TW201311559A - Silicon-containing carbon-based composite material in which fine lithium-coated silicon metal or silicon alloy particles are dispersed - Google Patents

Abstract

A composite material wherein fine silicon metal or silicon alloy particles, each of which has a lithium-containing layer on the surface, are dispersed in a silicon-containing carbon-based composite material. The composite material can be produced by a production method that comprises: a first step wherein fine lithium-coated silicon metal or silicon alloy particles are obtained by forming a lithium-containing layer on the surface of each silicon metal or silicon alloy particle; a second step wherein the fine lithium-coated silicon metal or silicon alloy particles are mixed with (A) a crosslinkable group-containing organic compound and (B) a silicon-containing compound that is crosslinkable with the crosslinkable group-containing organic compound, so that a cured product is obtained by a crosslinking reaction between the component (A) and the component (B); and a third step wherein the cured product is subjected to a heat treatment. The composite material is suitable for electrodes of electricity storage devices, especially electrodes of lithium or lithium ion secondary batteries.

Description

Cerium-containing carbon composite material in which lithium-coated metal ruthenium or ruthenium alloy fine powder is dispersed

The present invention relates to a cerium-containing carbon composite material, an electrode active material containing the composite material, an electrode including the active material, and a power storage device including the electrode.

A power storage device, particularly a lithium or lithium ion secondary battery, is being studied as one of high energy density secondary batteries. A ruthenium-containing carbon material obtained by thermally decomposing a ruthenium polymer is often reported as a negative electrode material of such a lithium ion secondary battery. For example, Japanese Patent Publication No. Hei 10-97853, and Solid State Ionics, 122, 71 (1999) describe the production of a battery that can be used for a large capacitor by using polydecane and coal tar pitch as precursors. Material. Further, it is described in Japanese Patent Laid-Open No. Hei 10-74506, Japanese Patent Application Laid-Open No. Hei 10-275617, No. 2004-273377, and J. Electrochem. Soc., 144, 2410 (1997). A battery having a large capacitance 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 or lithium ion secondary battery including an electrode including such a ruthenium-containing carbon material has a high reversible capacitance, but has a low initial charge and discharge efficiency and is insufficient in practical performance in terms of charge and discharge cycle characteristics.

On the other hand, research is being conducted in the industry to improve the cycle characteristics of negative electrode active materials using antimony or tin. For example, Japanese Patent Publication No. Hei 11-96993 discloses that an inorganic solid electrolyte containing lithium is applied to the surface of a negative electrode active material such as graphite, ruthenium or tin-based oxide to reduce the initial irreversible capacitance. In the surface of a negative electrode having a negative electrode active material containing ruthenium or tin, a layer containing LiF ⁺ and Li ₂ OH ⁺ is formed on the surface of the negative electrode, thereby suppressing decomposition reaction of the electrolytic solution. Improve cycle characteristics. Japanese Laid-Open Patent Publication No. 2007-66726 discloses that heat treatment is performed by disposing a mixture layer containing an active material powder containing a niobium or tantalum alloy, a binder, and lithium oxide on a current collector, thereby suppressing high temperature. The gas at the time of storage is generated, and the charge and discharge cycle characteristics are improved. A composite in which a powder of a metal ruthenium or a metal ruthenium alloy is dispersed in a ruthenium-containing carbon composite powder is described in Japanese Laid-Open Patent Publication No. 2005-310759.

However, the charge capacity of the lithium or lithium ion secondary battery including the electrode including the composite as the active material, the charge and discharge efficiency, or the retention rate of the capacitor during the repeated charge and discharge are insufficient, and the practical level has not yet been reached.

[Previous Technical Literature] [Patent Literature]

[Patent Document 1] Japanese Patent Laid-Open No. Hei 10-97853

[Patent Document 2] Japanese Patent Laid-Open No. Hei 10-74506

[Patent Document 3] Japanese Patent Laid-Open No. Hei 10-275617

[Patent Document 4] Japanese Patent Laid-Open Publication No. 2004-273377

[Patent Document 5] Japanese Patent Laid-Open No. Hei 11-96993

[Patent Document 6] Japanese Patent Laid-Open Publication No. 2006-179305

[Patent Document 7] Japanese Patent Laid-Open Publication No. 2007-66726

[Patent Document 8] Japanese Patent Laid-Open Publication No. 2005-310759

[Non-patent literature]

[Non-Patent Document 1] Solid State Ionics, 122, 71 (1999)

[Non-Patent Document 2] J. Electrochem. Soc., 144, 2410 (1997)

An object of the present invention is to provide a composite material preferably used for an electric storage device, particularly an electrode of a lithium or lithium ion secondary battery, an electrode active material containing the composite material, an electrode using the active material, and the like The storage device of the electrode.

The object of the present invention is achieved by a composite material containing a metal ruthenium or a ruthenium alloy fine powder having a lithium-containing layer dispersed on a surface of a ruthenium-containing carbon composite material.

The average particle diameter of the above metal ruthenium or iridium alloy fine powder is preferably from 10 nm to 10 μm.

The lithium content is preferably from 0.1 to 10% by mass based on the metal ruthenium or ruthenium alloy fine powder having a lithium-containing layer. When the lithium content is within this range, good conductivity and battery capacity can be maintained.

The above composite material can be obtained by the following steps: a first step of forming a lithium-containing layer on the surface of the metal ruthenium or iridium alloy fine powder to obtain a lithium-coated metal ruthenium or ruthenium alloy fine powder; and a second step of coating the above lithium a metal ruthenium or iridium alloy fine powder and (A) a crosslinkable group-containing organic compound and (B) a ruthenium-containing compound crosslinkable with the above crosslinkable group-containing organic compound, and the (A) component and the (B) component are mixed A crosslinking reaction is carried out to obtain a cured product; and a third step of heat-treating the cured product. Therefore, the present invention has the following state The method for producing a composite material, comprising: a first step of forming a lithium-containing layer on a surface of a metal ruthenium or iridium alloy fine powder to obtain a lithium-coated metal ruthenium or ruthenium alloy fine powder; and a second step, which a lithium-coated metal ruthenium or ruthenium alloy fine powder is mixed with (A) a crosslinkable group-containing organic compound and (B) a ruthenium-containing compound capable of crosslinking the above crosslinkable group-containing organic compound, and (A) component and (B) The component is subjected to a crosslinking reaction to obtain a cured product; and a third step of heat-treating the cured product.

Further, the composite material of the present invention can be obtained by the following steps: a first step of forming a lithium-containing layer on the surface of the metal ruthenium or iridium alloy fine powder to obtain a lithium-coated metal ruthenium or iridium alloy fine powder; (A) a crosslinkable group-containing organic compound and (B) a cross-linking reaction of a ruthenium-containing compound capable of crosslinking the above-mentioned crosslinkable group-containing organic compound to obtain a cured product; and a third step of providing a mechanical energy side The lithium-coated metal ruthenium or iridium alloy fine powder and the cured product are mixed and composited, and heat-treated.

Further, the composite material of the present invention can be obtained by the following steps: a first step of forming a lithium-containing layer on the surface of the metal ruthenium or iridium alloy fine powder to obtain a lithium-coated metal ruthenium or iridium alloy fine powder; (A) a crosslinkable group-containing organic compound and (B) a crosslinkable reaction of a ruthenium-containing compound capable of crosslinking the above-mentioned crosslinkable group-containing organic compound to obtain a cured product; and a third step of heating the cured product The ruthenium-containing carbon-based composite material is obtained by the treatment; and in the fourth step, the lithium-coated metal ruthenium or iridium alloy fine powder and the ruthenium-containing carbon-based composite material are mixed and composited while providing mechanical energy.

As a step of obtaining a lithium-coated metal ruthenium or ruthenium alloy fine powder, exemplified A method in which a metal ruthenium or iridium alloy fine powder is mixed with a lithium or lithium compound and heat-treated.

Examples of the lithium compound include LiOH (LiOH.H ₂ O), Li ₂ O, LiR (R is exemplified as an alkyl group, an organic decyloxy group), LiOR (R is the same as described above), LiCO ₃ , LiNO ₃ , and LiX ( X is a halogen atom such as fluorine or chlorine), a Li complex compound, and R _n Si(OLi) _4-n (R is the same as above, and n is a number of 1 to 3).

The electrode active material of the present invention comprises the above composite material.

The electrode of the present invention contains the above electrode active material. The above electrode can be preferably used for a power storage device, particularly a lithium or lithium ion secondary battery.

The composite material of the present invention has a high initial discharge capacitance, and the initial irreversible capacitance (the difference between the primary charging capacitance and the initial discharge capacitance) is lowered, so that it is preferably used for an electric storage device, particularly an electrode of a lithium or lithium ion secondary battery. . Further, the composite material of the present invention can be produced by a simple manufacturing process using inexpensive raw materials.

The electrode active material of the present invention is preferably used for an electrode of an electricity storage device, particularly a lithium or lithium ion secondary battery. Further, the electrode of the present invention can impart a high initial charge and discharge capacitance and a stable charge and discharge cycle characteristic to the battery. Thereby, the power storage device of the present invention can have a high initial charge and discharge capacitance and stable charge and discharge cycle characteristics.

(composite material)

The composite material of the present invention can be obtained by the following steps: a first step of forming a lithium-containing layer on the surface of a metal ruthenium or iridium alloy fine powder to obtain a lithium-coated gold a bismuth or bismuth alloy fine powder; a second step of the above lithium-coated metal ruthenium or iridium alloy fine powder and (A) a crosslinkable group-containing organic compound and (B) crosslinkable of the above crosslinkable group-containing organic compound The cerium-containing compound is mixed, and the component (A) and the component (B) are cross-linked to obtain a cured product; and in the third step, the cured product is subjected to heat treatment.

Moreover, the method for producing the composite material of the present invention is not limited to the above method, and the composite material of the present invention can be obtained by the following steps: a first step of forming a lithium-containing layer on the surface of the metal ruthenium or iridium alloy fine powder. Obtaining a lithium-coated metal ruthenium or ruthenium alloy fine powder; and a second step of crosslinking (A) a crosslinkable group-containing organic compound and (B) a ruthenium-containing compound capable of crosslinking the above crosslinkable group-containing organic compound And obtaining a cured product; and a third step of mixing and compositing the lithium-coated metal ruthenium or ruthenium alloy fine powder and the cured product while providing mechanical energy, and performing heat treatment.

Further, it may be obtained by the following steps: forming a lithium-containing layer on the surface of the metal ruthenium or iridium alloy fine powder to obtain a lithium-coated metal ruthenium or ruthenium alloy fine powder; and a second step of (A) a crosslinkable group-containing organic compound and (B) a ruthenium-containing compound capable of crosslinking the above-mentioned crosslinkable group-containing organic compound to carry out a crosslinking reaction to obtain a cured product; and a third step of heat-treating the cured product to obtain a cured product The ruthenium carbon composite material; and the fourth step of mixing and compositing the lithium-coated metal ruthenium or iridium alloy fine powder and the ruthenium-containing carbon composite material while providing mechanical energy.

As the fine metal powder of the metal ruthenium or iridium alloy, a powder obtained by pulverizing a high-purity metal ruthenium for a semiconductor or a ruthenium metal for chemical use, and pulverizing the ruthenium metal obtained by pulverizing the ruthenium metal by a rapid cooling method may be used. The amorphous cerium metal powder obtained by thermal decomposition, the metal cerium or cerium alloy fine powder prepared by reduction of chlorodecane gas.

Examples of the niobium alloy fine powder include an alloy of niobium and iron, copper, aluminum, manganese, and magnesium, and more specifically, SiAl, SiMn, SiMg, SiGe, Al-Si-Mg, and Al-Si-Mn are exemplified. Al-Si-Zn, Al-Si-Cu, Ni-Si-Al, Au _1-x Si _x , CaSi, CaBaSi, Fe-Si-W.

Examples of the lithium compound include LiOH (LiOH.H ₂ O), Li ₂ O, LiR (R is exemplified as an alkyl group, an organic decyloxy group), LiOR (R is the same as described above), LiCO ₃ , LiNO ₃ , and LiX ( X is a halogen atom such as fluorine or chlorine), a Li complex compound, and R _n Si(OLi) _4-n (R is the same as above, and n is a number of 1 to 3).

In the case of using a metal ruthenium powder having a ruthenium oxide film, it is preferred to form a lithium-containing layer using Li metal or surface-treated Li metal.

In the first step, for example, a metal ruthenium or ruthenium alloy fine powder having an average particle diameter of 10 nm to 10 μm is added to a solution obtained by dissolving a lithium compound in a solvent, and is dried under a nitrogen atmosphere and then dried. Thereby, a lithium-coated metal ruthenium or ruthenium alloy fine powder can be obtained. As another method, a lithium compound is added to a metal ruthenium or ruthenium alloy fine powder, and while stirring is provided while providing mechanical energy, a lithium-coated metal ruthenium or ruthenium alloy fine powder can also be obtained. The pulverizing apparatus, the mixing apparatus, and the surface treatment apparatus used in the mixing and stirring are not particularly limited. The pulverization, mixing or surface treatment may be a dry method or a wet method.

Examples of the pulverizing apparatus include those which are pulverized by pressure or striking force: for example, a Jaw Crusher, a Gyratory Crusher, a roll crusher, a roll mill, and an automatic machine. Milk thistle; A device for smashing a striking plate around a rotor that rotates at a high speed and pulverizing the workpiece by a shear force generated by a rotor and a striking plate: for example, a hammer mill, an impact crusher, a pin mill, an atomizer, a pulverizer ( Pulverizer, etc.; a device that presses a roller or a ball on a ring and rotates to grind and pulverize the treatment: for example, a ring roller mill, a ring ball mill, a centrifugal roller mill, a centrifugal ball mill (Ball Bearing Mill), An smashing device having a cylindrical pulverization chamber and pulverizing the treatment by a ball or a rod in the pulverization chamber as a pulverization medium and rotating or vibrating thereof: for example, a pot mill, a ball mill a vibrating mill, a planetary ball mill, etc.; having a cylindrical pulverizing chamber in which a pulverizing medium such as a ball or a bead is placed by a dish or a ring stirring mechanism inserted in the medium a device for pulverizing and treating a workpiece by shearing or rubbing: for example, a tower mill, an attritor, a sand mill, etc.; and a medium such as high-pressure air sprayed from a nozzle as a super high-speed jet body collides with particles, By particles The blow means are comminuted treated: for example, a jet mill and the like.

Examples of the mixing device include a mixer having a stirring shaft inside the mixing tank and a stirring blade attached to the shaft to mix the powder: for example, a super mixer (Super Mixer) or a high speed mixer (High- Speed Mixer), Henschel mixer, etc.; a continuous mixer that includes a vertical cylinder with a powder inlet and a spindle with a mixing blade, the spindle is supported by the upper bearing and the discharge side is vacant: for example Flexomix a mixer or the like; a continuous mixer that feeds a raw material on a disk having a stirring needle and rotates the disk at a high speed to perform mixing by shearing: for example, a jet jet mixer, a spiral needle Mixer (Spiral Pin Mixer) and so on.

Examples of the surface treatment device include a hybridizer manufactured by Nara Machinery Co., Ltd., a mechanofusion manufactured by Hosokawa Micron Co., Ltd., a nobilta, and the like.

The mixing and stirring method and apparatus described above can be similarly used in the step of mixing and compositing a lithium-coated metal ruthenium or ruthenium alloy fine powder with a cured product or a ruthenium-containing carbon composite material while providing mechanical energy.

The lithium-coated metal ruthenium or iridium alloy fine powder obtained as described above is preferably further subjected to heat treatment. The heat treatment temperature is not particularly limited, but is usually 200 ° C to 800 ° C.

The lithium-containing layer on the surface of the above-mentioned metal ruthenium or iridium alloy fine powder is preferably from 5 nm to 500 nm. Further, in order to maintain good conductivity and battery capacity, the lithium atom content is preferably from 0.1 to 10% by mass based on the total of the lithium-coated metal ruthenium or ruthenium alloy fine powder. Such a lithium-coated metal ruthenium or ruthenium alloy fine powder can be adjusted, for example, by a lithium atom to a lithium-coated metal ruthenium or iridium by a step of forming a lithium-containing layer on the surface of the metal ruthenium or iridium alloy fine powder. The alloy fine powder is obtained in an amount of 0.1 to 10% by mass in total.

In the step of forming a lithium-containing layer on the surface of the metal ruthenium or iridium alloy fine powder, a lithium-containing layer bonded to the ruthenium atom can be obtained by the following reaction.

2Si+2LiOH=2≡SiOLi+H ₂

The crosslinkable group in the component (A) is not particularly limited as long as it is a crosslinkable group, and examples thereof include an aliphatic unsaturated group, an epoxy group, an acryl group, a methacryl group, and an amine. A base, a hydroxyl group, a thiol group or a halogenated alkyl group. Specific examples of the aliphatic unsaturated group include a vinyl group, a propylene group, and the like. An alkenyl group such as a butenyl group, a pentenyl group or a hexenyl group; an alkynyl group such as an ethyl group, a propynyl group or a pentynyl group. Further, specific examples of the epoxy group include glycidyl group, glycidoxy group, epoxycyclohexyl group, 3-glycidoxypropyl group, and 2-(3,4-epoxycyclohexyl)ethyl group. . Further, specific examples of the acrylonitrile group include 3-propenyloxypropyl group. Further, specific examples of the methacryl oxime group include 3-methacryloxypropyl group. Further, specific examples of the amine group include 3-aminopropyl group and N-(2-aminoethyl)-3-aminopropyl group. Specific examples of the hydroxyl group include a hydroxyalkyl group such as a hydroxyethyl group and a hydroxypropyl group; and a hydroxyaryl group such as a hydroxyphenyl group. As the thiol group, specifically, a 3-mercaptopropyl group is exemplified. As the halogenated alkyl group, specifically, a 3-chloropropyl group is exemplified.

Further, 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, and is preferably at least 15% by mass, and more preferably at least 30% by mass, in terms of excellent crosslinkability.

The above component (A) may contain no ruthenium atom or may contain a ruthenium atom.

The component (A) which does not contain a ruthenium atom is preferably an organic compound having at least one aromatic ring in the molecule from the viewpoint of facilitating the formation of a graphene structure or the like, which is excellent in carbonization efficiency by heat.

Specific examples of such a component (A) include an aliphatic hydrocarbon compound having no cross-linking group at the terminal of the molecular chain and/or a side chain of the molecular chain, and a molecular group at the end of the molecular chain and/or molecular chain. An aliphatic hydrocarbon compound having no cross-linking group and having a hetero atom other than a carbon atom such as a nitrogen atom, an oxygen atom or a boron atom in the molecular chain, and having crosslinkability in the molecule An aromatic hydrocarbon compound containing no ruthenium atom, and a halogen-free cyclic compound having a cross-linking group in a molecule and further having a hetero atom other than a carbon atom such as a nitrogen atom, an oxygen atom or a boron atom.

Specific examples of the aliphatic hydrocarbon compound include a compound represented by the following formula: R ¹ -(CH ₂ ) _m -R ¹

CH ₃ -(CH ₂ ) _m -(CHR ¹ ) _n -CH ₃

CH ₃ -(CH ₂ 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

(wherein R ¹ is a crosslinkable group, and examples thereof include an aliphatic unsaturated group, an epoxy group, an acryl fluorenyl group, a methacryl fluorenyl group, an amine group, a hydroxyl group, a decyl group, or a halogenated alkyl group, specifically In the formula, m and n are each an integer of 1 or more, and x is an integer of 1 or more.

In addition, specific examples of the aromatic hydrocarbon compound include (R ¹ ) _x R ² wherein R ¹ is a crosslinkable group, and the same groups as described above are exemplified. Further, in the formula, x is an integer of 1 or more. Further, 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 specifically, the following group is exemplified.

Specific examples of such an aromatic hydrocarbon compound include α- or β-methylstyrene, α- or β-ethylstyrene, methoxystyrene, phenylstyrene, chlorostyrene, and o , m- or p-methyl styrene, ethyl styrene, methyl decyl styrene, hydroxy styrene, cyanostyrene, nitrostyrene, amino styrene, carboxy styrene, sulfomethoxy styrene Sodium styrene sulfonate, vinyl pyridine, vinyl thiophene, vinyl pyrrolidone, vinyl naphthalene, vinyl anthracene, vinyl biphenyl.

In the formula, when x is 2, R ² represents a divalent aromatic group, and specifically, the following group is exemplified.

Specific examples of such an aromatic hydrocarbon compound include divinylbenzene, divinylbiphenyl, vinylbenzyl chloride, divinylpyridine, divinylthiophene, divinylpyrrolidone, and divinylene. Naphthalene, divinyl Toluene, divinylethylbenzene, divinyl fluorene. The aromatic hydrocarbon compound is preferably divinylbenzene in terms of excellent thermal decomposition properties of the obtained cured product.

Further, in the formula, when x is 3, R ² represents a trivalent aromatic group, and specifically, the following group is exemplified.

Specific examples of such an aromatic hydrocarbon compound include trivinylbenzene and trivinylnaphthalene.

In addition, as the aromatic compound having a hetero atom, an aromatic compound represented by the following formula is specifically exemplified.

In the formula, R ¹ is a crosslinkable group, and the same groups as described above are exemplified.

Further, specific examples of the cyclic compound having a hetero atom include a cyclic compound represented by the following formula.

[Chemical 6] In the formula, R ¹ is a crosslinkable group, and the same groups as described above are exemplified.

The component (A) containing a ruthenium atom is not particularly limited as long as it has a crosslinkable group, and examples thereof include a monomer, an oligomer or a polymer containing a ruthenium atom. For example, a decane containing a structural unit characterized by a 矽-矽 bond, a decazane containing a structural unit characterized by a 矽-nitrogen-矽 bond, and a ruthenium-oxygen-oxime bond are included. a structural unit of a decane, a carbon decane comprising a structural unit having a fluorene-carbon-hydrazine bond, and a mixture thereof.

As the decane of the above (A) component, for example, an average unit formula: R ³ ₄ Si or an average unit formula: (R ³ ₃ Si) _a (R ³ ₂ Si) _b (R ³ Si) _c (Si) _d ( In the formula, R ³ each independently represents the above crosslinkable group, a saturated aliphatic hydrocarbon group or an aromatic hydrocarbon group, an alkoxy group, a hydrogen atom or a halogen atom having a carbon number of 1 to 20, which is substituted or unsubstituted, a And b, c and d represent 0 or a positive number, wherein a+b+c+d=1, at least one of R ³ in one molecule, preferably both of which are represented by the above-mentioned crosslinkable group).

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

As the alkyl group, a C ₁ - C ₁₂ alkyl group is preferred, and a C ₁ - C ₆ alkyl group is more preferred. The alkyl group is preferably a linear or branched alkyl group, a cycloalkyl group, or a cycloalkyl group (containing a linear or branched alkyl group (preferably a methylene group, a pendant ethyl group, etc., C ₁ -C _{6 )} Any of an alkyl group having a combination of an alkyl group and a carbocyclic ring (preferably a C ₃ - C ₈ ring).

The linear or branched alkyl group is preferably a linear or branched C ₁ -C ₆ alkyl group, and examples thereof include a methyl group, an ethyl group, a n-propyl group, an isopropyl group, a butyl group, and a third group. Butyl group, pentyl group, hexyl group and the like are particularly preferably a methyl group.

The cycloalkyl group is preferably a C ₄ -C ₆ alkyl group, and examples thereof include a cyclobutyl group, a cyclopentyl group, and a cyclohexyl group, and a cyclopentyl group and a cyclohexyl group are preferred.

The aryl group is preferably a C ₆ -C ₁₂ aryl group, and examples thereof include a phenyl group, a naphthyl group, and a tolyl group.

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

The hydrocarbon group may have a substituent, and examples of the substituent include a halogen such as a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom; a hydroxyl group; a methoxy group, an ethoxy group, a n-propoxy group, an isopropoxy group, or the like. C ₁ -C ₆ alkoxy; amine; guanamine; nitro; epoxy. The substituent may be bonded to any of a hydrocarbon chain, a saturated ring, and an aromatic ring.

The alkoxy group is exemplified by a methoxy group, an ethoxy group, a n-propoxy group, and an isopropoxy group.

The halogen atom is exemplified by a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom.

The above decane can be produced by various known methods. For example, a method of performing a dehalogenation reaction of a halodecane in the presence of an alkali metal (Macromolecules, 23, 3423 (1990), etc.), a method for carrying out anionic polymerization of diterpene (Macromolecules, 23, 4494 (1990), etc.), a method for dehalogenation of halodecane by electrode reduction (J .Chem. Soc., Chem. Commun., 1161 (1990), J. Chem. Soc., Chem. Commun., 897 (1992), etc., method for dehalogenation of halodecanes in the presence of magnesium (WO98/29476, etc.), a method of performing a dehydrogenation reaction of hydroquinanes in the presence of a metal catalyst (Japanese Patent Laid-Open No. Hei-4-334551, etc.).

As the decazane of the above (A) component, for example, an average unit formula: (R ³ ₃ SiNR ⁴ ) _a (R ³ ₂ SiNR ⁴ ) _b (R ³ SiNR ⁴ ) _c (SiNR ⁴ ) _d (wherein And R ³ each independently represents the above crosslinkable group, a saturated aliphatic hydrocarbon group or an aromatic hydrocarbon group, an alkoxy group, a hydrogen atom or a halogen atom having a carbon number of 1 to 20, which is substituted or unsubstituted, and R ⁴ represents a hydrogen atom or a saturated aliphatic hydrocarbon group or an aromatic hydrocarbon group having a carbon number of 1 to 20 which is substituted or unsubstituted, and a, b, c and d represent 0 or a positive number, wherein a+b+c+d= 1, wherein at least one of R ³ in one molecule, preferably at least two of them is represented by the above crosslinkable group. Here, the saturated aliphatic hydrocarbon group, the aromatic hydrocarbon group, the alkoxy group, and the halogen atom have the same meanings as defined for the above decane.

The above decazane can be prepared by methods well known in the art. The preparation method of polyazane is described, for example, in U.S. Patent Nos. 4,312,970, 4, 460, 419, 4,395, 460, 4,404, 153, 4, 482, 689, 4, </ </ RTI> 4, </ RTI> 4, 540, 803, 4, 454, 344, 4, 835, 238, and 4,774, 312. No. 4929742 and No. 4916200 in. Further described in J. Mater. Sci., 22, 2609 (1987).

As the alkane of the above (A) component, for example, an average unit formula: (R ³ ₃ SiO _1/2 ) _a (R ³ ₂ SiO _2/2 ) _b (R ³ SiO _3/2 ) _c (SiO can be used. _4/2 ) _d (wherein R ³ independently represents the above crosslinkable group, a saturated aliphatic hydrocarbon group or an aromatic hydrocarbon group having a carbon number of 1 to 20 or a substituted or unsubstituted, alkoxy group, hydrogen An atom or a halogen atom; a, b, c, and d are each 0 or more and 1 or less and satisfy the number of a+b+c+d=1, wherein a, b, and c are not 0 at the same time, and R in one molecule At least one of ³ , preferably both of which are represented by the above crosslinkable group). Here, the saturated aliphatic hydrocarbon group, the aromatic hydrocarbon group, the alkoxy group, and the halogen atom have the same meanings as defined for the above decane.

The above oxiranes can be prepared by methods well known in the art. The method for preparing the decane is not particularly limited. Most commonly, the oxiranes are prepared by hydrolysis of organochlorostanes. Such methods and other methods are described in Noll, Chemistry and Technology of Silicones, Chapter 5 (Translated 2nd German Edition, Academic Press, 1968).

As the carbon decane of the above component (A), for example, an average unit formula: (R ³ ₃ SiCR ⁵ R ⁶ ) _a (R ³ ₂ SiCR ⁵ R ⁶ ) _b (R ³ SiCR ⁵ R ⁶ ) _c (SiCR ^{5 can be used.} R ⁶ ) _d (wherein R ³ independently represents the above crosslinkable group, a saturated aliphatic hydrocarbon group or an aromatic hydrocarbon group having a carbon number of 1 to 20 or a substituted or unsubstituted, alkoxy group or a hydrogen atom; Or a halogen atom, R ⁵ and R ⁶ each independently represent a hydrogen atom or a saturated aliphatic hydrocarbon group or an aromatic hydrocarbon group having a carbon number of 1 to 20 which is substituted or unsubstituted, and a, b, c, and d represent 0 or A positive number, wherein a+b+c+d=1, at least one of R ³ in one molecule, preferably at least two of them are represented by the above-mentioned crosslinkable group. Here, the saturated aliphatic hydrocarbon group, the aromatic hydrocarbon group, the alkoxy group, and the halogen atom have the same meanings as defined for the above decane.

The above carbon decane can be produced by a method well known in the art. The preparation method of the carbon decane is described, for example, in Macromolecules, 21, 30 (1988), and U.S. Patent No. 3,293,194.

The shape of the decane, the decane, the decane, and the carbene is not particularly limited, and may be a solid, a liquid, a paste or the like, and is preferably a solid in terms of workability and the like.

In the above-mentioned fluorene-based polymer compounds, if the cerium content is not significantly lower, the chemical stability is sufficient, the operation at room temperature and air is relatively easy, the raw material price and the manufacturing process cost are low, and the economy is sufficient. The industrial advantage such as sex is preferably a decane having a unit having a ruthenium-oxygen-oxime bond, more preferably a polyoxyalkylene.

The component (A) may be one or a mixture of two or more of the above organic compounds, 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, particularly preferably 10% by mass to 50% by mass.

The component (B) is a ruthenium-containing compound capable of crosslinking the component (A). As such a component (B), for example, a decane, a decane, a decane, a carbene or a mixture thereof may be mentioned, and specifically, a monomer having an Si-O-Si bond and an oligomer are exemplified. Or a oxane such as a polymer; a decane, a silane having a Si-Si bond, an oligomer or a polymer; a monomer, oligomer or polymerization having a Si-(CH ₂ ) _n -Si bond; An alkyl group; a monomer, oligomer or polymerization having a Si-(C ₆ H ₄ ) _n -Si or Si-(CH ₂ CH ₂ C ₆ H ₄ CH ₂ CH ₂ ) _n -Si bond An aryl group such as a monomer, an oligomer or a polymer having a Si-N-Si bond; having a Si—O—Si bond, a Si—Si bond, and a Si—(CH _{2 )} a ruthenium-containing copolymer compound having at least two bonds of an _n- Si bond, a Si-(C ₆ H ₄ ) _n -Si bond, and a Si-N-Si bond; and a mixture thereof. Further, in the formula, n is an integer of 1 or more. The component (B) is preferably a hydrogen atom having a deuterium atom bonded thereto.

The oxime of the above component (B) can be used, for example, by an average unit formula: (R ⁷ ₃ SiO _1/2 ) _a (R ⁷ ₂ SiO _2/2 ) _b (R ⁷ SiO _3/2 ) _c (SiO _4/2 ) _d (wherein R ⁷ independently represents a monovalent hydrocarbon group, a hydrogen atom, a halogen atom, an epoxy group-containing organic group, an acryl-containing fluorenyl group-containing organic group, a methacryl-containing fluorenyl group-containing organic group, and an amine group-containing group. An organic group, a mercapto group-containing organic group, an alkoxy group or a hydroxyl group; a, b, c and d are each 0 or more and 1 or less and satisfy the number of a+b+c+d=1, wherein a, b and c are different The time is 0).

Specific examples of the one-valent hydrocarbon group of R ⁷ include an alkyl group, an alkenyl group, an aralkyl group, and an aryl group. Alkyl group is preferably C ₁ ~ C ₁₂ alkyl group, and particularly preferably C ₁ ~ C ₆ alkyl group. Alkyl group may be straight-chain or branched alkyl, cycloalkyl, or cycloalkyl extension (a linear or branched alkylene group of (preferably methylene, ethyl and the like extending C ₁ ~ C ₆ extends Any of an alkyl group and an alkyl group in combination with a carbocyclic ring (preferably 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 exemplified by methyl, ethyl, n-propyl, isopropyl, butyl, and third. Butyl, pentyl, hexyl. The cycloalkyl group is preferably a C ₄ -C ₆ cycloalkyl group, and specifically, a cyclobutyl group, a cyclopentyl group, or a cyclohexyl group is exemplified. Alkenyl group is preferably a C ₂ ~ C ₁₂ alkenyl group, and particularly preferably C ₂ ~ 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 ~ C ₁₂ aralkyl group. Specific examples of the C ₇ -C ₁₂ aralkyl group include a benzyl group, a phenethyl group, and a phenylpropyl group. The aryl group is preferably a C ₆ -C ₁₂ aryl group, and specifically exemplified by a phenyl group, a naphthyl group, and a tolyl group. The monovalent hydrocarbon group may also have a substituent. Specific examples of the substituent include a halogen such as a fluorine atom, a chlorine atom, a bromine atom or an iodine atom; a hydroxyl group; and an alkoxy group such as a methoxy group, an ethoxy group, a n-propoxy group or an isopropoxy group. Specific examples of such a substituted monovalent hydrocarbon group include 3-chloropropyl, 3,3,3-trifluoropropyl, perfluorobutylethyl, and perfluorooctylethyl.

Further, specific examples of the halogen atom of R ⁷ include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom, and a chlorine atom is preferred.

Further, examples of the epoxy group-containing organic group of R ⁷ include glycidyloxyalkyl groups such as 3-glycidoxypropyl group and 4-glycidoxybutyl group; 2-(3, 4) -Epoxycyclohexyl)-ethyl, 3-(3,4-epoxycyclohexyl)-propyl and the like epoxycyclohexylalkyl; 4-oxiranylbutyl, 8-oxiranyl An oxiranyl group such as an octyl group is preferably a glycidoxyalkyl group, more preferably a 3-glycidoxypropyl group.

Further, the propylene-containing fluorenyl group-containing or methacryl-containing fluorenyl group-containing organic group of R ⁷ is specifically exemplified by 3-propenyloxypropyl group, 3-methylpropenyloxypropyl group, and 4- Acryloxybutyl, 4-methylpropenyloxybutyl, preferably 3-methylpropenyloxypropyl.

Further, examples of the amino group-containing organic group of R ⁷ include 3-aminopropyl group, 4-aminobutyl group, and N-(2-aminoethyl)-3-aminopropyl group. Preferred is 3-aminopropyl, N-(2-aminoethyl)-3-aminopropyl.

Further, specific examples of the mercapto group-containing organic group of R ⁷ include 3-mercaptopropyl group and 4-mercaptobutyl group.

Further, specific examples of the alkoxy group of R ⁷ include a methoxy group, an ethoxy group, a n-propoxy group, and an isopropoxy group, and a methoxy group or an ethoxy group is preferred.

Further, at least one of the molecules, preferably at least two R ⁷ are an alkenyl group, a hydrogen atom, a halogen atom, an epoxy group-containing organic group, an acryl-containing fluorenyl group-containing organic group, and a methacryl-containing fluorenyl group-containing organic group. An amine group-containing organic group, a mercapto group-containing organic group, an alkoxy group, or a hydroxyl group.

Further, a, b, c, and d are each 0 or more and 1 or less, and satisfy the number of a+b+c+d=1. Among them, a, b and c are not 0 at the same time.

Such a siloxane is represented by a structural unit represented by (R ⁷ ₃ SiO _1/2 ), (R ⁷ ₂ SiO _2/2 ), (R ⁷ SiO _3/2 ), and (SiO _4/2 ). The composition of at least one unit, specifically, a linear polyoxyalkylene containing (R ⁷ ₃ SiO _1/2 ) and (R ⁷ ₂ SiO _2/2 ) units; comprising (R ⁷ ₂ SiO _2/2 a cyclic polysiloxane of the unit; a branched _polyoxane comprising (R ⁷ SiO _3/2 ) or (SiO _4/2 ) units; comprising (R ⁷ ₃ SiO _1/2 ) and (R ⁷ SiO) _{a polyoxane of 3/2} ) unit; a polyoxyalkylene comprising (R ⁷ ₃ SiO _1/2 ) and (SiO _4/2 ) units; comprising (R ⁷ SiO _3/2 ) and (SiO _4/2 a unit polyoxyalkylene; a polyoxyalkylene comprising (R ⁷ ₂ SiO _2/2 ) and (R ⁷ SiO _3/2 ) units; comprising (R ⁷ ₂ SiO _2/2 ) and (SiO _4/2 ) a polyoxyalkylene unit; a polyoxyalkylene comprising (R ⁷ ₃ SiO _1/2 ), (R ⁷ ₂ SiO _2/2 ), and (R ⁷ SiO _3/2 ) units; comprising (R ⁷ ₃ SiO _{1 /2} ), (R ⁷ ₂ SiO _2/2 ) and (SiO _4/2 ) units of polyoxyalkylene; comprising (R ⁷ ₃ SiO _1/2 ), (R ⁷ SiO _3/2 ) and (SiO _{4 /2} ) a polyoxyalkylene unit; a polyoxyalkylene comprising (R ⁷ ₂ SiO _2/2 ), (R ⁷ SiO _3/2 ) and (SiO _4/2 ) units; comprising (R ⁷ ₃ SiO _{1 /2} ), (R ⁷ ₂ SiO _2/2 ), (R ⁷ SiO _3/2 ), and polysiloxanes of (SiO _4/2 ) units. Preferably, the number of repetitions of the structural unit represented by (R ⁷ ₃ SiO _1/2 ), (R ⁷ ₂ SiO _2/2 ), (R ⁷ SiO _3/2 ), and (SiO _4/2 ) is preferably It is in the range of 1 to 10,000, more preferably in the range of 1 to 1,000, and particularly preferably in the range of 3 to 500.

The dioxane can be prepared by methods well known in the art. The method for producing the decane is not particularly limited, and most commonly, it can be produced by hydrolysis of an organochloromethane. Such methods and other methods are described in Noll, Chemistry and Technology of Silicones, Chapter 5 (Translated 2nd German Edition, Academic Press, 1968).

Further, the oxime may be a ruthenium-containing copolymer compound with a polymer. For example, the following ruthenium-containing copolymer compound can be used as a ruthenium oxide: a ruthenium-containing copolymer compound having a Si-O-Si bond and a Si-Si bond; having a Si-O-Si bond and a Si-N-Si bond Cerium-containing copolymer compound; ruthenium-containing copolymer compound having Si-O-Si bond and Si-(CH ₂ ) _n -Si bond; having Si-O-Si bond and Si-(C ₆ H ₄ ) _n -Si A ruthenium-containing copolymer compound or the like having a bond or a Si-(CH ₂ CH ₂ C ₆ H ₄ CH ₂ CH ₂ ) _n -Si bond. Furthermore, in the formula, n is the same as described above.

Further, the decanes are, for example, represented by the formula: R ⁷ ₄ Si or an average unit formula: (R ⁷ ₃ Si) _a (R ⁷ ₂ Si) _b (R ⁷ Si) _c (Si) _d (wherein R ^{7 is} independently Is a monovalent hydrocarbon group, a hydrogen atom, a halogen atom, an epoxy group-containing organic group, an acryl-containing fluorenyl group-containing organic group, a methacryl-containing fluorenyl group-containing organic group, an amine group-containing organic group, a fluorenyl group-containing organic group, an alkoxy group or a hydroxyl group. Wherein at least one of the molecules, preferably at least two R ⁷ are an alkenyl group, a hydrogen atom, a halogen atom, an epoxy group-containing organic group, an acryl-containing fluorenyl group-containing organic group, a methacryl-containing fluorenyl group-containing organic group , an amine group-containing organic group, a mercapto group-containing organic group, an alkoxy group or a hydroxyl group; a, b, c and d are each 0 or more and 1 or less and satisfy the number of a+b+c+d=1, wherein a, b and c are not represented by 0).

The decane is represented by the formula R ⁷ ₄ Si or by at least one of the structural units represented by (R ⁷ ₃ Si), (R ⁷ ₂ Si), (R ⁷ Si), and (Si) Specific examples of the composition include linear polydecane including (R ⁷ ₃ Si) and (R ⁷ ₂ Si) units; cyclic polydecane containing (R ⁷ ₂ Si) units; and (R ⁷ Si) Or a branched polydecane (polycarbene acetylene) of the (Si) unit; a polydecane comprising (R ⁷ ₃ Si) and (R ⁷ Si) units; a polydecane comprising (R ⁷ ₃ Si) and (Si) units a polydecane comprising (R ⁷ Si) and (Si) units; a polydecane comprising (R ⁷ ₂ Si) and (R ⁷ Si) units; a polydecane comprising (R ⁷ ₂ Si) and (Si) units; a polydecane comprising (R ⁷ ₃ Si), (R ⁷ ₂ Si) and (R ⁷ Si) units; a polydecane comprising (R ⁷ ₃ Si), (R ⁷ ₂ Si) and (Si) units; a polydecane of R ⁷ ₃ Si), (R ⁷ Si) and (Si) units; a polydecane comprising (R ⁷ ₂ Si), (R ⁷ Si) and (Si) units; comprising (R ⁷ ₃ Si), (R ⁷ ₂ Si), (R ⁷ Si) and (Si) units of polydecane, and the like. The preferred number of repeating units of the 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, and more preferably 3 to Within the range of 1,000, it is especially within the range of 3 to 500.

The decane can be produced by various known methods. For example, a method of performing a dehalogenation reaction of a halodecane in the presence of an alkali metal (Macromolecules, 23, 3423 (1990), etc.), a method for carrying out anionic polymerization of diterpene (Macromolecules, 23, 4494 (1990), etc.), a method for dehalogenation of halodecane by electrode reduction (J .Chem. Soc., Chem. Commun., 1161 (1990), J. Chem. Soc., Chem. Commun., 897 (1992), etc., method for dehalogenation of halodecanes in the presence of magnesium (WO 98/29476, etc.), a method of performing a dehydrogenation reaction of hydroquinanes in the presence of a metal catalyst (Japanese Patent Laid-Open No. Hei-4-334551, etc.).

Further, the decane may be a ruthenium-containing copolymer compound with other polymers. For example, the following ruthenium-containing copolymer compound can be used as a decane: a ruthenium-containing copolymer compound having a Si-Si bond and a Si-O-Si bond; a ruthenium-containing copolymer having a Si-Si bond and a Si-N-Si bond a compound; a ruthenium-containing copolymer compound having a Si-Si bond and a Si-(CH ₂ ) _n -Si bond; having a Si-Si bond and a Si-(C ₆ H ₄ ) _n -Si bond or Si-(CH ₂ CH) ₂ C ₆ H ₄ CH ₂ CH ₂ ) The ruthenium-containing copolymer compound of the _n- Si bond or the like.

As other decanes, a general formula: [(R ⁸ ) ₂ HSi] _e R ⁹ (wherein R ^{8 is} independently a substituted or unsubstituted one-valent hydrocarbon group; e is an integer of 2 or more; R ⁹ An antimony compound represented by an evalent organic group). In the formula, as the one-valent hydrocarbon group of R ⁸ , the same one as the above-mentioned R ⁷ one-valent hydrocarbon group is exemplified. e is an integer of 2 or more, preferably an integer of 2-6. Further, R ⁹ is an e-valent organic group, and when e is 2, R ⁹ is a divalent organic group, and specifically, an alkyl group, an alkenyl group, an alkylene group, an alkyl group, and an aromatic group are exemplified. a aryl group, an aryl aryl group, an aryl group, an alkyl group, and more specifically exemplified by the group: -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 -.

Further, when e is 3, R ⁹ is a trivalent organic group, and specifically, the following groups are exemplified.

Further, as the indane alkane, for example, an average unit formula: (R ⁷ ₃ SiNR ¹⁰ ) _a (R ⁷ ₂ SiNR ¹⁰ ) _b (R ⁷ SiNR ¹⁰ ) _c (SiNR ¹⁰ ) _d (wherein R ^{7 is} independently Is a monovalent hydrocarbon group, a hydrogen atom, a halogen atom, an epoxy group-containing organic group, an acryl-containing fluorenyl group-containing organic group, a methacryl-containing fluorenyl group-containing organic group, an amine group-containing organic group, a fluorenyl group-containing organic group, an alkoxy group or a hydroxyl group. Wherein at least one of the molecules, preferably at least two R ⁷ are an alkenyl group, a hydrogen atom, a halogen atom, an epoxy group-containing organic group, an acryl-containing fluorenyl group-containing organic group, a methacryl-containing fluorenyl group-containing organic group , an amine group-containing organic group, a mercapto group-containing organic group, an alkoxy group or a hydroxyl group; R ¹⁰ is a hydrogen atom or a substituted or unsubstituted one-valent hydrocarbon group; a, b, c and d are each 0 or more and 1 or less and The number of a+b+c+d=1 is satisfied, where a, b, and c are not equal to 0). As the one-valent hydrocarbon group of R ¹⁰ , a group identical to the one-valent hydrocarbon group of R ^{7 is} exemplified. R ^{10 is} preferably a hydrogen atom or an alkyl group, and particularly preferably a hydrogen atom or a methyl group.

The indane alkane is composed of at least one of structural units represented by (R ⁷ ₃ SiNR ¹⁰ ), (R ⁷ ₂ SiNR ¹⁰ ), (R ⁷ SiNR ¹⁰ ), and (SiNR ¹⁰ ), specifically Illustrative: a linear polyazide comprising (R ⁷ ₃ SiNR ¹⁰ ) and (R ⁷ ₂ SiNR ¹⁰ ) units; a cyclic polyazide comprising (R ⁷ ₂ SiNR ¹⁰ ) units; comprising (R ⁷ SiNR ^a branched polyazide of ¹⁰ or (SiNR ¹⁰ ) unit; a polyazane comprising (R ⁷ ₃ SiNR ¹⁰ ) and (R ⁷ SiNR ¹⁰ ) units; comprising (R ⁷ ₃ SiNR ¹⁰ ) and (SiNR ¹⁰ a polyazane of the unit; a polyazane comprising (R ⁷ SiNR ¹⁰ ) and (SiNR ¹⁰ ) units; a polyazane comprising (R ⁷ ₂ SiNR ¹⁰ ) and (R ⁷ SiNR ¹⁰ ) units; a polyazinane of (R ⁷ ₂ SiNR ¹⁰ ) and (SiNR ¹⁰ ) units; a polyazane comprising (R ⁷ ₃ SiNR ¹⁰ ), (R ⁷ ₂ SiNR ¹⁰ ) and (R ⁷ SiNR ¹⁰ ) units; a polyazinane of (R ⁷ ₃ SiNR ¹⁰ ), (R ⁷ ₂ SiNR ¹⁰ ) and (SiNR ¹⁰ ) units; agglomerates comprising (R ⁷ ₃ SiNR ¹⁰ ), (R ⁷ SiNR ¹⁰ ) and (SiNR ¹⁰ ) units a decazane; a polyazane comprising (R ⁷ ₂ SiNR ¹⁰ ), (R ⁷ SiNR ¹⁰ ), and (SiNR ¹⁰ ) units; comprising (R ⁷ ₃ SiNR ¹⁰ ), (R ⁷ ₂ SiNR ¹⁰ ), (R ⁷ SiNR ¹⁰ ), and polyazane of the (SiNR ¹⁰ ) unit. The preferred number of repetitions of the structural unit represented by (R ⁷ ₃ SiNR ¹⁰ ), (R ⁷ ₂ SiNR ¹⁰ ), (R ⁷ SiNR ¹⁰ ), and (SiNR ¹⁰ ) is preferably in the range of 2 to 10,000, respectively. It is preferably in the range of 3 to 1,000, and particularly preferably in the range of 3 to 500.

The indane alkane can be prepared by methods well known in the art. The preparation method of such a decane alkane is described, for example, in U.S. Patent Nos. 4,312,970, 4, 460, 419, 4,395, 460, 4,404, 153, 4, 482, 689, 4, 297, 728, 4, 540, 803, 4, 454, 344, 4, 835, 238, No. 4774312, No. 4297742, and No. 4916200. Further described in J. Mater. Sci., 22, 2609 (1987).

The decane alkane may also be a ruthenium-containing copolymer compound with other polymers. For example, the following ruthenium-containing copolymer compound can be used as the polyazide: a ruthenium-containing copolymer compound having a Si-N-Si bond and a Si-O-Si bond; having a Si-N-Si bond and a Si-Si bond Rhodium copolymer compound; rhodium-containing copolymer compound having Si-N-Si bond and Si-(CH ₂ ) _n -Si bond; having Si-N-Si bond and Si-(C ₆ H ₄ ) _n -Si bond Or a ruthenium-containing copolymer compound of Si-(CH ₂ CH ₂ C ₆ H ₄ CH ₂ CH ₂ ) _n -Si bond or the like. Furthermore, in the formula, n is the same as described above.

As the carbon decane, for example, an average unit formula: (R ⁷ ₃ SiR ¹¹ ) _a (R ⁷ ₂ SiR ¹¹ ) _b (R ⁷ SiR ¹¹ ) _c (SiR ⁷ ) _d (wherein, R ^{7 is} independently a monovalent value a hydrocarbon group, a hydrogen atom, a halogen atom, an epoxy group-containing organic group, an acryl-containing fluorenyl group-containing organic group, a methacryl-containing fluorenyl group-containing organic group, an amine group-containing organic group, a mercapto group-containing organic group, an alkoxy group or a hydroxyl group, wherein At least one, preferably at least two, of R ⁷ is an alkenyl group, a hydrogen atom, a halogen atom, an epoxy group-containing organic group, an acryl-containing fluorenyl group-containing organic group, a methacryl-containing fluorenyl group-containing organic group, and an amine group. a base group, a mercapto group-containing organic group, an alkoxy group, or a hydroxyl group; R ¹¹ is an alkylene group or an extended aryl group; a, b, c and d are each 0 or more and 1 or less and satisfy a+b+c+d =1, where a, b, and c are not represented by 0). The alkylene group of R ¹¹ is represented, for example, by the formula -(CH ₂ ) _n -, and further, the extended aryl group of R ⁵ is represented, for example, by the formula -(C ₆ H ₄ ) _n -. Furthermore, in the formula, n is the same as described above.

The carbon alkane is 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 ), and specifically, for example, Illustrative: linear polycarbocarbones containing (R ⁷ ₃ SiR ¹¹ ) and (R ⁷ ₂ SiR ¹¹ ) units; cyclic polycarbon decanes containing (R ⁷ ₂ SiR ¹¹ ) units; containing (R ⁷ SiR ¹¹ ) Or a branched polycarbon decane of (SiR ¹¹ ) unit; a polycarbon decane comprising (R ⁷ ₃ SiR ¹¹ ) and (R ⁷ SiR ¹¹ ) units; comprising a combination of (R ⁷ ₃ SiR ¹¹ ) and (SiR ¹¹ ) units a carbon decane; a polycarbon decane comprising (R ⁷ SiR ¹¹ ) and (SiR ¹¹ ) units; a polycarbon decane comprising (R ⁷ ₂ SiR ¹¹ ) and (R ⁷ SiR ¹¹ ) units; comprising (R ⁷ ₂ SiR ¹¹ ) And a polycarbosilane of the (SiR ¹¹ ) unit; a polycarbon decane comprising (R ⁷ ₃ SiR ¹¹ ), (R ⁷ ₂ SiR ¹¹ ) and (R ⁷ SiR ¹¹ ) units; comprising (R ⁷ ₃ SiR ¹¹ ), ( a polycarbodecane of R ⁷ ₂ SiR ¹¹ ) and (SiR ¹¹ ) units; a polycarbon decane comprising (R ⁷ ₃ SiR ¹¹ ), (R ⁷ SiR ¹¹ ) and (SiR ¹¹ ) units; comprising (R ⁷ ₂ SiR ¹¹ , (R ⁷ SiR ¹¹ ) and (SiR ¹¹ ) units of polycarbon decane; comprising (R ⁷ ₃ SiR ¹¹ ), (R ⁷ ₂ SiR ¹¹ ), (R ⁷ SiR ¹¹ And polycarbosilane such as (SiR ¹¹ ) unit. The preferred number of repeats of the structural unit represented by (R ⁷ ₃ SiR ¹¹ ), (R ⁷ ₂ SiR ¹¹ ), (R ⁷ SiR ¹¹ ), and (SiR ¹¹ ) is preferably in the range of 2 to 10,000, respectively. The range is from 3 to 1,000, and particularly preferably from 3 to 500.

The carbon decanes can be prepared by methods well known in the art. A method for preparing a carbon decane and a method for preparing a carbon decane are described, for example, in Macromolecules, 21, 30 (1988), U.S. Patent No. 3,293,194.

The carbon decane may also be a ruthenium-containing copolymer compound with other polymers. For example, the following ruthenium-containing copolymer compound can be used as a carbon decane: a ruthenium-containing copolymer compound having a Si—(CH ₂ ) _n —Si bond and a Si—O—Si bond; having Si—(CH ₂ ) _n —Si a ruthenium-containing copolymer compound having a bond and a Si-Si bond; a ruthenium-containing copolymer compound having a Si-(CH ₂ ) _n -Si bond and a Si-N-Si bond; having a Si-(CH ₂ ) _n -Si bond and _{Si- (C 6 H 4) n} -Si bonds of the silicon-containing copolymer compound; having _{Si- (C 6 H 4) n} -Si bonds and Si-O-Si bonds of the silicon-containing copolymer compound; having Si- ( C ₆ H ₄ ) _n- Si bond and Si-Si bond ruthenium containing copolymer compound; having Si-(C ₆ H ₄ ) _n -Si bond or Si-(CH ₂ CH ₂ C ₆ H ₄ CH ₂ CH ₂ a ruthenium-containing copolymer compound having an _n- Si bond and a Si-N-Si bond. Furthermore, in the formula, n is the same as described above.

As the component (B), it is more preferable to have an average unit formula: (R ⁷ ₃ SiO _1/2 ) _a (R ⁷ ₂ SiO _2/2 ) _b (R ⁷ SiO _3/2 ) _c (SiO _4/2 ) _d (wherein R ^{7 is} independently a monovalent hydrocarbon group, a hydrogen atom, a halogen atom, an epoxy group-containing organic group, an acryl-containing fluorenyl group-containing organic group, a methacryl-containing fluorenyl group-containing organic group, an amine group-containing organic group, and a fluorenyl group-containing group. An organic group, an alkoxy group or a hydroxyl group; a, b, c and d are each 0 or more and 1 or less and satisfy the number of a+b+c+d=1, wherein a, b and c are not represented by 0) The alkane is particularly preferably a polyoxyalkylene.

Specific examples of the crosslinking reaction include an addition reaction such as a hydrazine hydrogenation reaction, a Michael addition reaction, or a Diels-Alder reaction; decondensation, dehydrogenation, dehydration, deamination, and the like. Reaction; ring-opening reaction such as epoxy ring opening, ester ring opening; free radical reaction such as peroxide, UV (Utlraviolet). In particular, the (A) component has an aliphatic unsaturated group, and the (B) component has In the case where a hydrogen atom having a deuterium atom is bonded, the deuterium hydrogenation reaction can be carried out in the presence of a catalyst for hydrogenation.

Specific examples of the catalyst for the hydrogenation reaction include platinum fine powder, platinum black, platinum-supported ceria micropowder, platinum-carrying activated carbon, chloroplatinic acid, platinum tetrachloride, and chloroplatinic acid alcohol solution. A complex of platinum and an olefin, a complex of platinum and an alkenyl alkane. The content is not particularly limited, and the amount of the metal atom in the catalyst is preferably in the range of 0.1 to 1,000 ppm based on the total mass of the component (A) and the component (B). Jia is in the range of 1 to 500 ppm.

Further, when the component (A) has an aliphatic unsaturated group and the component (B) has a hydrogen atom to which a ruthenium atom is bonded, the component (A) has a hydrogen atom to which a ruthenium atom is bonded, and When the component (B) has an aliphatic unsaturated group, the amount of each component used is not particularly limited, and the aliphatic unsaturated group (Mo) in the component (A) or the component (B) is a component (B). Or the amount of the hydrogen atom bonded to the atom in the (A) component in the range of 0.1 to 50 moles, preferably in the range of 0.1 to 30 moles, more preferably 0.1 to 10 The amount within the range of Moore. The reason for this is that if the amount of the hydrogen atom to which the ruthenium atom is bonded does not reach the lower limit of the above range, the carbonization yield tends to decrease in the case of the cured product obtained by calcination, and on the other hand, if it exceeds the above range, There is a tendency that the performance of the composite material obtained by calcining the obtained hardened material as an electrode active material is lowered.

Further, when the component (A) has an aliphatic unsaturated group and the component (B) has an aliphatic unsaturated group, an acryl fluorenyl group, a methacryl fluorenyl group or a hydrogen atom bonded to a ruthenium atom, (B) component has aliphatic unsaturation And when the component (A) has an aliphatic unsaturated group, an acryl fluorenyl group, a methacryl fluorenyl group or a hydrogen atom bonded to a ruthenium atom, the radical initiator may also be used by heat and / or light to carry out a free radical reaction.

Specific examples of the radical initiator include organic peroxides such as a dialkyl peroxide, a dinonyl peroxide, a peroxyester, and a peroxydicarbonate, or an organic azo compound. Specific examples of the organic peroxide include: benzoic acid peroxide, di-p-chlorobenzothymidine peroxide, di-2,4-dichlorobenzamide peroxide, and dibutylbutyl peroxide. , dicumyl peroxide, tert-butyl perbenzoate, 2,5-di(t-butylperoxy)-2,3-dimethylhexane, tert-butyl peracetate, peroxidation Bis(o-methylbenzhydrazide), bis(m-methylbenzonitrile), bis(p-methylbenzhydryl) peroxide, peroxy-2,3-dimethylbenzhydrazide, peroxidation -2,4-dimethylbenzhydrazide, peroxy-2,6-dimethylbenzhydrazide, peroxy-2,3,4-trimethylbenzhydrazide, peroxy-2,4,6 - methyl substituted benzamidine peroxide such as trimethylbenzhydrazide; tert-butyl perbenzoate, dicumyl peroxide, 2,5-dimethyl-2,5-di (p. Tributylperoxy)hexane, tert-butyl peroxyisopropylmonocarbonate, tert-butyl peroxyacetate, mixtures of these. Further, specific examples of the organic azo compound include 2,2'-azobisisobutyronitrile and 2,2'-azobis(4-methoxy-2,4-dimethylpentyl). Nitrile), 2,2'-azobis(2,4-dimethylvaleronitrile), 2,2'-azobisisobutylvaleronitrile, 1,1'-azobis(1-cyclohexyl) Alkylcarbonitrile).

The content of the radical initiator is not particularly limited, and is preferably in the range of 0.1 to 10% by mass based on the total amount of the component (A) and the component (B), and more preferably 0.5. An amount in the range of ~5 mass% by weight.

Further, when the component (A) has an aliphatic unsaturated group and the component (B) has an aliphatic unsaturated group, an acryl fluorenyl group, a methacryl fluorenyl group, or a hydrogen atom bonded to a ruthenium atom, When the component (B) has an aliphatic unsaturated group and the component (A) has an aliphatic unsaturated group, an acryl fluorenyl group, a methacryl fluorenyl group or a hydrogen atom bonded to a halogen atom, the use of each component The amount is not particularly limited, and is an aliphatic unsaturated group, an acryl fluorenyl group, a methacryl fluorenyl group or a hydrogen atom bonded to a ruthenium atom in the other component with respect to the aliphatic unsaturated group 1 mole in one component. The amount in the range of 0.1 to 50 moles is preferably in the range of 0.1 to 30 moles, and more preferably in the range of 0.1 to 10 moles. The reason is that when the amount of the aliphatic unsaturated group, the acryl fluorenyl group, the methacryl fluorenyl group, or the hydrogen atom to which the ruthenium atom is bonded is less than the lower limit of the above range, there is a case where the cured product obtained by calcination is used. On the other hand, when the content exceeds the above range, the performance of the composite material obtained by calcining the obtained cured product tends to be lowered as an electrode active material.

In the case of forming a cured product obtained by mixing a lithium-coated metal ruthenium or a ruthenium alloy fine powder in the component (A) and the component (B) and crosslinking the component (A) and the component (B), for example, It is produced by the method of the following I or II, and then moved to the step of heat treatment (calcination).

I: After the lithium-coated niobium or niobium alloy fine powder is mixed with the component (A) and the component (B), pre-curing is performed at a temperature of 300 ° C or lower, particularly 60 to 300 ° C. The obtained cured product may be directly used in the next calcination step, or may be used in the next calcination step after being pulverized into a particle size having an average particle diameter of 0.1 to 30 μm, more preferably 1 to 20 μm.

II: In the case where the cured product is formed into spherical particles, for example, a lithium-coated cerium or cerium alloy fine powder or a cross-linking composition containing the component (A) and the component (B) is preferably sprayed in hot air. The crosslinking reaction is carried out by emulsification or dispersion in a medium which is incompatible with the crosslinkable composition.

When one of the components (A) or (B) has an aliphatic unsaturated group and the other has a hydrogen atom bonded to a halogen atom, the component (A) and the component (B) may be mixed. The crosslinkable composition of the catalyst for hydrogenation reaction with hydrazine is sprayed in the form of fine particles in hot air and crosslinked by a hydrogenation reaction to obtain a fine particle-like cured product powder.

On the other hand, a crosslinkable composition in which the component (A) and the component (B) and the catalyst for hydrogenation reaction are mixed may be added to an aqueous solution of an emulsifier, and the mixture may be emulsified by stirring to form crosslinkability. The fine particles of the composition are then crosslinked by a hydrogenation reaction to form a fine particle-like cured product powder.

The emulsifier is not particularly limited, and specific examples thereof include a mixture of an ionic surfactant, a nonionic surfactant, an ionic surfactant, and a nonionic surfactant. In particular, it is preferred to use more than one ionic surfactant and more than one in terms of uniform dispersibility and stability of the oil-in-water emulsion produced by mixing the crosslinkable composition with water. A mixture of ionic surfactants.

In addition, a metal oxide such as cerium oxide (colloidal cerium oxide) or titanium oxide is used in combination with an emulsifier, and carbonization is carried out while maintaining cerium oxide on the surface of the cured product powder to form a carbon surface. A stable film that increases the carbonization yield or inhibits surface oxidation that occurs when the carbon material is placed.

The particle size of the cured product powder is not particularly limited, and a composite material having an average particle diameter of 1 to 20 μm suitable as an electrode active material by calcination is preferred, and a preferred average particle diameter is preferably 5 to 30 μm. In the range of 5 to 20 μm, it is particularly preferable.

Further, the crosslinking of the cured powder obtained in the above manner can be further promoted, and the carbonization yield by calcination can be further improved, and the heat treatment is further carried out at 150 to 300 ° C in air.

The composite material of the present invention can be obtained by a step of heat-treating (calcining) a cured product containing the component (A) and the component (B).

The calcination conditions are not particularly limited, and it is preferred to carry out calcination at 300 to 1500 ° C in an inert gas or a vacuum. Examples of the inert gas include nitrogen gas, helium gas, and argon gas. Further, a reducing gas such as hydrogen may be contained in the inert gas. The calcination temperature is more preferably in the range of 500 ° C to 1000 ° C. The calcination time is also not particularly limited, and may be, for example, 10 minutes to 10 hours, and preferably 30 minutes to 3 hours.

The calcination can be carried out in a carbonization furnace of a fixed bed or a fluidized bed type, and the heating method and type of the carbonization furnace are not particularly limited as long as it is a furnace having a function of raising the temperature to a specific temperature. Specific examples of the carbonization furnace include a Reidhammer furnace, a piercing furnace, a separate furnace, and an environmental continuous furnace (Oxynon Furnace).

The composite material of the present invention obtained as described above is characterized in that a metal ruthenium or ruthenium alloy fine powder having a lithium-containing layer on its surface is dispersed in the ruthenium-containing carbon composite particles. If the composite material of the present invention is used, an initial irreversible capacitance with a high initial discharge capacitance can be obtained (primary charge) An electrode with a reduced capacitance between the primary capacitor and the primary discharge capacitor.

The ruthenium-containing carbon composite material preferably has a ruthenium atom bonded to an oxygen atom and a carbon atom and has an amorphous structure. Such a structure can be confirmed by ²⁹ Si MAS (Magic Angle Spinning) NMR (Nuclear Magnetic Resonance) or X-ray diffraction analysis. When the ruthenium-containing carbon composite material is crystallized, the charge/discharge cycle characteristics or the initial charge and discharge efficiency are lowered.

Further, it is preferable that the density of the Si-C bond of the niobium-containing carbon composite material at the interface between the metal niobium or niobium alloy fine powder and the niobium-carbon-containing composite material as the matrix is higher than that of the niobium-containing carbon composite material. The density of Si-C bonds other than the interface portion of the metal ruthenium or iridium alloy fine powder. It is speculated that such a structure inhibits the destruction of the metal ruthenium or iridium alloy fine powder in the matrix. Such a structure can be confirmed by a bonding state surface analysis method by TEM (Transmission Electron Microscope)-EELS (Electron Energy-Loss Spectroscopy) analysis.

The surface of the composite material of the present invention may be subjected to a surface coating treatment using carbon.

The carbon surface coating method of the composite material is arbitrary. For example, the carbon film derived from the (D1) vapor-deposited carbon source may be subjected to a thermochemical vapor deposition treatment on the surface of the composite material at a temperature of 800 ° C or higher in a non-oxidizing atmosphere. Further, it is also possible to obtain a composite material which is covered with a carbon phase derived from an organic material which is carbonized by heat by mixing (D2) an organic material which is carbonized by heat and further calcined. Further, (D3) mechanical energy may be provided to coat the carbon black on the surface of the composite material.

The apparatus used for the thermal chemical vapor deposition treatment is not particularly limited as long as it is a device having a mechanism of heating to 800 ° C or higher in a non-oxidizing atmosphere, and may be appropriately selected depending on the purpose. A continuous method, a batch method, and a device using the same may be used, and specifically, a fluidized bed reactor, a rotary furnace, a vertical moving layer reactor, a tunneling furnace, a batch furnace, and a batch type rotary furnace are exemplified. Continuously rotating the furnace.

Specific examples of the (D1) vapor deposition carbon source used for the thermal chemical vapor deposition treatment include methane, ethane, ethylene, acetylene, propane, butane, butene, pentane, isobutane, hexane, and the like. Aliphatic hydrocarbon or a mixture thereof; benzene, divinylbenzene, monovinylbenzene, ethylvinylbenzene, toluene, xylene, styrene, ethylbenzene, diphenylmethane, naphthalene, phenol, A An aromatic hydrocarbon such as phenol, nitrobenzene, chlorobenzene, hydrazine, coumarone, pyridine, hydrazine or phenanthrene; gas diesel, phenolic oil, eucalyptus oil, and naphtha derived from a tar distillation step; The exhaust gas or the mixture produced by the calcination step. Usually methane or acetylene.

The non-oxidizing environment can be introduced into the thermochemical vapor deposition treatment device by using the vapor deposition carbon source gas or its vaporization gas; non-oxidizing gas such as argon gas, helium gas, hydrogen gas or nitrogen gas; and the mixed gas or the like. Get it inside.

In the case where the organic material and the composite material which have been carbonized by heat are mixed (D2) and then calcined to obtain a composite material which is covered with a carbon phase derived from an organic material which is carbonized by heat, the calcination can be carried out in the same manner as described above. . (D2) The organic material which is carbonized by heat, specifically, is a liquid or waxy paraffin wax at a normal temperature, polyethylene, polypropylene, polystyrene, polymethyl methacrylate, urethane. Ester resin, AS (acrylonitrile-styrene, acrylonitrile-styrene) resin, ABS (acrylonitrile-butadiene-styrene) resin, polyvinyl chloride, polyacetal, aromatic polycarbonate resin, aromatic A family of polyester resins, coal tars, phenol resins, epoxy resins, urea resins, melamine resins, fluororesins, quinone imine resins, urethane resins, furan resins, and mixtures thereof. Among them, a high molecular weight aromatic compound such as an aromatic polycarbonate, an aromatic polyester, a coal tar, a phenol resin, a fluororesin, a quinone imine resin or a furan resin, or a melamine resin is preferable. The reason for this is that the carbonization efficiency of heat utilization, which is easy to form a graphene structure or the like, is good.

In the case where the surface of the composite material is coated with carbon, the amount of carbon coating is preferably 1 to 50% by mass, more preferably 5 to 30% by mass, more preferably 5 to 30% by mass, more preferably 5~20 mass (% by weight). The reason for this is that even when only a composite material is used as the electrode active material, it is possible to have better conductivity and to suppress a decrease in charge and discharge capacitance of the electrode.

The composite material of the present invention may be in the form of particles having an average particle diameter of 5 nm to 50 μm. The average particle diameter is preferably from 10 nm to 40 μm, more preferably from 100 nm to 30 μm, and even more preferably from 1 μm to 20 μm.

The composite material of the present invention can be used as an electrode active material. The electrode active material of the present invention may be in the form of particles, and in this case, the average particle diameter is preferably from 1 to 50 μm, more preferably from 1 to 40 μm, still more preferably from 1 to 30 μm.

The electrode active material comprising the composite material of the present invention can be manufactured by a simple manufacturing process to have a high initial discharge capacitance and an initial irreversible electricity The electrode (the difference between the initial charging capacitor and the initial discharging capacitor) is reduced. Therefore, the electrode active material can be preferably used as an electrode active material for a nonaqueous electrolyte secondary battery. The electrode active material is particularly preferably used as an active material for an electrode of a lithium or lithium ion secondary battery.

(electrode)

The electrode of the present invention is characterized in that it contains the above electrode active material, and the shape and preparation method of the electrode are not particularly limited. As a method for preparing the electrode of the present invention, a method of preparing an electrode by mixing a composite material and a binder is specifically exemplified; and the obtained paste is crimped to a set by mixing the composite material with a binder and a solvent. A method of producing an electrode by applying a method such as an electrode to an electric body or a method of drying it to form an electrode. Further, the thickness of the paste applied to the current collector is, for example, 30 to 500 μm, preferably about 50 to 300 μm. Further, the drying method after coating is not particularly limited, and is preferably a heating vacuum drying treatment. The film thickness of the electrode material on the current collector after the drying treatment is, for example, 10 to 300 μm, preferably about 20 to 200 μm. In the case where the composite material is fibrous, the electrode can be produced by arranging it in a uniaxial direction, by using a structure such as a woven fabric, and by bundling or knitting a conductive fiber such as a metal or a conductive polymer. When the electrodes are formed, the terminals can also be combined as needed.

The current collector is not particularly limited, and specific examples thereof include a wire mesh or a foil of a metal such as copper, nickel, or the like.

Specific examples of the binder include a fluorine resin (polyvinylidene fluoride, polytetrafluoroethylene, etc.), a styrene-butadiene resin, carboxymethyl cellulose, sodium carboxymethyl cellulose, and polyacrylic acid. Sodium polyacrylate Amine, polyamine, styrene-butadiene rubber. The amount of the binder to be used is not particularly limited, and the lower limit thereof is in the range of 5 to 30 parts by mass, preferably 5 to 20 parts by mass, based on 100 parts by mass of the composite material. Inside. When the amount of the binder used is outside the above range, for example, the adhesion strength of the composite material to the surface of the current collector is insufficient, and the insulating layer which causes an increase in the internal resistance of the electrode is formed. The method for preparing the paste is not particularly limited, and examples thereof include a method of mixing a composite material in a mixed solution (or dispersion) of a binder and an organic solvent.

As the solvent, a solvent which can dissolve or disperse 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 to be used is not particularly limited as long as it is in the form of a paste. For example, it is usually in the range of 0.01 to 500 parts by mass, preferably 0.01 to 400 parts by mass, based on 100 parts by mass of the composite material. Within the range of the portion, it is preferably in the range of 0.01 to 300 parts by mass.

Further, any of the additional materials may be formulated in the electrode of the present invention. For example, an electrode can be produced by adding a conductive auxiliary agent. The ratio of use of the conductive auxiliary agent is not particularly limited, and is preferably in the range of 2 to 60 parts by mass, more preferably 5 to 40 parts by mass, based on 100 parts by mass of the composite material. It is preferably in the range of 5 to 20 parts by mass. This is because the conductivity is excellent, and the decrease in the charge and discharge capacitance of the electrode can be suppressed.

Examples of the conductive auxiliary agent include carbon black (Ketjen black, acetylene black, etc.), carbon fiber, and carbon nanotube. The conductive auxiliary agents may be used singly or in combination of two or more. Further, the conductive auxiliary agent may be mixed, for example, in a paste containing a composite material, a binder, and a solvent.

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

(power storage device)

A power storage device according to the present invention is characterized by comprising the above electrode. Examples of such a power storage device include a lithium primary battery, a lithium secondary battery, a lithium ion secondary battery, a capacitor, a hybrid capacitor (redox capacitor), an organic radical battery, and a double-layer carbon battery, and particularly preferably lithium or Lithium ion secondary battery. The lithium ion secondary battery can be, for example, a battery element including a negative electrode including the above electrode, a positive electrode capable of occluding or releasing lithium, an electrolyte, a separator, a current collector, a gasket, a sealing plate, and a casing, and the like. Manufacturing. The lithium secondary battery can be produced, for example, by using a battery element including a positive electrode including the above electrode, a negative electrode containing metal lithium, an electrolytic solution, a separator, a current collector, a gasket, a sealing plate, and a casing.

A 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. 1 and 2 .

Fig. 1 is a schematic exploded cross-sectional view showing a button-shaped battery of a lithium ion secondary battery as an example of the battery of the present invention.

The lithium ion secondary battery shown in Fig. 1 comprises: a casing 1 having an open upper cylindrical shape on its upper surface, and a gasket 2 having a double-opened cylindrical shape having an inner circumference substantially the same as the outer circumference of the outer casing 1. 3. The SUS plate 4, the current collector 5, the negative electrode 6, which comprises the composite material of the present invention as an electrode active material, the separator 7, the positive electrode 8, the current collector 9, and the sealing plate 10.

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

In the lithium ion secondary battery shown in Fig. 1, a gasket 2 is fitted to the wall surface of the outer casing 1, and has a sealing plate 10 having a shape slightly larger than the inner cylindrical surface of the liner 2 and having a bottomed cylindrical shape. The inner peripheral surface is further fitted to the outer peripheral surface of the spacer 2. Thereby, the outer casing 1 and the sealing plate 10 are formed to be insulated by the gasket 2, and the outer casing 1, the gasket 2, the gasket 3, the SUS plate 4, the current collector 5, the negative electrode 6, the separator 7, the positive electrode 8, and the set A button-shaped battery having the same axis of the electric body 9 and the sealing plate 10.

The positive electrode 8 in the lithium ion secondary battery shown in FIG. 1 is not particularly limited, and may be composed of, for example, a positive electrode active material, a conductive auxiliary agent, a binder, or the like. Examples of the positive electrode active material include metal oxides such as LiCoO ₂ , LiNiO ₂ , and LiMn ₂ O ₄ , polyanion oxides such as LiFePO ₄ and Li ₂ FeSiO ₄ , and spinel LiMn ₂ O ₄ . The positive electrode active materials may be used singly or in combination of two or more. As the conductive auxiliary material and the binder, the same as described above is exemplified.

2 is a lithium hydride produced as an example of the battery of the present invention. A schematic exploded cross-sectional view of a button cell of a secondary battery.

The lithium secondary battery shown in FIG. 2 includes a casing 1 having a bottom cylindrical shape having an open upper surface, and a gasket 2 having a double-opened cylindrical shape having an inner circumference substantially the same as the outer circumference of the outer casing 1, and a gasket 3, The SUS plate 4, the negative electrode 6 containing metal lithium, the separator 7, the positive electrode 8 including the composite material of the present invention as an electrode active material, the current collector 9', and the sealing plate 10.

In the outer casing 1 of the lithium secondary battery shown in FIG. 2, a substantially annular gasket 3 having a size slightly smaller than the inner circumference of the outer casing 1 is accommodated, and the gasket 3 is placed on the gasket 3 to have a size slightly smaller than the inner circumference of the outer casing 1. Disc-shaped SUS plate 4. A substantially disk-shaped negative electrode 6 having a size slightly smaller than the inner circumference of the outer casing 1 is disposed on the SUS plate 4. A separator 7 as a disk-shaped member having a size substantially the same as the inner circumference of the outer casing 1 is placed on the negative electrode 6, and the separator 7 is impregnated with an electrolytic solution. Further, the separator 7 may include two or more disk-shaped members. A positive electrode 8 and a current collector 9' having a size substantially the same as that of the negative electrode 6 are disposed on the separator 7. The current collector 9' is made of a foil containing a metal such as copper or nickel, a mesh or the like, and is integrated with the positive electrode 8 to be integrated.

In the lithium secondary battery shown in FIG. 2, a gasket 2 is fitted to the wall surface of the outer casing 1, and the sealing plate 10 having a shape slightly larger than the inner peripheral surface of the inner peripheral surface of the gasket 2 has a bottomed cylindrical shape. The inner peripheral surface is further fitted to the outer peripheral surface of the spacer 2. Thereby, the outer casing 1 and the sealing plate 10 are formed to be insulated by the gasket 2, and the outer casing 1, the gasket 2, the gasket 3, the SUS plate 4, the negative electrode 6, the separator 7, the positive electrode 8, the current collector 9', and A button-shaped battery having the same axis of the sealing plate 10.

The electrolyte solution contained in the lithium or lithium ion secondary battery shown in FIGS. 1 and 2 is not particularly limited, and a known one can be used. For example, a nonaqueous lithium or lithium ion secondary battery can be produced by using a solution in which an electrolyte is dissolved in an organic solvent as an electrolytic solution. The electrolyte may, for example, be a lithium salt such as LiPF ₆ , LiClO ₄ , LiBF ₄ , LiClF ₄ , LiAsF ₆ , LiSbF ₆ , LiAlO ₄ , LiAlCl ₄ , LiCl or LiI. Examples of the organic solvent include carbonates (propylene carbonate, ethylene carbonate, diethyl carbonate, etc.), lactones (γ-butyrolactone, etc.), and chain ethers (1, 2-). Dimethoxyethane, dimethyl ether, diethyl ether, etc.), cyclic ethers (tetrahydrofuran, 2-methyltetrahydrofuran, dioxolane, 4-methyldioxolan, etc.), cyclobutanthine ( Cyclopentane, etc.), anthracene (dimethyl hydrazine, etc.), nitriles (acetonitrile, propionitrile, benzonitrile, etc.), guanamines (N,N-dimethylformamide, N,N An aprotic solvent such as dimethylacetamide or the like, or a polyoxyalkylene glycol (diethylene glycol or the like). The organic solvent may be used singly or as a mixed solvent of two or more kinds. The electrolyte concentration is, for example, 0.3 to 5 moles, preferably 0.5 to 3 moles, and more preferably about 0.8 to 1.5 moles, relative to 1 L of the electrolytic solution.

Various additives may also be added to the above electrolyte as needed. As preferred additives, for example, fluoromethyl methyl carbonate, 4-fluoro-1,3-dioxiran-2-one or 4,5-difluoro-1,3-dioxolane- Halogenated carbonates such as 2-ketone; ethylene carbonate, methyl vinyl carbonate, ethyl vinyl carbonate, 4-vinyl ethylene carbonate. These additives are formulated to suppress the decomposition reaction of the electrolyte and increase the cycle life of the battery. The concentration of the additives in the electrolyte is preferably in the range of 0.1 to 50% by weight.

The separators 4 and 12 in the lithium or lithium ion secondary battery shown in Fig. 1 and Fig. 2 are not particularly limited, and a known separator such as a porous polypropylene non-woven fabric or a porous polyethylene non-woven fabric can be used. Olefin porous membrane Wait.

The power storage device of the present invention is not limited to the examples shown in Figs. 1 and 2, and can be applied to various forms such as a laminate shape, a package shape, a button shape, a chewing gum shape, a battery pack shape, and a rectangular shape. The power storage device of the present invention, particularly a lithium or lithium ion secondary battery, is preferably used as a portable camera, a computer, a word processor, a tape recorder, a mobile phone, etc., using the characteristics of light weight, high capacitance, and high energy density. A power source for an electronic device, a power source for a hybrid vehicle or an electric vehicle, and a power source for power storage.

[Examples]

Hereinafter, the present invention will be described in detail based on examples and comparative examples, but the present invention is not limited to the examples. Further, the X-ray diffraction, the transmission electron microscope, the X-ray photoelectron spectroscopy, and the evaluation of the battery characteristics in the examples and the comparative examples were carried out as follows.

[X-ray diffraction]

Device: RINT2000 manufactured by Rigaku Co., Ltd.

X-ray generating device: target Cu

Tube voltage: 40 kV

Tube current: 40 mA

2θ=10-90

Divergence slit: 2/3°

Divergence length: 10 mm

Scattering slit: 2/3°

Light receiving slit: 0.3 mm

[Transmissive electron microscope]

Device: JEOL-2100F TEM manufactured by JEOL Ltd.

[Electron Energy-Loss Spectroscopy, EELS]

Device: GIF CCD manufactured by Gatan

[Battery characteristics]

The charge and discharge characteristics of the lithium ion secondary battery using the composite material of the present invention were measured in the following manner using HJR-110mSM6 manufactured by Hokuto Denko.

The first charge and discharge were performed at a constant current of 0.1 C (37.2 mAh/g) per 1 g of the composite material at a rate of 372 mAh/g with respect to graphite of 10/1. Further, the first charging is completed at the time point when the battery voltage is lowered to 0 V, and the initial charging capacitance (mAh/g) is obtained. The first discharge is completed at the point where the battery voltage reaches 3 V, and the initial discharge capacitance (mAh/g) is obtained. During the switching of charging and discharging, it is placed in the open circuit for 30 minutes. After the second time, the charging was performed at a constant current of 0.5 C. After the battery voltage reached 0.02 V, the battery was switched to a constant voltage and the current value was further changed to 1/10, and the charging capacity was obtained. Further, the discharge was completed at a time point when the battery voltage reached 1.5 V at 0.5 C, and the discharge capacity was obtained. Furthermore, the cycle characteristics are also performed under the same conditions. The initial charge and discharge efficiency (CE%) is set as the percentage (%) of the initial discharge capacitance with respect to the initial charge capacitance. The capacity retention rate after the cycle test is set to the discharge capacitance after the specific cycle and the discharge capacitance of the second cycle. Percentage (%).

[Preparation Example 1] (Preparation of bismuth micropowder 1)

Will be 0.5 g of LiOH. 4.5 g of metal bismuth fine powder was added to the solution obtained by dissolving H ₂ O in 5 g of distilled water (high-purity metal ruthenium for semiconductors manufactured by Dow Corning Co., Ltd., 9.99999% by weight, average particle size 1 μm) After stirring for 24 hours under a nitrogen atmosphere, the mixture was dried by heating at 350 ° C to obtain a brown lithium surface-treated fine powder (fine powder 1). Further, the Li-O-Si structure was observed in the vicinity of 2θ of 16°-18°, 22°-23°, 28°-29°, and 34° by the X-ray diffraction (CuKα) of the fine powder. The unique diffraction peak.

[Preparation Example 2] (Preparation of 矽Micropowder 2)

A chemical metal cerium fine powder (having a particle size of 150 μm, containing Fe: 0.3%, Al: 0.3%, and Ca: 0.03% as a metal other than cerium) was coarsely pulverized by a jaw crusher, and hexane was further used. The medium was dispersed and pulverized by a ball mill and a bead mill until it became a fine powder having an average particle diameter of about 1 μm. The obtained suspension was filtered, and after desolvation in a nitrogen atmosphere, the coarse fraction was cut by an air-type precision classifier manufactured by Nisshin Engineering Co., Ltd. to obtain a powder having an average particle diameter of about 0.8 μm. Add 0.5 g of LiOH to 4.5 g of powder under nitrogen. H ₂ O, the mixture was ground for 5 minutes using a Mixer Mill MM301 ball mill apparatus manufactured by Retsch Co., Ltd., and the powder was taken out under a nitrogen atmosphere after the tank was sufficiently cooled. The obtained treated body was heated in a muffle furnace at 550 ° C to obtain a brownish lithium surface-treated fine powder (fine powder 2). The characteristic of the Li-O-Si structure is observed in the vicinity of 2θ of 16°-18°, 22°-23°, 28°-29°, and 34° by the X-ray diffraction (CuKα) of the fine powder. The diffraction peak.

[Preparation Example 3] (Preparation of bismuth micropowder 3)

2.66 g of LiCO ₃ was mixed in 4.5 g of metal cerium fine powder (Ground silicon material manufactured by Dow Corning Co., Ltd.), and treated with a planetary ball mill manufactured by Fritsch, Germany, at 300 rpm for 12 hours, thereby obtaining a brown lithium surface. Treat 矽 micro powder (矽 micro powder 3). The characteristic diffraction originating from the Li-O-Si structure is observed in the vicinity of 2θ of 21°-22°, 26°-27°, and 36°-37° by the X-ray diffraction (CuKα) of the fine powder. peak.

[Preparation Example 4] (Preparation of 矽Micropowder 4)

2.5 g of LiOH was stirred while stirring at 50 ° C. H ₂ O was added dropwise to an aqueous solution obtained by dissolving 6.8 g of methyltrimethoxydecane in 25 g of distilled water, followed by concentration to obtain an aqueous solution containing 20% by mass of lithium methyl niobate. 1.95 g of the above aqueous solution was added to 2.0 g of a metal cerium fine powder (manufactured by Aldrich Co., Ltd., average particle diameter: 100 nm), and the mixture was stirred under a nitrogen atmosphere for 2 hours, and then dried by heating at 600 ° C to obtain a brown lithium surface treatment. Powder (矽 micro powder 4). Li-O-Si derived from X-ray diffraction (CuKα) of the fine powder was observed at 2θ of 18°-19°, 26°-27°, 33°-34°, and 38°-39°. The characteristic diffraction peak of the structure.

[Preparation Example 5] (Preparation of ruthenium-containing carbon composite material powder 1)

DVB 570 (divinylbenzene and vinyl ethylbenzene as the main component of the main component, the content of divinylbenzene in the main component is 60% by mass) manufactured by Nippon Steel Chemical Industry Co., Ltd. The mixed viscosity of 15.49 g is 20 mPa. a methylhydroquinoxane copolymer terminated by a trimethyldecaneoxy group at both ends of the molecular chain of s (content of a hydrogen atom bonded to a halogen atom = 1.58 mass%) 9.51 g (bonding in the copolymer) Hydrogen atoms with deuterium atoms relative to ethylene in DVB 570 above The crosslinkable composition was prepared by using a platinum 1,3-divinyltetramethyldioxane complex platinum catalyst of 10 ppm on a platinum metal basis. The obtained crosslinkable composition was pre-cured at 120 ° C, and maintained at 600 ° C for 2 hours and then at 1,000 ° C under a nitrogen atmosphere using an environmentally controlled muffle furnace equipped with a temperature control program. Calcination was carried out for 1 hour, and pulverization and classification were carried out to obtain a cerium-containing carbon-based composite material powder 1 having an average particle diameter of about 10 μm.

[Example 1]

19.4 g of the bismuth micropowder prepared in the above Preparation Example 1 and DVB 570 (divinylbenzene and vinylethylbenzene) manufactured by Nippon Steel Chemical Industry Co., Ltd. were mixed as the main component, and the main component was divinylbenzene. The content is 60% by mass) 15.49 g and the viscosity is 20 mPa. a methylhydroquinoxane copolymer terminated by a trimethyldecaneoxy group at both ends of the molecular chain of s (content of a hydrogen atom bonded to a halogen atom = 1.58 mass%) 9.51 g (bonding in the copolymer) a platinum catalyst having a hydrogen atom of a halogen atom in an amount of 1 mole relative to a vinyl 1 molar in the above DVB 570) and a platinum 1,3-divinyltetramethyldioxane complex ( A crosslinkable composition was prepared with a platinum metal of 10 ppm). The block-like cured product obtained by hardening the crosslinkable composition at 120 ° C is placed in a lidded alumina container, and an environmentally controlled muffle furnace with a temperature control program is used for nitrogen gas. The mixture was calcined under the environment at 600 ° C for 2 hours and then at 1,000 ° C for 1 hour. After cooling, the mixture was pulverized by a pulverizer (Masscollorer) having a clearance of 20 μm to obtain a cerium-containing carbon-based composite powder in which a lithium-coated metal cerium fine powder having an average particle diameter of about 10 μm was dispersed.

According to TGA (Thermogravimetric Analysis), the content of the zero-valent cerium fine powder in the cerium-containing carbon-based composite material powder in which the lithium-coated metal cerium fine powder was dispersed was 37.9% by mass. According to TEM observation, it was confirmed that the cerium fine powder was dispersed in the cerium-containing carbon composite material. In the TEM-EELS analysis of the combined transmission electron microscope and Electron Energy-Loss Spectroscopy (EELS), energy was observed near 63 eV on the surface of the bismuth powder in the yttrium-containing carbon composite. Loss of the peak, confirming the presence of Li. Further, according to the analysis of the bonding state surface of the TEM-EELS analysis, the density of the Si-C bond and the matrix (the cerium-containing carbon system) at the interface between the metal cerium fine powder and the cerium-containing carbon composite material as the matrix are known. The density of Si-C bonds in the composite) is significantly higher.

The above-described prepared cerium-containing carbon-based composite material in which the lithium-coated metal cerium fine powder was dispersed was added in an amount of 85 mass%, and carbon black was 5 mass%, and mixed for 15 minutes. Then, 5 parts by mass of a solution of polyvinylidene fluoride-containing N-methyl-2-pyrrolidone was added so that the polyvinylidene fluoride was 10% by mass in terms of the solid content, and an appropriate amount of N- was further added. Methyl-2-pyrrolidone was mixed and mixed for 15 minutes to prepare a slurry. Thereafter, the slurry was applied onto a copper foil roll by a doctor blade method. The electrode obtained in the manner as described above was dried at 100 ° C for 1 hour, and pressed at a pressure of 10 KN using a roll press (manufactured by Faroji Seisakusho Co., Ltd.) to prepare an electrode having a thickness of about 20 μm. . The production and evaluation of the lithium ion secondary battery were carried out using the obtained electrode. The characteristics of the battery are shown in Table 1.

[Embodiment 2]

In addition to using the fine powder 2 prepared in the above Preparation Example 2 instead of the fine powder 1 A ruthenium-containing carbon-based composite material powder in which a lithium-coated metal ruthenium fine powder was dispersed was obtained in the same manner as in Example 1.

According to the TEM observation, it was confirmed that the cerium fine powder was dispersed in the cerium-containing carbon composite material. In the TEM-EELS analysis of the combined electron microscope and electron energy loss spectroscopy (EELS), the surface of the ruthenium-containing powder in the ruthenium-containing carbon composite was observed near 63 ev. The energy loss peak confirms the presence of Li.

Using the above-described ruthenium-containing carbon-based composite material in which the lithium-coated metal ruthenium fine powder was dispersed, an electrode was produced in the same manner as in Example 1 to prepare and evaluate a lithium ion secondary battery. The characteristics of the battery are shown in Table 1.

[Example 3]

Using a dental mixer, the micro-powder 32.4 g, diphenyl bis(dimethylvinyl nonyloxy) decane 30 g (containing 14.06% by mass of vinyl) prepared in the above Preparation Example 3 had a mixed viscosity of 20 mPa. a methyl hydrogen polyoxyalkylene terminated by a trimethyldecaneoxy group at both ends of the molecular chain of s (content of a hydrogen atom bonded to a halogen atom = 1.58 mass%) 9.8 g (the bond in the copolymer is The hydrogen atom of the ruthenium atom is 1 mole of the vinyl 1 molar in the above diphenyl bis(dimethylvinyl decyloxy) decane) and the 1,3-divinyltetramethyl group of platinum The dioxane complex platinum catalyst was 10 ppm on a platinum metal to prepare a crosslinkable composition. Thereafter, the composition was hardened in nitrogen at 150 ° C, thereby preparing a cured product. The above-mentioned hardened material was put into 3.7 g in an SSA-S grade alumina boat, and the boat was placed in a degreasing furnace. Thereafter, the inside of the degreasing furnace was maintained under reduced pressure for 10 minutes, and then returned to normal pressure with high-purity nitrogen gas (99.99%). Repeat this operation once. Thereafter, one side is supplied with high purity at a flow rate of 2 L/min. Nitrogen gas was heated at a rate of 2 ° C /min, and calcined at 600 ° C for 2 hours. The obtained calcined product was pulverized by a ball mill and classified by a 300 wire mesh. 2.2 g of the calcined product obtained by pulverization and classification was placed in an SSA-S grade alumina boat, and the boat was placed in a muffle furnace. The inside of the muffle furnace was maintained under reduced pressure for 60 minutes, and then returned to normal pressure using high-purity nitrogen gas (99.99%). Repeat this operation once. Thereafter, while supplying high-purity argon gas at a flow rate of 100 mL/min, the temperature was raised at a rate of 5 ° C /min, and calcination was carried out at 1000 ° C for 1 hour, thereby obtaining a niobium-containing carbon material.

According to the TGA analysis, the content of the zero-valent cerium fine powder in the cerium-containing carbon-based composite material powder in which the lithium-coated metal cerium fine powder was dispersed was 10.0% by mass.

Using the above-described ruthenium-containing carbon-based composite material in which the lithium-coated metal ruthenium fine powder was dispersed, an electrode was produced in the same manner as in Example 1 to prepare and evaluate a lithium ion secondary battery. The characteristics of the battery are shown in Table 1.

[Example 4]

The fine powder prepared in the above Preparation Example 4 was 6.4 g, and the viscosity was 773 mPa. s ((CH ₃ ) ₃ SiO _1/2 ) _1.0 (CH ₂ =CHSiCH ₃ O _2/2 ) _2.7 (C ₆ H ₅ SiO _3/2 ) _2.5 (hereinafter referred to as MD(Vi)T resin) 0.82 g The medium mixing viscosity is 5446 mPa. s ((CH ₃ ) ₃ SiO _1/2 ) _1.0 (HSiCH ₃ O _2/2 ) _3.4 (C ₆ H ₅ SiO _3/2 ) _3.8 (hereinafter referred to as MD(H)T resin) 0.74 g (this MD (H) The hydrogen atom of the T resin bonded with a halogen atom is about 1 mole relative to the vinyl 1 mole of the above MD(Vi)T resin) and the platinum 1,3-divinyltetramethyl The bismuthoxane complex platinum catalyst was prepared at 10 ppm on a platinum metal to prepare a crosslinkable composition. The block-shaped cured product obtained by hardening the crosslinkable composition at 200 ° C was placed in a lidded alumina container, and an environmentally controlled muffle furnace with a temperature control program was used for nitrogen gas. The mixture was calcined under the environment at 600 ° C for 2 hours and then at 1,000 ° C for 1 hour. After cooling, the mixture was pulverized by a pulverizer (Masscollorer) having a gap of 20 μm to obtain a cerium-containing carbon-based composite material powder in which a lithium-coated metal cerium fine powder having an average particle diameter of about 10 μm was dispersed.

According to the TGA analysis, the content of the zero-valent cerium fine powder in the cerium-containing carbon-based composite material powder in which the lithium-coated metal cerium fine powder was dispersed was 80.0% by mass.

Using the above-described ruthenium-containing carbon-based composite material in which the lithium-coated metal ruthenium fine powder was dispersed, an electrode was produced in the same manner as in Example 1 to prepare and evaluate a lithium ion secondary battery. The characteristics of the battery are shown in Table 1.

[Comparative Example 1]

A cerium-containing carbon-based composite material powder in which a metal cerium fine powder was dispersed was obtained in the same manner as in Example 1 except that 1.5 g of the metal cerium powder manufactured by Dow Corning Co., Ltd. was used instead of the cerium fine powder 1. Using the obtained cerium-containing carbon-based composite material powder in which the metal cerium fine powder was dispersed as an active material, an electrode was produced in the same manner as in Example 1 to prepare and evaluate a lithium ion secondary battery. The characteristics of the battery are shown in Table 1.

The initial charge and discharge efficiency (CE%) of the lithium ion secondary battery using the composite material powder of Comparative Example 1 as an active material was remarkably lowered, and the capacity retention ratio was also lowered.

[Comparative Example 2]

The cerium-containing carbon-based composite material powder 1 prepared in the above Preparation Example 5 and the metal cerium powder manufactured by Dow Corning Co., Ltd. were mixed at a ratio of 37.9 mass% of the metal cerium powder. Using the mixture as an active substance to An electrode was fabricated in the same manner as in Example 1 to prepare and evaluate a lithium ion secondary battery. The characteristics of the battery are shown in Table 1.

Any of the initial discharge capacity, the initial discharge efficiency (CE%), and the capacity retention ratio of the lithium ion secondary battery using the mixture of Comparative Example 2 as the active material was remarkably lowered.

[Comparative Example 3]

Using the ruthenium-containing carbon-based composite material powder 1 prepared in the above Preparation Example 5 as an active material, an electrode was produced in the same manner as in Example 1 to prepare and evaluate a lithium ion secondary battery. The characteristics of the battery are shown in Table 1.

[Industrial availability]

The initial irreversible capacitance (the difference between the primary charging capacitor and the primary discharging capacitor) of the electrode active material of the present invention is lowered, has a high initial discharge capacitance, and has stable charge and discharge cycle characteristics, and is preferably used for a power storage device, especially An electrode for a lithium or lithium ion secondary battery. Further, the electrode active material of the present invention can be produced by using a simple raw material and using a simple manufacturing process. Moreover, the electrode of the present invention can impart a higher initial discharge capacitance to the battery and a stable charge and discharge cycle characteristic. Therefore, the initial irreversible capacitance of the power storage device of the present invention is lowered, has a high initial discharge capacitance, and has stable charge and discharge cycle characteristics.

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Fig. 1 shows a lithium ion secondary battery as an example of the electricity storage device of the present invention.

Fig. 2 is a view showing a lithium secondary battery as an example of the electricity storage device of the present invention.

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Claims (12)

A composite material in which a metal ruthenium or ruthenium alloy fine powder having a lithium-containing layer on a surface thereof is dispersed in a ruthenium-containing carbon composite material. The composite material of claim 1, wherein the metal niobium or tantalum alloy fine powder has an average particle diameter of 10 nm to 10 μm. The composite material according to claim 1 or 2, wherein the lithium content is 0.1 to 10% by mass of the metal cerium or cerium alloy fine powder having the lithium-containing layer. An electrode active material comprising the composite material according to any one of claims 1 to 3. An electrode comprising the electrode active material of claim 4. A power storage device comprising the electrode of claim 5. The power storage device of claim 6, which is a lithium or lithium ion secondary battery. A method for producing a composite material, comprising: in the first step, forming a lithium-containing layer on a surface of a metal ruthenium or iridium alloy fine powder to obtain a lithium-coated metal ruthenium or ruthenium alloy fine powder; and in the second step, the lithium-coated metal ruthenium or The bismuth alloy fine powder is mixed with (A) a crosslinkable group-containing organic compound and (B) a ruthenium-containing compound crosslinkable with the above crosslinkable group-containing organic compound to crosslink the component (A) and the component (B) The reaction is carried out to obtain a cured product; and in the third step, the cured product is subjected to heat treatment. A method for producing a composite material, comprising: a first step of forming a lithium-containing layer on a surface of a metal ruthenium or iridium alloy fine powder to obtain a lithium-coated metal ruthenium or ruthenium alloy fine powder; and a second step of causing (A) crosslinking Organic compounds and (B) crosslinkable The ruthenium-containing compound containing a crosslinkable group-containing organic compound is subjected to a crosslinking reaction to obtain a cured product; and in the third step, the lithium-coated metal ruthenium or ruthenium alloy fine powder and the cured product are mixed and compounded while providing mechanical energy. And heat treatment. A method for producing a composite material, comprising: a first step of forming a lithium-containing layer on a surface of a metal ruthenium or iridium alloy fine powder to obtain a lithium-coated metal ruthenium or ruthenium alloy fine powder; and a second step of causing (A) crosslinking The organic compound and (B) crosslink the ruthenium-containing compound containing the crosslinkable organic compound to obtain a cured product; and the third step, heat-treating the cured product to obtain a ruthenium-containing carbon composite In the fourth step, the lithium-coated metal ruthenium or iridium alloy fine powder and the ruthenium-containing carbon-based composite material are mixed and composited while providing mechanical energy. The method of producing a composite material according to any one of claims 9 to 10, wherein the first step comprises the step of mixing a metal ruthenium or iridium alloy fine powder with a lithium or lithium compound and performing heat treatment. The method of claim 11, wherein the lithium compound is LiOH (LiOH.H ₂ O), Li ₂ O, LiR (R is an alkyl group, an organic decyloxy group), LiOR (R is the same as the above), LiCO ₃ , LiNO ₃ , LiX (X is a halogen atom), Li complex compound, R _n Si(OLi) _4-n (R is the same as above, n is a number from 1 to 3) or a mixture thereof.