Production and evaluation of secondary battery)
The measurement was performed in the same manner as in Example 1 except that the constant current charge / discharge measurement was performed at a current value of 0.3 mA. Table 2 shows the characteristics of the battery of Example 3.

[Example 4]
(Preparation of silicon-containing cured product)
DVB570 (manufactured by Nippon Steel Chemical Co., Ltd., 57.0 mass (weight)% divinylbenzene and 38.9 mass (weight)% vinylethylbenzene are the main components, and the content of divinylbenzene in the main components is about 60 mass (weight). )%) To 28.45 g, the molecular chain both ends trimethylsiloxy group-blocked methyl hydrogen polysiloxane having a viscosity of 20 mPa · s (content of silicon atom-bonded hydrogen atoms = 1.58 mass (weight)%) 6.25 g The amount of silicon-bonded hydrogen atoms in this copolymer is about 0.3 mol per mol of vinyl group in DVB570) and platinum catalyst of 1,3-divinyltetramethyldisiloxane complex platinum as platinum metal A crosslinkable composition was prepared by mixing 10 ppm. Thereafter, the composition was cured at 150 ° C. in nitrogen to prepare a cured product.

(Preparation of silicon-containing carbon material)
20.28 g of the cured product was put into an SSA-S grade alumina boat, and the boat was placed in a degreasing furnace. Thereafter, the inside of the degreasing furnace was maintained at a reduced pressure for 10 minutes, and then returned to normal pressure with high-purity nitrogen (99.99%). This operation was repeated once in total. Thereafter, while supplying high-purity nitrogen at a flow rate of 2 L / min, the temperature was raised at a rate of 2 ° C./min and calcined at 600 ° C. for 2 hours. The obtained fired product was pulverized with a ball mill and classified with 300 mesh. 2.14 g of the fired product obtained after pulverization and classification was put into an SSA-S grade alumina boat, and the boat was placed in a muffle furnace. The inside of the muffle furnace was maintained at a reduced pressure for 60 minutes, and then returned to normal pressure with high-purity nitrogen (99.99%). This operation was repeated once in total. Thereafter, high-purity argon was supplied at a flow rate of 100 mL / min, the temperature was raised at a rate of 5 ° C./min, and baked at 1000 ° C. for 1 hour to obtain a silicon-containing carbon material. Table 1 shows the chemical composition of the silicon-containing carbon material and the ratio of sp2 peak area / sp3 peak area.

(Production of electrodes)
It carried out similarly to Example 1 and produced the electrode of thickness about 50 micrometers.

(Production and evaluation of secondary battery)
The measurement was performed in the same manner as in Example 1 except that the constant current charge / discharge measurement was performed at a current value of 0.4 mA. Table 2 shows the characteristics of the battery of Example 4.

[Example 5]
(Preparation of silicon-containing cured product)
DVB570 (manufactured by Nippon Steel Chemical Co., Ltd., 57.0 mass (weight)% divinylbenzene and 38.9 mass (weight)% vinylethylbenzene are the main components, and the content of divinylbenzene in the main components is about 60 mass (weight). )%) 8.54 g, viscosity 20 mPa · s molecular chain both ends trimethylsiloxy group-blocked methyl hydrogen polysiloxane (content of silicon-bonded hydrogen atoms = 1.58 mass (weight)%) 12.50 g (above Mixing 10 ppm of platinum metal with 1,3-divinyltetramethyldisiloxane complex platinum catalyst of platinum and platinum catalyst in an amount of about 2 mol of silicon-bonded hydrogen atoms in this copolymer with respect to 1 mol of vinyl group in DVB570 Thus, a crosslinkable composition was prepared. Thereafter, the composition was cured at 150 ° C. in nitrogen to prepare a cured product.

(Preparation of silicon-containing carbon material)
20.21 g of the cured product was put into an SSA-S grade alumina boat, and the boat was placed in a degreasing furnace. Thereafter, the inside of the degreasing furnace was maintained at a reduced pressure for 10 minutes, and then returned to normal pressure with high-purity nitrogen (99.99%). This operation was repeated once in total. Thereafter, while supplying high-purity nitrogen at a flow rate of 2 L / min, the temperature was raised at a rate of 2 ° C./min and calcined at 600 ° C. for 2 hours. The obtained fired product was pulverized with a ball mill and classified with 300 mesh. 1.93 g of the fired product obtained after pulverization and classification was put into an SSA-S grade alumina boat, and the boat was placed in a muffle furnace. The inside of the muffle furnace was maintained at a reduced pressure for 60 minutes, and then returned to normal pressure with high-purity nitrogen (99.99%). This operation was repeated once in total. Thereafter, while supplying high-purity argon at a flow rate of 100 mL / min, the temperature was increased at a rate of 5 ° C./min, and baked at 1000 ° C. for 1 hour to obtain a silicon-containing carbon material. Table 1 shows the chemical composition of the silicon-containing carbon material and the ratio of sp2 peak area / sp3 peak area.

(Production of electrodes)
In the same manner as in Example 1, an electrode having a thickness of about 45 μm was produced.

(Production and evaluation of secondary battery)
The measurement was performed in the same manner as in Example 1 except that the constant current charge / discharge measurement was performed at a current value of 0.4 mA. Table 2 shows the characteristics of the battery of Example 5.

[Comparative Example 1]
(Preparation of silicon-containing cured product)
DVB570 (manufactured by Nippon Steel Chemical Co., Ltd., 57.0% by weight of divinylbenzene and 38.9% by weight of vinylethylbenzene are the main components, and the content of divinylbenzene in the main component is about 60% by weight) In 15.49 g, 2.65 g (content of silicon atom-bonded hydrogen atom = 1.58 mass (weight)%) of the molecular chain both ends trimethylsiloxy group-blocked methylhydrogenpolysiloxane having a viscosity of 20 mPa · s (in the DVB570) The amount of silicon atom-bonded hydrogen atoms in the copolymer is about 0.25 mol per mol of vinyl group) and platinum catalyst of 1,3-divinyltetramethyldisiloxane complex platinum in platinum is mixed at 10 ppm as platinum metal. Thus, a crosslinkable composition was prepared. Thereafter, the composition was cured at 120 ° C. in nitrogen to prepare a cured product.

(Preparation of silicon-containing carbon material)
4 g of the cured product was put into a carbon container, and the container was placed in oxynon. Then, it baked over 1 hour at 1000 ° C. while supplying high purity nitrogen containing 4% hydrogen at a flow rate of 10 L / min. The obtained fired product was pulverized with a ball mill and classified with 300 mesh to obtain a silicon-containing carbon material. Table 1 shows the chemical composition of the obtained silicon-containing carbon material and the ratio of sp2 peak area / sp3 peak area.

(Production of electrodes)
An electrode having a thickness of about 40 μm was produced in the same manner as in Example 1.

(Production and evaluation of secondary battery)
The measurement was performed in the same manner as in Example 1 except that the constant current charge / discharge measurement was performed at a current value of 0.4 mA. Table 3 shows the characteristics of the battery of Comparative Example 1.

[Comparative Example 2]
(Preparation of silicon-containing cured product)
10 g of tetramethyldivinyldisiloxane (manufactured by Toray Dow Corning Co., Ltd.), methylhydrogenpolysiloxane blocked with trimethylsiloxy group-blocked methylhydrogenpolysiloxane having a viscosity of 20 mPa · s (content of silicon-bonded hydrogen atoms = 1.58 mass (weight) )%) 6.7 g (amount in which the silicon-bonded hydrogen atom in the copolymer is about 1 mol per 1 mol of vinyl group in the tetramethyldivinyldisiloxane) and platinum 1,3-divinyltetra A crosslinkable composition was prepared by mixing 10 ppm of a methyldisiloxane complex platinum catalyst as platinum metal. Thereafter, the composition was cured at 120 ° C. in nitrogen to prepare a cured product.

(Preparation of silicon-containing carbon material)
4.0 g of the cured product was put into an SSA-S grade alumina boat, and the boat was placed in a degreasing furnace. Thereafter, the inside of the degreasing furnace was maintained at a reduced pressure for 10 minutes, and then returned to normal pressure with high-purity nitrogen (99.99%). This operation was repeated once in total. Thereafter, while supplying high-purity nitrogen at a flow rate of 2 L / min, the temperature was raised at a rate of 2 ° C./min and calcined at 600 ° C. for 2 hours. The obtained fired product was pulverized with a ball mill and classified with 300 mesh. A carbon container was charged with 2.0 g of the fired product obtained after pulverization and classification, and the container was placed in an oxynon furnace. Then, while supplying 4% by volume of hydrogen-containing high-purity nitrogen at a flow rate of 10 L / min, firing was performed at 1100 ° C. for 1 hour to obtain a silicon-containing carbon material. Table 1 shows the chemical composition of the silicon-containing carbon material and the ratio of sp2 peak area / sp3 peak area.

(Production of electrodes)
An electrode having a thickness of about 40 μm was produced in the same manner as in Example 1.

(Production and evaluation of secondary battery)
The measurement was performed in the same manner as in Example 1 except that the constant current charge / discharge measurement was performed at a current value of 0.4 mA. Table 3 shows the characteristics of the battery of Comparative Example 2.

[Comparative Example 3]
(Preparation of silicon-containing cured product)
17.2 g of tetramethyltetravinylpolysiloxane (manufactured by Toray Dow Corning Co., Ltd.) and methylhydrogenpolysiloxane blocked with trimethylsiloxy group-blocked methylhydrogenpolysiloxane having a viscosity of 20 mPa · s (content of silicon-bonded hydrogen atoms = 1.58) 12.5 g (mass (weight)%) (amount of silicon atom-bonded hydrogen atoms in the copolymer to be about 1 mol with respect to 1 mol of vinyl groups in the tetramethyldivinyldisiloxane) and 1,3 of platinum A crosslinkable composition was prepared by mixing 10 ppm of divinyltetramethyldisiloxane complex platinum catalyst as platinum metal. Thereafter, the composition was cured at 120 ° C. in nitrogen to prepare a cured product.

(Preparation of silicon-containing carbon material)
28.78 g of the cured product was put into an SSA-S grade alumina boat, and the boat was placed in a degreasing furnace. Thereafter, the inside of the degreasing furnace was maintained at a reduced pressure for 10 minutes, and then returned to normal pressure with high-purity nitrogen (99.99%). This operation was repeated once in total. Thereafter, while supplying high-purity nitrogen at a flow rate of 2 L / min, the temperature was raised at a rate of 2 ° C./min and calcined at 600 ° C. for 2 hours. The obtained fired product was pulverized with a ball mill and classified with 300 mesh. 1.59 g of the fired product obtained after pulverization and classification was put into an SSA-S grade alumina boat, and the boat was placed in a muffle furnace. The inside of the muffle furnace was maintained at a reduced pressure for 60 minutes, and then returned to normal pressure with high-purity nitrogen (99.99%). This operation was repeated once in total. Thereafter, while supplying high-purity argon at a flow rate of 100 mL / min, the temperature was increased at a rate of 5 ° C./min, and baked at 1000 ° C. for 1 hour to obtain a silicon-containing carbon material. Table 1 shows the chemical composition of the silicon-containing carbon material and the ratio of sp2 peak area / sp3 peak area.

(Production of electrodes)
An electrode having a thickness of about 40 μm was produced in the same manner as in Example 1.

(Production and evaluation of secondary battery)
The measurement was performed in the same manner as in Example 1 except that the constant current charge / discharge measurement was performed at a current value of 0.4 mA. Table 3 shows the characteristics of the battery of Comparative Example 3.

* In the table, “sp2 carbon / sp3 carbon” means that the peak area of 99-160 ppm in the ¹³ C MAS NMR spectrum of each example is derived from sp2 carbon, and the peak area of 11-49 ppm is derived from sp3 carbon. It means the ratio of the peak area derived from the sp2 carbon atom / the peak area derived from the sp3 carbon atom obtained from the peak area of each peak obtained by an approximation method using a Gaussian waveform.

1: Case, 2: Gasket, 3: Washer, 4: SUS plate, 5: Current collector, 6: Negative electrode, 7: Separator, 8: Positive electrode, 9, 9 ': Current collector, 10: Sealing plate

Claims (23)

1. Composition formula: SiO _x C _y (wherein x is 0.8 to 1.7, y is 1.4 to 7.5), and ¹³ C MAS NMR spectrum (sp2 carbon atom-derived peak area / sp3 A silicon-containing carbon-based composite material having a carbon atom-derived peak area ratio of 1.6 to 46.0.
2. The composite according to claim 1, which is obtained by heat-treating (A) a crosslinkable group-containing organic compound and (B) a cured product obtained by crosslinking reaction of a silicon-containing compound capable of crosslinking the crosslinkable group-containing organic compound. material.
3. The composite material according to claim 2, wherein the heat treatment is performed at 300 to 1500 ° C in an inert gas or in a vacuum.
4. The composite material according to claim 2 or 3, wherein the crosslinkable group is selected from the group consisting of an aliphatic unsaturated group, an epoxy group, an acrylic group, a methacryl group, an amino group, a hydroxyl group, a mercapto group, and a halogenated alkyl group. .
5. The composite material according to claim 2, wherein the component (A) has an aromatic group.
6. The component (A) has the general formula:
   

   

   The composite material according to claim 5, wherein R ¹ is a crosslinkable group, x is an integer of 1 or more, and R ² is an x-valent aromatic group. .
7. The composite material according to claim 2, wherein the component (A) contains a silicon atom.
8. The composite material according to claim 7, wherein the component (A) is siloxane, silane, silazane, carbosilane, or a mixture thereof.
9. The siloxane has an average unit formula:
   

   

   (In the formula, each R ³ independently represents a crosslinkable group, a monovalent substituted or unsubstituted saturated aliphatic hydrocarbon group or aromatic hydrocarbon group having 1 to 20 carbon atoms, an alkoxy group, a hydrogen atom, or A, b, c and d are each a number satisfying 0 or more and 1 or less and satisfying a + b + c + d = 1, provided that a, b and c are not all 0; The composite material according to claim 8, wherein at least one of R ^{3 in} the molecule is a crosslinkable group.
10. The composite material according to any one of claims 2 to 9, wherein the component (B) is siloxane, silane, silazane, carbosilane, or a mixture thereof.
11. The siloxane has an average unit formula:
    

    

    (In the formula, each R ⁷ independently represents a monovalent hydrocarbon group, a hydrogen atom, a halogen atom, an epoxy group-containing organic group, an acrylic group-containing organic group, a methacryl group-containing organic group, an amino group-containing organic group, or a mercapto group. A group-containing organic group, an alkoxy group or a hydroxy group; a, b, c and d are each a number satisfying 0 or more and 1 or less and satisfying a + b + c + d = 1, provided that both a, b and c are The composite material according to claim 10, wherein the composite material is not represented by 0).
12. The composite material according to claim 2, wherein the crosslinking reaction is an addition reaction, a condensation reaction, a ring-opening reaction, or a radical reaction.
13. The cured product is obtained by a hydrosilylation reaction between the component (A) having an aliphatic unsaturated group and the component (B) having a silicon atom-bonded hydrogen atom. The composite material described in 1.
14. The cured product is obtained by a hydrosilylation reaction between the component (A) having a silicon atom-bonded hydrogen atom and the component (B) having an aliphatic unsaturated group. The composite material described in 1.
15. The cured product obtained by radical reaction between the component (A) having an aliphatic unsaturated group and the component (B) having an aliphatic unsaturated group, an acrylic group, a methacryl group or a silicon atom-bonded hydrogen atom The composite material according to claim 2, wherein
16. The cured product was obtained by a radical reaction between the component (A) having an aliphatic unsaturated group, acrylic group, methacryl group, or silicon-bonded hydrogen atom and the component (B) having an aliphatic unsaturated group. The composite material according to claim 2, which is a material.
17. The composite material according to any one of claims 1 to 16, which is in an amorphous form.
18. The composite material according to any one of claims 1 to 17, which is in the form of particles having an average particle diameter of 5 nm to 50 µm.
19. An electrode active material comprising the composite material according to claim 1.
20. 20. The electrode active material according to claim 19, which is a particle having an average particle diameter of 1 to 50 μm.
21. An electrode comprising the electrode active material according to claim 19 or 20.
22. An electricity storage device comprising the electrode according to claim 21.
23. The electricity storage device according to claim 22, which is a lithium or lithium ion secondary battery.

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