JP2003178751A - Electrode, and battery using the same - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a battery with high capacitive density and stable charging/ discharging characteristics. <P>SOLUTION: A compound having diazine N, N'-dioxide structure expressed by the formula (1) is used as an electrode activator, and stylene-butadiene latex is used as a binder. In the formula, n, m, n', m' independently represent integer of not less than 0, and the order of condensation of diazine ring and benzene ring may be alternate or random. Substituents R<SB>1</SB>, R<SB>2</SB>, R<SB>3</SB>, R<SB>4</SB>, R<SP>a</SP>, R<SP>b</SP>, R<SP>c</SP>, and R<SP>d</SP>, represent independently hydrogen atom, halogen atom, or a specific group, where, when n is not less than 2, R<SP>a</SP>and R<SP>b</SP>may be the same or different from each other, and when n' is not less than 2, R<SP>c</SP>and R<SP>d</SP>may be the same or different from each other. Further, those substituents may form a ring structure by themselves. <P>COPYRIGHT: (C)2003,JPO

Description

Detailed Description of the Invention

[0001]

TECHNICAL FIELD The present invention relates to an electrode and a battery using the same. More specifically, the electrode active material contains a compound having a diazine N, N'-dioxide structure and is formed by using a binder containing styrene-butadiene latex as a main component, and has a high capacity density. The present invention relates to a battery having excellent charge / discharge stability.

[0002]

2. Description of the Related Art A battery converts chemical energy generated by a redox reaction occurring in a positive electrode and a negative electrode into electric energy and takes it out, or converts electric energy into chemical energy and stores it. ,
It is used as a power source in various devices.

With the rapid spread of portable electronic devices in recent years,
There is an increasing demand for batteries with high capacity density. In order to meet this demand, batteries using alkali metal ions having a small mass per unit charge have been developed. Among these, batteries using lithium ions are used in various portable devices as large-capacity batteries having excellent stability. Such a lithium-ion battery uses a lithium-containing heavy metal oxide and a carbon material electrode as the active materials of the positive electrode and the negative electrode, respectively, and charges them by utilizing the insertion reaction and desorption reaction of lithium ions with respect to these active materials. It is discharging.

However, since such a lithium ion battery utilizes a heavy metal compound having a high specific gravity as an active material for the positive electrode, the battery capacity per unit mass is not sufficient and the lithium ion battery functions as a battery having a high capacity density. There was a problem that I could not.

Therefore, attempts have been made to develop a large capacity battery using a lighter weight electrode material. For example, US Pat. No. 4,833,048 and Japanese Patent No.
Japanese Patent No. 2,715,778 discloses a battery which utilizes an electrochemical redox reaction based on the generation and dissociation of the disulfide bond by using an organic compound having a disulfide bond as an active material of a positive electrode.

However, since this battery uses an organic compound composed of a low mass element such as sulfur or carbon as an electrode material, it has a tentative effect in terms of constructing a battery of high capacity density. However, there was a problem that the efficiency of recombining dissociated disulfide bonds was low and the stability of charge and discharge was insufficient.

As a battery using an organic compound as an active material, a battery using a conductive polymer as an electrode material has been proposed. This battery is charged and discharged by a doping reaction and a dedoping reaction of electrolyte ions with respect to a conductive polymer. Note that the doping reaction described here is defined as a reaction that stabilizes excitons such as charged solitons and polarons generated by the electrochemical redox reaction of a conductive polymer by counterions, while the dedoping reaction is , A reverse reaction of a doping reaction, that is, a reaction of electrochemically oxidizing or reducing excitons stabilized by counterions.

US Pat. No. 4,442,187 discloses a battery using such a conductive polymer as a positive electrode or a negative electrode. This battery is expected to be developed as a high capacity density battery because the conductive polymer is composed of a low mass element such as carbon or nitrogen.

However, the conductive polymer generally has a property that excitons generated by an electrochemical redox reaction delocalize over a wide range of the π-electron conjugated system and interact with each other. Therefore, there is a problem that the concentration of excitons generated is limited, and as a result, the capacity of the battery is limited.

Therefore, a battery using such a conductive polymer as an electrode material is still insufficient in terms of high capacity density of the battery.

[0011]

As described above, it is theoretically difficult to manufacture a large-capacity battery that exceeds the current situation with a lithium-ion battery that uses a heavy metal oxide of high mass as the active material of the positive electrode. In addition, various batteries using a low-mass compound instead of a high-mass heavy metal oxide as an electrode active material have been proposed, but a battery having a high capacity density and excellent stability has not yet been obtained.

Further, the binder used for the electrode is an amount of the active material which sufficiently binds the active material with the current collector and the conductivity-imparting agent and causes an oxidation-reduction reaction accompanied by electron transfer during charge and discharge, that is, It is used to improve the ratio (utilization rate) of the active material involved in the electrode reaction. However, unless a binder suitable for the active material is used as the binder for such an electrode, it is difficult to obtain a sufficiently high utilization rate of the active material.

Therefore, an object of the present invention is to use a specific electrode active material and a binder suitable for the specific electrode active material, and thus a battery having a high capacity density and excellent charge / discharge stability, and suitable for forming such a battery. To provide a transparent electrode.

[0014]

Means for Solving the Problems As a result of intensive studies, the inventors of the present invention have identified a specific organic compound which has not been used as an active material of an electrode until now, although it is composed of only low mass atoms. It has been found that an excellent electrode can be obtained by combining a compound, that is, a compound having a diazine N, N'-dioxide structure, with a specific binder, that is, styrene-butadiene latex. According to the present invention, such a compound having a specific diazine N, N′-dioxide structure is used as an active material in an electrode,
Further, by using a latex containing a copolymer of styrene and butadiene as a main component as a binder for the electrode, a novel battery having a high capacity density and excellent charge / discharge stability, and such a battery are provided. Formable electrodes can be provided.

That is, the present invention contains a compound represented by the following general formula (1) having a diazine N, N'-dioxide structure as an electrode active material, and the electrode active material contains styrene-butadiene latex as a main component. The present invention relates to an electrode, which is bound by a binding agent of

[0016]

[Chemical 3]

[In the formula, n, m, n'and m'each independently represent an integer of 0 or more. The order of condensation of the diazine ring and the benzene ring may be alternating or random. Further, the substituents R ₁ , R ₂ , R ₃ , R ₄ , R ^a , R ^b ,
R ^c and R ^d are each independently a hydrogen atom, a halogen atom, a hydroxyl group, a nitro group, a nitroso group, a cyano group, a carboxyl group, a substituted or unsubstituted alkyl group, a substituted or unsubstituted alkenyl group, a substituted or Unsubstituted cycloalkyl group, substituted or unsubstituted aromatic hydrocarbon group, substituted or unsubstituted aromatic heterocyclic group,
Substituted or unsubstituted aralkyl group, substituted or unsubstituted amino group, substituted or unsubstituted alkoxy group, substituted or unsubstituted aryloxy group, substituted or unsubstituted alkoxycarbonyl group, substituted or unsubstituted aryloxycarbonyl Represents a group or a substituted or unsubstituted acyl group. However, when n is 2 or more, R ^a
And R ^b may be the same or different, and when n ′ is 2 or more, R ^c and R ^d may be the same or different. In addition, one or more atoms of these substituents may be substituted with a sulfur atom, a silicon atom, a phosphorus atom, or a boron atom, and the substituents may form a ring structure. The present invention also provides substituents R ₁ , R ₂ and R of a compound represented by the following general formula (1) having a diazine N, N′-dioxide structure.
_It contains, as an electrode active material, an oligomer or polymer compound having as a structural unit a divalent group having two bonds instead of two substituents among ₃ , R ₄ , R ^a , R ^b , R ^c and R ^d. And an electrode characterized in that the electrode active material is bound by a binder containing styrene-butadiene latex as a main component.

[0018]

[Chemical 4]

[In the formula, n, m, n'and m'each independently represent an integer of 0 or more. The order of condensation of the diazine ring and the benzene ring may be alternating or random. Further, the substituents R ₁ , R ₂ , R ₃ , R ₄ , R ^a , R ^b ,
R ^c and R ^d are each independently a hydrogen atom, a halogen atom, a hydroxyl group, a nitro group, a nitroso group, a cyano group, a carboxyl group, a substituted or unsubstituted alkyl group, a substituted or unsubstituted alkenyl group, a substituted or Unsubstituted cycloalkyl group, substituted or unsubstituted aromatic hydrocarbon group, substituted or unsubstituted aromatic heterocyclic group,
Substituted or unsubstituted aralkyl group, substituted or unsubstituted amino group, substituted or unsubstituted alkoxy group, substituted or unsubstituted aryloxy group, substituted or unsubstituted alkoxycarbonyl group, substituted or unsubstituted aryloxycarbonyl Represents a group or a substituted or unsubstituted acyl group. However, when n is 2 or more, R ^a
And R ^b may be the same or different, and when n ′ is 2 or more, R ^c and R ^d may be the same or different. In addition, one or more atoms of these substituents may be substituted with a sulfur atom, a silicon atom, a phosphorus atom, or a boron atom, and the substituents may form a ring structure. ] The present invention also provides a compound or oligomer or polymer compound having the above diazine N, N'-dioxide structure,
The present invention relates to an electrode containing as a reaction starting material, a product or an intermediate product in at least a discharge reaction of an electrode reaction.

The present invention also relates to a battery having the above-mentioned electrode as a positive electrode and / or a negative electrode.

The present invention also relates to a battery having the above electrode as a positive electrode.

The present invention also relates to a battery characterized by being a secondary battery having the above-mentioned electrode as both the positive electrode and the negative electrode or as either one of the electrodes.

The present invention also relates to the above battery, wherein the secondary battery is a lithium secondary battery.

[0024]

DESCRIPTION OF THE PREFERRED EMBODIMENTS FIG. 1 shows the configuration of one embodiment of the battery of the present invention. The battery shown in FIG. 1 has a positive electrode 5 and a negative electrode 3.
And are stacked so as to face each other with the separator 4 containing the electrolyte interposed therebetween. The positive electrode 5 is arranged on the positive electrode current collector 6, the negative electrode 3 is arranged on the negative electrode current collector 1,
Between the negative electrode current collector 1 and the positive electrode current collector 6, for the purpose of preventing electrical contact between the negative electrode current collector 1 and the positive electrode current collector 6, the negative electrode current collector 1 and the positive electrode current collector 6 have a frame shape surrounding the periphery of the positive electrode, the negative electrode, and the separator, and are made of an insulating material such as plastic resin An insulating packing 2 made of material is arranged. When a solid electrolyte or gel electrolyte is used, these electrolytes can be interposed between the electrodes instead of the separator.

In this embodiment, the active material used in the negative electrode 3 or the positive electrode 5 or both electrodes in such a structure is represented by the general formula (1) having the diazine N, N'-dioxide structure. A compound or a divalent group having two bonds instead of two substituents among the substituents R ₁ , R ₂ , R ₃ , R ₄ , R ^a , R ^b , R ^c and R ^d of the compound. An oligomer or polymer compound having a structural unit (hereinafter, these compounds are appropriately referred to as "diazine N, N '
-Dioxide compound "), and styrene-butadiene latex is used as a binder.

From the viewpoint of battery capacity, the battery of the present invention has a positive electrode containing the above-mentioned diazine N, N'-dioxide compound as a positive electrode active material, and a lithium secondary battery containing lithium ion as an electrolyte cation. Preferably.

[1] Active Material The active material of the electrode in the present invention is a material that directly contributes to the electrode reaction such as charge reaction and discharge reaction, and plays a central role in the battery system.

[1-1] Compound having diazine N, N'-dioxide structure Diazine N used as an active material in the present invention,
The N′-dioxide compound includes a diazine compound represented by the general formula (1) (n + m + in the general formula (1).
n '+ m' = 0), a polyacene type compound (which satisfies n + m + n '+ m' ≧ 1 in the general formula (1)), and a divalent group having two bonds in the ring of these compounds as a structural unit. And an oligomer or polymer compound having These diazines N, N '
The dioxide compound may be used alone or in combination of two or more. The diazine N, N′-dioxide compound in the present invention functions as an electrode active material in the electrode and is used as a reaction starting material, a product or an intermediate product in the discharge reaction of the electrode reaction, or in the discharge reaction and the charge reaction. It is contained in the electrode.

In the general formula (1), the substituent R ₁ ,
Examples of the halogen atom of R ₂ , R ₃ , R ₄ , R ^a , R ^b , R ^c, and R ^d include fluorine, chlorine, bromine, iodine, etc., which may be used alone or in combination of two or more. be able to.

Examples of the substituted or unsubstituted alkyl group include methyl group, ethyl group, propyl group, isopropyl group, n-butyl group, s-butyl group, isobutyl group, t-butyl group and n-pentyl group. , N-hexyl group,
n-heptyl group, n-octyl group, hydroxymethyl group, 1-hydroxyethyl group, 2-hydroxyethyl group, 2-hydroxyisobutyl group, 1,2-dihydroxyethyl group, 1,3-dihydroxyisopropyl group,
2,3-dihydroxy-t-butyl group, 1,2,3-trihydroxypropyl group, chloromethyl group, 1-chloroethyl group, 2-chloroethyl group, 2-chloroisobutyl group, 1,2-dichloroethyl group, 1,3-dichloroisopropyl group, 2,3-dichloro-t-butyl group, 1,
2,3-trichloropropyl group, bromomethyl group, 1-
Bromoethyl group, 2-bromoethyl group, 2-bromoisobutyl group, 1,2-dibromoethyl group, 1,3-dibromoisopropyl group, 2,3-dibromo-t-butyl group,
1,2,3-tribromopropyl group, iodomethyl group,
1-iodoethyl group, 2-iodoethyl group, 2-iodoisobutyl group, 1,2-diiodoethyl group, 1,3-diiodoisopropyl group, 2,3-diiodo-t-butyl group, 1,2,3-tri Iodopropyl group, aminomethyl group, 1-aminoethyl group, 2-aminoethyl group, 2-aminoisobutyl group, 1,2-diaminoethyl group, 1,3
-Diaminoisopropyl group, 2,3-diamino-t-butyl group, 1,2,3-triaminopropyl group, cyanomethyl group, 1-cyanoethyl group, 2-cyanoethyl group, 2
-Cyanoisobutyl group, 1,2-dicyanoethyl group,
1,3-dicyanoisopropyl group, 2,3-dicyano-
t-butyl group, 1,2,3-tricyanopropyl group, nitromethyl group, 1-nitroethyl group, 2-nitroethyl group, 2-nitroisobutyl group, 1,2-dinitroethyl group, 1,3-dinitroisopropyl group , 2,3-dinitro-t-butyl group, 1,2,3-trinitropropyl group and the like, which may be used alone or in combination of two or more.

Examples of the substituted or unsubstituted alkenyl group include vinyl group, allyl group, 1-butenyl group,
2-butenyl group, 3-butenyl group, 1,3-butanedienyl group, 1-methylvinyl group, styryl group, 2,2-diphenylvinyl group, 1,2-diphenylvinyl group, 1-
Methylallyl group, 1,1-dimethylallyl group, 2-methylallyl group, 1-phenylallyl group, 2-phenylallyl group, 3-phenylallyl group, 3,3-diphenylallyl group, 1,2-dimethylallyl group, 1-phenyl-1-
Examples thereof include a butenyl group and a 3-phenyl-1-butenyl group, which may be used alone or in combination of two or more.

The substituted or unsubstituted cycloalkyl group includes, for example, a cyclopropyl group, a cyclobutyl group, a cyclopentyl group, a cyclohexyl group, a 4-methylcyclohexyl group and the like, which have one kind or a combination of two or more kinds. be able to.

Examples of the substituted or unsubstituted aromatic hydrocarbon group include phenyl group, 1-naphthyl group and 2-
Naphthyl group, 9-fluorenyl group, 1-anthryl group,
2-anthryl group, 9-anthryl group, 1-phenanthryl group, 2-phenanthryl group, 3-phenanthryl group, 4-phenanthryl group, 9-phenanthryl group, 1
-Naphthacenyl group, 2-naphthacenyl group, 9-naphthacenyl group, 1-pyrenyl group, 2-pyrenyl group, 4-pyrenyl group, 2-biphenylyl group, 3-biphenylyl group,
4-biphenylyl group, p-terphenyl-4-yl group, p-terphenyl-3-yl group, p-terphenyl-2-yl group, m-terphenyl-4-yl group, m-terphenyl -3-yl group, m-terphenyl-2-yl group, o-tolyl group, m-tolyl group, p-tolyl group, p-
t-butylphenyl group, p- (2-phenylpropyl)
Phenyl group, 3-methyl-2-naphthyl group, 4-methyl-1-naphthyl group, 4-methyl-1-anthryl group,
4'-methylbiphenylyl group, 4 "-t-butyl-p
-Terphenyl-4-yl group, derivatives thereof, and the like can be given, and these can be used alone or in combination of two or more.

Examples of the substituted or unsubstituted aromatic heterocyclic group include 1-pyrrolyl group, 2-pyrrolyl group, 3-pyrrolyl group, pyrazinyl group, 2-pyridinyl group, 3-pyridinyl group, 4-pyridinyl group, 1-indolyl group, 2-indolyl group, 3-indolyl group, 4-indolyl group, 5-
Indolyl group, 6-indolyl group, 7-indolyl group,
1-isoindolyl group, 2-isoindolyl group, 3-isoindolyl group, 4-isoindolyl group, 5-isoindolyl group, 6-isoindolyl group, 7-isoindolyl group, 2-furyl group, 3-furyl group, 2-benzofuranyl group, 3-benzofuranyl group, 4-benzofuranyl group, 5
-Benzofuranyl group, 6-benzofuranyl group, 7-benzofuranyl group, 1-isobenzofuranyl group, 3-isobenzofuranyl group, 4-isobenzofuranyl group, 5-isobenzofuranyl group, 6-isobenzo Furanyl group, 7-isobenzofuranyl group, 2-quinolyl group, 3-quinolyl group, 4-quinolyl group, 5-quinolyl group, 6-quinolyl group, 7-quinolyl group, 8-quinolyl group, 1-isoquinolyl group Group, 3-isoquinolyl group, 4-isoquinolyl group, 5-
Isoquinolyl group, 6-isoquinolyl group, 7-isoquinolyl group, 8-isoquinolyl group, 2-quinoxalinyl group, 5
-Quinoxalinyl group, 6-quinoxalinyl group, 1-carbazolyl group, 2-carbazolyl group, 3-carbazolyl group, 4-carbazolyl group, 9-carbazolyl group, 1-phenanthridinyl group, 2-phenanthridinyl group, 3-
Phenanthridinyl group, 4-phenanthridinyl group, 6
-Phenanthridinyl group, 7-phenanthridinyl group,
8-phenanthridinyl group, 9-phenanthridinyl group, 10-phenanthridinyl group, 1-acridinyl group, 2-acridinyl group, 3-acridinyl group, 4-acridinyl group, 9-acridinyl group, 1 , 7-phenanthroline-2-yl group, 1,7-phenanthroline-3
-Yl group, 1,7-phenanthrolin-4-yl group,
1,7-phenanthrolin-5-yl group, 1,7-phenanthrolin-6-yl group, 1,7-phenanthrolin-8-yl group, 1,7-phenanthrolin-9-yl Group, 1,7-phenanthrolin-10-yl group, 1,8
-Phenanthrolin-2-yl group, 1,8-phenanthrolin-3-yl group, 1,8-phenanthroline-4-
Yl group, 1,8-phenanthrolin-5-yl group, 1,
8-phenanthrolin-6-yl group, 1,8-phenanthrolin-7-yl group, 1,8-phenanthroline-9
-Yl group, 1,8-phenanthroline-10-yl group,
1,9-phenanthrolin-2-yl group, 1,9-phenanthrolin-3-yl group, 1,9-phenanthrolin-4-yl group, 1,9-phenanthrolin-5-yl Group, 1,9-phenanthrolin-6-yl group, 1,9-
Phenanthroline-7-yl group, 1,9-phenanthroline-8-yl group, 1,9-phenanthroline-10-
An yl group, a 1,10-phenanthrolin-2-yl group,
1,10-phenanthrolin-3-yl group, 1,10-
Phenanthrolin-4-yl group, 1,10-phenanthrolin-5-yl group, 2,9-phenanthroline-1-
Yl group, 2,9-phenanthrolin-3-yl group, 2,
9-phenanthrolin-4-yl group, 2,9-phenanthrolin-5-yl group, 2,9-phenanthroline-6
-Yl group, 2,9-phenanthrolin-7-yl group,
2,9-phenanthrolin-8-yl group, 2,9-phenanthrolin-10-yl group, 2,8-phenanthrolin-1-yl group, 2,8-phenanthrolin-3-yl group Group, 2,8-phenanthrolin-4-yl group, 2,8-
Phenanthrolin-5-yl group, 2,8-phenanthrolin-6-yl group, 2,8-phenanthrolin-7-yl group, 2,8-phenanthrolin-9-yl group, 2, 8
-Phenanthrolin-10-yl group, 2,7-phenanthrolin-1-yl group, 2,7-phenanthroline-3
-Yl group, 2,7-phenanthrolin-4-yl group,
2,7-phenanthrolin-5-yl group, 2,7-phenanthrolin-6-yl group, 2,7-phenanthrolin-8-yl group, 2,7-phenanthrolin-9-yl group Group, 2,7-phenanthrolin-10-yl group, 1-phenazinyl group, 2-phenazinyl group, 1-phenothiazinyl group, 2-phenothiazinyl group, 3-phenothiazinyl group, 4-phenothiazinyl group, 10 -Phenothiazinyl group, 1-phenoxazinyl group, 2-phenoxazinyl group, 3-phenoxazinyl group, 4-phenoxazinyl group, 10-phenoxazinyl group, 2-oxazolyl group,
4-oxazolyl group, 5-oxazolyl group, 2-oxadiazolyl group, 5-oxadiazolyl group, 3-flazanyl group, 2-thienyl group, 3-thienyl group, 2-methylpyrrol-1-yl group, 2-methylpyrrole- 3-yl group, 2-methylpyrrol-4-yl group, 2-methylpyrrol-5-yl group, 3-methylpyrrol-1-yl group,
3-methylpyrrol-2-yl group, 3-methylpyrrol-4-yl group, 3-methylpyrrol-5-yl group, 2-
t-butylpyrrol-4-yl group, 3- (2-phenylpropyl) pyrrol-1-yl group, 2-methyl-1-indolyl group, 4-methyl-1-indolyl group, 2-methyl-3-indolyl group Group, 4-methyl-3-indolyl group, 2-t-butyl-1-indolyl group, 4-t-butyl-1-indolyl group, 2-t-butyl-3-indolyl group, 4-t-butyl- Examples thereof include a 3-indolyl group and derivatives thereof, and these can be used alone or in combination of two or more.

Examples of the substituted or unsubstituted aralkyl group include benzyl group, 1-phenylethyl group, 2
-Phenylethyl group, 1-phenylisopropyl group, 2
-Phenylisopropyl group, phenyl-t-butyl group,
α-naphthylmethyl group, 1-α-naphthylethyl group, 2
-Α-naphthylethyl group, 1-α-naphthylisopropyl group, 2-α-naphthylisopropyl group, β-naphthylmethyl group, 1-β-naphthylethyl group, 2-β-naphthylethyl group, 1-β-naphthyl group Isopropyl group, 2-β
-Naphthylisopropyl group, 1-pyrrolylmethyl group, 2
-(1-pyrrolyl) ethyl group, p-methylbenzyl group,
m-methylbenzyl group, o-methylbenzyl group, p-chlorobenzyl group, m-chlorobenzyl group, o-chlorobenzyl group, p-bromobenzyl group, m-bromobenzyl group, o-bromobenzyl group, p- Iodobenzyl group, m
-Iodobenzyl group, o-iodobenzyl group, p-hydroxybenzyl group, m-hydroxybenzyl group, o-hydroxybenzyl group, p-aminobenzyl group, m-aminobenzyl group, o-aminobenzyl group, p-nitro Benzyl group, m-nitrobenzyl group, o-nitrobenzyl group, p-cyanobenzyl group, m-cyanobenzyl group, o
-Cyanobenzyl group, 1-hydroxy-2-phenylisopropyl group, 1-chloro-2-phenylisopropyl group and the like can be mentioned, and these can be used alone or in combination of two or more.

The substituted or unsubstituted amino group is --N
X ¹ X ² is a group represented by, and the substituents X ¹ and X ² are each independently a hydrogen atom, the above-mentioned substituted or unsubstituted alkyl group, a substituted or unsubstituted alkenyl group,
A substituted or unsubstituted cycloalkyl group, a substituted or unsubstituted aromatic hydrocarbon group, a substituted or unsubstituted aromatic heterocyclic group, a substituted or unsubstituted aralkyl group, and the like,
These can be used alone or in combination of two or more.

The substituted or unsubstituted alkoxy group and the substituted or unsubstituted alkoxycarbonyl group are groups represented by -OX ³ and -COOX ⁴ , respectively, and the substituents X ³ and X ⁴ are, for example, The above-mentioned substituted or unsubstituted alkyl group, substituted or unsubstituted cycloalkyl group, substituted or unsubstituted aralkyl group and the like can be mentioned, and these can have one kind alone or two or more kinds in combination.

The substituted or unsubstituted aryloxy group and the substituted or unsubstituted aryloxycarbonyl group are groups represented by -OX ⁵ and -COOX ⁶ , respectively, and the substituents X ⁵ and X ⁶ are, respectively, , For example,
The above-mentioned substituted or unsubstituted aromatic hydrocarbon group, substituted or unsubstituted aromatic heterocyclic group and the like can be mentioned, and these can have one kind alone or two or more kinds in combination.

Further, the substituted or unsubstituted acyl group is -C.
(═O) X ⁷ is a group represented by ( ⁷ ), and examples of the substituent X ⁷ include a hydrogen atom, the above-mentioned substituted or unsubstituted alkyl group, a substituted or unsubstituted alkenyl group, a substituted or unsubstituted cycloalkyl group. A substituted or non-substituted aromatic hydrocarbon group, a substituted or non-substituted aromatic heterocyclic group, a substituted or non-substituted aralkyl group, and the like, which may be used alone or in combination of two or more.

Examples of the divalent group forming a ring include tetramethylene group, pentamethylene group, hexamethylene group, diphenylmethane-2,2'-diyl group, diphenylethane-3,3'-diyl group and diphenyl. Propane
Examples include 4,4′-diyl group, 1,3-butadiene-1,4-diyl group, and derivatives thereof.

Further, in the above-mentioned substituent, one or more atoms may be substituted with a sulfur atom, a silicon atom, a phosphorus atom or a boron atom. Examples of the group substituted with a sulfur atom include a hydroxyl group, a carboxyl group, an alkoxy group, an alkoxycarbonyl group, an aryloxy group, an aryloxycarbonyl group, an acyl group, and other oxygen-containing groups whose oxygen atom is a sulfur atom. Mention may be made of substituted substituents. Examples of the substituents include mercapto group, dithiocarboxyl group, hydroxy (thiocarbonyl) group, mercaptocarbonyl group, methylthio group, methoxythiocarbonyl group, methylthiocarbonyl group, methyldithiocarboxyl group, phenylthio group, phenoxythiocarbonyl group. , Phenylthiocarbonyl group, phenyldithiocarbonyl group, methylthiocarbonyl group, phenylthiocarbonyl group, and the like. Examples of the group substituted with a silicon atom include a substituent in which the carbon atom of the above-mentioned alkyl group, alkenyl group, cycloalkyl group, and aralkyl group is replaced with a silicon atom. Examples of the substituent include a silyl group, a methylsilyl group, a silylmethyl group, an ethylsilyl group, a (methylsilyl) methyl group, a dimethylsilyl group, a trimethylsilyl group, a t-butyldimethylsilyl group, and a triisopropylsilyl group. Examples of the group substituted with a phosphorus atom include a substituent in which the nitrogen atom of the above amino group is replaced with a phosphorus atom. Examples of the substituent include a phosphino group, a trimethylphosphino group, a triphenylphosphino group, and the like. Examples of the group substituted with a boron atom include a substituent in which the nitrogen atom of the above amino group is replaced with a boron atom. Examples of the substituent include a dimethylboryl group and a diphenylboryl group.

The above-mentioned diazine N, N'-dioxide compound in the present invention preferably has as low solubility as possible in the electrolytic solution in order to prevent a decrease in capacity due to the dissolution of this compound in the electrolytic solution, that is, it is hardly soluble or It is preferably insoluble. The solubility of the diazine N, N'-dioxide compound in the electrolytic solution is, for example, 1 gram or less, more preferably 0.5 gram or less, and further preferably 0.5 gram or less, relative to 100 grams of the solvent for the electrolytic solution such as propylene carbonate. It is less than 0.1 gram.

From the viewpoint of solubility in an electrolytic solution, a polyacene type diazine N, N'-dioxide compound having a diazine ring as a terminal ring, an oligomer or a polymer type compound having a structural unit The compound having a diazine ring as a terminal ring preferably has a substituent other than a hydrogen atom at the 2nd and 3rd positions of the terminal diazine ring, such as a methyl group, an ethyl group, an n-propyl group, an isopropyl group, Isobutyl group, n-butyl group, sec-butyl group,
It is more preferable to have a low-polarity substituent such as an alkyl group such as a tert-butyl group.

From the viewpoint of solubility in the electrolytic solution and capacity density, the diazine N, N'-dioxide compound has a condensed ring composed of three or more rings (that is, the general formula (1)). Preferably satisfies n + m + n ′ + m ′ ≧ 2), and mainly has a condensed ring having one or more benzene rings in the condensed ring from the viewpoint of solubility in an electrolytic solution (that is, n + n ′ in the general formula (1)). ≧ 1), and mainly from the viewpoint of capacity density, the condensed ring has a condensed ring having two or more diazine N, N′-dioxide rings (that is, m + m in the general formula (1)). It is preferable that '≧ 1 is satisfied).

The diazine N, N'- in the present invention
From the viewpoint of solubility in an electrolytic solution and capacity density, a dioxide compound has two bonds in a condensed ring of a polyacene type compound represented by the general formula (1) (wherein n + m + n ′ + m ′ ≧ 2). It is preferably an oligomer or polymer compound having a hand-held divalent group as a structural unit.

Regarding the molecular weight of the diazine N, N'-dioxide compound, a high molecular weight is preferable from the viewpoint of solubility in the electrolytic solution, but from the viewpoint of solubility in the reaction solvent during production, N + m + for polyacene type compounds
n '+ m' is preferably 20 or less, and n + m +
n '+ m' is more preferably 10 or less, and the weight average molecular weight (standard sample: polystyrene) of the oligomer or polymer compound is preferably 200,000 or less, more preferably 100,000 or less.

The diazine N, N'-dioxide compound in the present invention can be produced by a known synthetic method such as oxidizing the corresponding diazine compound with a peroxide or a peracid. For example, regarding synthetic methods using urea peroxide, see Synlet, September 1990, 53.
Pages 3-535 (Synlett, P533-535, September 1990)
It is described in. Further, in the case of the compound represented by the following formula (2), a dichloromethane solution of metachloroperbenzoic acid is added to a dichloromethane solution of phenazine and stirred at room temperature, and then a saturated aqueous solution of sodium carbonate is added to neutralize the solution. It can be obtained by purification according to the method.

Diazine N in oligomer or polymer form,
The N'-dioxide compound can be produced, for example, as follows. Condensation of a condensed ring compound having a diazine ring (pyrazine ring) in the condensed ring An oligomer or polymer compound containing a divalent group having two bond hands as a structural unit in the condensed ring is reacted with a peroxide to cause condensation. It can be obtained by N-oxidizing the nitrogen atom in the ring. As another method, a polyacene type diazine N, N '
A dihalide compound in which two of the substituents on the condensed ring of the dioxide compound are halogens can be obtained by dehalogenation by adding a zero-valent nickel compound in an organic solvent.

The diazine N, N'-dioxide compound in the present invention preferably has low solubility in an electrolytic solution as described above, but among the above methods, the polyacene type diazine compound is oxidized to give N. In the method of oxidization, if the condensation degree is too high, the solubility in solvents other than the solvent for the electrolytic solution (solvent used in the preparation reaction) also decreases, making the diazine ring difficult to oxidize or making purification difficult. There is a possibility that a problem such as becoming worn out may occur. If the unoxidized diazine ring remains or impurities remain, the capacity is lowered, so that the condensation degree is preferably within the above range. Similarly, in the method of oxidizing a polymer compound having a condensed ring having a diazine ring in a structural unit to form an N-oxide, if the molecular weight is too high, the diazine ring becomes difficult to oxidize or becomes difficult to purify. It is desirable that the molecular weight be in the above-mentioned range because it may cause a decrease in

Specific examples of the compound having a diazine N, N'-dioxide structure in the present invention include compounds represented by the following formulas (2) to (11) and formulas (12) to (12).
An oligomer or polymer compound having a structural unit represented by (26) can be mentioned.

[0051]

[Chemical 5]

[0052]

[Chemical 6]

[0053]

[Chemical 7]

[0054]

[Chemical 8]

[0055]

[Chemical 9]

[0056]

[Chemical 10]

[0057]

[Chemical 11]

[0058]

[Chemical 12]

[0059]

[Chemical 13]

[0060]

[Chemical 14]

[0061]

[Chemical 15]

[0062]

[Chemical 16]

[0063]

[Chemical 17]

[0064]

[Chemical 18]

[0065]

[Chemical 19]

[0066]

[Chemical 20]

[0067]

[Chemical 21]

[0068]

[Chemical formula 22]

[0069]

[Chemical formula 23]

[0070]

[Chemical formula 24]

[0071]

[Chemical 25]

[0072]

[Chemical formula 26]

[0073]

[Chemical 27]

[0074]

[Chemical 28]

[0075]

[Chemical 29]

[1-2] Other Active Material Materials In the electrode of the present invention, as described above, the diazine N, N′-dioxide compound is used as the active material, and either or both of the positive electrode and the negative electrode of the battery are used. Used as one electrode. The diazine N, N′-dioxide compound has a characteristic that it has excellent capacity density because it has a smaller mass density than a metal oxide-based active material, and is particularly preferably used as a positive electrode active material. .

In the battery of the present invention, the diazine N,
When the N′-dioxide compound is used as the active material of one of the positive electrode and the negative electrode, the following conventionally known materials can be used as the active material of the other electrode. Further, a conventionally known active material may be mixed with a diazine N, N′-dioxide compound and used as a composite active material for both electrodes or one of electrodes.

When a diazine N, N'-dioxide compound is used as the negative electrode active material, metal oxide particles, a disulfide compound, a conductive polymer or the like can be used as the positive electrode active material. As the metal oxide, Li
Lithium manganate such as MnO ₂ , Li _x Mn ₂ O ₄ (0 <x <2) or lithium manganate having a spinel structure, MnO ₂ , LiCoO ₂ , LiNiO ₂ , Li _x V ₂
O ₅ (0 <x <2) and the like can be mentioned. Examples of the disulfide compound include dithioglycol and 2,5-dimercapto-
1,3,4-thiadiazole, S-triazine-2,
Examples of the conductive polymer include polyacetylene, polyphenylene, polyaniline, and polypyrrole. These positive electrode active materials may be used alone or in combination of two or more. Further, such a conventionally known active material may be mixed with the diazine N, N′-dioxide compound to be used as a composite active material.

On the other hand, as the positive electrode active material, the diazine N,
When the N′-dioxide compound is used, examples of the negative electrode active material include graphite, amorphous carbon, lithium metal, lithium alloy, lithium ion storage carbon, and conductive polymer. A combination of two or more species can be used. Further, such a conventionally known active material may be mixed with the diazine N, N′-dioxide compound to be used as a composite active material.

The shape of the active material is not particularly limited. For example, in the case of lithium metal or lithium alloy, in addition to thin film, bulk, powdered, fibrous, and flake. It is possible to use the shape of the like.

[2] Binder In the present invention, in order to strengthen the bond between the active material and other electrode constituent materials, styrene-butadiene latex is mixed as a binder. As the styrene / butadiene latex, any styrene / butadiene latex such as a commercially available product can be appropriately used according to desired characteristics. The styrene-butadiene latex used in the present invention is a latex containing a copolymer of styrene and butadiene as a main component, and the composition ratio of styrene and butadiene, the polymerization conditions, the molecular weight, and the molecular weight distribution are appropriately selected according to desired characteristics. The set one can be used.

The styrene / butadiene latex used in the present invention contains a styrene / butadiene copolymer containing a styrene / butadiene copolymer having a monomer unit copolymerizable with styrene and butadiene. be able to. Examples of the copolymerizable monomer include, for example, methyl (meth) acrylate,
Ethyl (meth) acrylate, propyl (meth) acrylate, butyl (meth) acrylate, acrylic acid, methacrylic acid, and other (meth) acrylic acid-based monomers, itaconic acid, fumaric acid, maleic acid, and other unsaturated dicarboxylic acid-based monomers , (Meth) acrylonitrile, (meth) acrylamide, and the like. Furthermore, styrene-based monomers other than styrene, (meth) acrylic acid ester-based monomers other than the above, conjugated diene-based monomers other than butadiene, and the like are also included.

Commercially available styrene-butadiene latex is usually an emulsion-polymerized SBR prepared by an emulsion-polymerization method.
Are commercially available as solid products and latex products, and have a styrene content of 23.5% by mass.

In the styrene-butadiene latex used in the present invention, as a compounding agent for rubber, a vulcanizing agent such as sulfur or an organic sulfur-containing compound, a vulcanization accelerator, a vulcanization accelerating aid, and a vulcanization retarder. , An antioxidant, a reinforcing agent such as carbon black, a softening agent (plasticizer), a tackifier, a coloring agent, a curing agent, and a dispersant.

Further, other binder may be used in combination within the range in which desired characteristics are obtained. In that case, the amount of styrene-butadiene latex in the binder is preferably 60% by mass or more, more preferably 80% by mass or more, and 90% by mass.
The above is more preferable. Other binders include polyvinylidene fluoride, vinylidene fluoride-hexafluoropropylene copolymer, vinylidene fluoride-tetrafluoroethylene copolymer, polytetrafluoroethylene, polypropylene, polyethylene, resin binders such as polyimide. To be

[3] Conductive Auxiliary Material and Ion Conductive Aid Material In the present invention, a conductive auxiliary material or an ionic conductive auxiliary material is used for the purpose of lowering impedance when forming the electrode containing the diazine N, N′-dioxide compound. You may mix an auxiliary material. Examples of the conductive auxiliary material include carbonaceous fine particles such as graphite, carbon black and acetylene black, and conductive polymers such as polyaniline, polypyrrole, polythiophene, polyacetylene and polyacene. Examples of the ion conduction auxiliary material include gel electrolyte and solid electrolyte.

[4] Catalyst In the present invention, a catalyst that promotes the redox reaction may be mixed with the electrode material in order to carry out the electrode reaction more smoothly. Such catalysts include polyaniline, polypyrrole,
Examples thereof include conductive polymers such as polythiophene, polyacetylene and polyacene, basic compounds such as pyridine derivatives, pyrrolidone derivatives, benzimidazole derivatives, benzothiazole derivatives and acridine derivatives, and metal ion complexes.

[5] Current Collector and Separator In the present invention, as the negative electrode current collector 1 and the positive electrode current collector 6,
A metal foil such as nickel, aluminum, copper, gold, silver, aluminum alloy, stainless steel, a metal flat plate, a mesh electrode, a carbon electrode or the like can be used. Further, such a current collector may have a catalytic effect, or the active material and the current collector may be chemically bonded. In addition, for the purpose of preventing electrical contact between the negative electrode current collector 1 and the positive electrode current collector 6, an insulating packing 2 made of a plastic resin or the like may be arranged between them.

As the separator used to prevent the contact between the positive electrode 5 and the negative electrode 3, a porous film or a non-woven fabric can be used.

[6] Electrolyte In the present invention, the electrolyte is responsible for transporting charge carriers between the electrodes, and generally has an ionic conductivity of 10 ⁻⁵ to 10 ⁻¹ S / cm at room temperature. Is desirable. As the electrolyte in the present invention, for example, an electrolytic solution in which an electrolyte salt is dissolved in a solvent can be used.

As such an electrolyte salt, for example, L
iPF ₆ , LiClO ₄ , LiBF ₄ , LiCF ₃ SO ₃ ,
_{Li (CF 3 SO 2) 2} N, Li (C 2 F 5 SO 2) 2 N, Li (C
Conventionally known materials such as F ₃ SO ₂ ) ₃ C and Li (C ₂ F ₅ SO ₂ ) ₃ C can be used.

As the solvent for the electrolyte salt, for example, ethylene carbonate, propylene carbonate, dimethyl carbonate, diethyl carbonate, methyl ethyl carbonate, γ-butyrolactone, tetrahydrofuran,
Organic solvents such as dioxolane, sulfolane, dimethylformamide, dimethylacetamide and N-methyl-2-pyrrolidone can be used. In the present invention, these solvents can be used alone or as a mixed solvent of two or more kinds.

In the present invention, it is also possible to use a polymer electrolyte. The polymer compound may be used in a gel state containing an electrolytic solution, or the polymer compound itself may be used as a solid electrolyte.

Examples of such a polymer compound include polyvinylidene fluoride, vinylidene fluoride-ethylene copolymer, vinylidene fluoride-monofluoroethylene copolymer, vinylidene fluoride-trifluoroethylene copolymer, vinylidene fluoride. -Tetrafluoroethylene copolymer, vinylidene fluoride-hexafluoropropylene copolymer, vinylidene fluoride-hexafluoropropylene-
Vinylidene fluoride polymer compounds such as tetrafluoroethylene terpolymer; acrylonitrile-methyl methacrylate copolymer, acrylonitrile-ethyl methacrylate copolymer, acrylonitrile-methyl acrylate copolymer, acrylonitrile-ethyl acrylate copolymer, Acrylonitrile-methacrylic acid copolymers, acrylonitrile-acrylic acid copolymers, acrylonitrile-vinyl acetate copolymers and other acrylonitrile polymer compounds; polyethylene oxide, ethylene oxide-propylene oxide copolymers, and their acrylate esters and Methacrylate ester and the like can be used, and they can be used alone or in combination of two or more.

Further, in the present invention, an inorganic solid electrolyte may be used. As the inorganic solid electrolyte, CaF ₂ ,
Examples thereof include AgI, LiF, β-alumina and glass materials.

As the electrolyte of the battery of the present invention, an electrolytic solution and a gel electrolyte are preferable, and an electrolytic solution is particularly preferable, in view of high ion conductivity. When a diazine N, N′-dioxide compound having low solubility in an electrolytic solution is used as an active material, it is preferable to use the electrolytic solution as the electrolyte. On the other hand, when a diazine N, N'-dioxide compound having a relatively high solubility in an electrolytic solution is used as an active material, a solid electrolyte that does not easily dissolve the diazine N, N'-dioxide compound in the electrolyte is used. You may use.

[7] Shape of Battery The shape and appearance of the battery of the present invention are not particularly limited, and conventionally known ones can be adopted. That is, as the shape of such a battery of the present invention, for example, an electrode laminated body or a wound body, a metal case,
Examples include those sealed with a resin case or a laminate film made of a synthetic resin film and a metal foil such as an aluminum foil. In addition, examples of the appearance of the battery include a cylindrical type, a square type, a coin type, and a sheet type.

[8] Laminated Form of Electrode In the present invention, the laminated form of the positive electrode and the negative electrode is not particularly limited, and it may be formed by any laminating method. It is possible to adopt a form in which a laminate and a current collector are laminated on both sides, or a form in which these are wound.

[9] Thickener In the present invention, a thickener may be used for the purpose of improving the uniformity of the slurry during electrode production. Examples of the thickener include polysaccharides such as cellulose, methyl cellulose, hydroxymethyl cellulose, ethyl cellulose, polyvinyl alcohol, polyacrylic acid or a salt thereof, starch phosphate, and casein.

[10] Method of Manufacturing Electrodes and Battery In the present invention, the method of manufacturing electrodes and batteries is not particularly limited, and conventionally known methods can be adopted.

As a method of manufacturing the electrode, a method of adding a solvent to the constituent material of the electrode to form a slurry and applying it to the electrode current collector can be mentioned.

As a method for manufacturing a battery, the prepared electrode is laminated with a counter electrode via a separator, or this is further wound, the obtained product is wrapped in an outer package, and an electrolytic solution is injected to seal it. Etc.

In the production of the battery of the present invention, the diazine N, N'-dioxide compound may be used as it is, or a compound which can be converted into a diazine N, N'-dioxide compound by an electrode reaction may be used. You may use.

[0104]

EXAMPLES The present invention will be specifically described below with reference to examples, but the present invention is not limited to these examples.

Example 1 1.7 g of powder of the diazine N, N'-dioxide compound represented by the formula (5), 0.3 g of acetylene black powder, 0.3 g of artificial graphite powder, and styrene-butadiene latex powder. 40 wt% solution 0.156 g, methylcellulose 2 wt% solution 1.9
g and 0.5 ml of water were mixed and homogenized using a homogenizer to obtain a slurry. 15 mg of the obtained slurry
A thin film was formed on the surface of an aluminum foil (positive electrode current collector) by the doctor blade method, and this was punched out into a circle having a diameter of 12 mm to form an electrode serving as a positive electrode.

Next, the obtained electrode was immersed in an electrolytic solution so that the voids in the electrode were impregnated with the electrolytic solution. As the electrolyte,
Ethylene carbonate / diethyl carbonate mixed solution containing 1 mol / l LiPF ₆ electrolyte salt (mixing ratio 3:
7 (volume ratio) was used. On the electrode impregnated with the electrolytic solution, a porous film separator also impregnated with the electrolytic solution was laminated thereon. Further, a lithium metal plate serving as a negative electrode was laminated, and a copper foil (negative electrode current collector) provided with a frame-shaped insulating packing was laminated. A pressure was applied to the laminated body thus produced by a caulking machine to obtain a sealed coin-type battery.

The coin battery manufactured as described above was used as 0.1
The battery was charged with a constant current of mA, and immediately after the voltage increased to 4.3 V, discharging was performed with a constant current of 0.1 mA. as a result,
During discharging, a voltage flat portion where the voltage was constant at 4.0 V was observed, and it was confirmed that the battery was operating as a battery. Further, charging / discharging was repeated 10 times in the range of 4.3 to 1.5V.
As a result, even if the charging / discharging was repeatedly performed, the voltage was 4.0 V during discharging.
It was confirmed that the voltage was constant in the vicinity, and it was confirmed that this battery was operating as a secondary battery. When the capacity per active material was calculated, it was 150 mAh / g, and the capacity per electrode (excluding the current collector) was 105 mA / g.

(Example 2) Instead of the diazine N, N'-dioxide compound represented by the formula (5) used in Example 1, a diazine N, N'-represented by the formula (9) was used.
An electrode to be a positive electrode was prepared in the same manner as in Example 1 except that the dioxide compound was used, and a battery was prepared in the same manner as in Example 1 except that this electrode was used as a positive electrode.

The battery thus obtained was charged and discharged in the same manner as in Example 1. As a result, a voltage flat portion was recognized around 3.9 V, and it was confirmed that the battery was operating as a battery. Furthermore, when the change in voltage due to repeated charge and discharge for 10 cycles was measured by the same method as in Example 1, a voltage flat portion was observed, and it was confirmed that this battery was operating as a secondary battery.

(Examples 3 and 4) Instead of the diazine N, N'-dioxide compound represented by the formula (5) used in Example 1, a compound represented by the formula (11) in Example 3, In Example 4, except that the compound represented by the formula (24) was used, an electrode to be a positive electrode was produced in the same manner as in Example 1, and the same as in Example 1 except that this electrode was used as the positive electrode. Then, a battery was manufactured.

The obtained battery was charged and discharged in the same manner as in Example 1. As a result, the battery using the compound represented by the formula (11) at the time of discharging was in the vicinity of the formula (2
In the battery using the compound represented by 4), a voltage flat portion was recognized around 4.0V. It was confirmed that the obtained battery was operating as a battery.

Further, when the voltage change due to the repeated charge and discharge of 10 cycles was measured by the same method as in Example 1, a voltage flat portion was observed, and it was confirmed that these batteries can operate as secondary batteries. Was done.

Comparative Example 1 The same procedure as in Example 1 was carried out except that 1.7 g of graphite powder was used instead of the diazine N, N′-dioxide compound represented by the formula (5) used in Example 1. A battery was produced in the same manner as in Example 1 except that an electrode serving as a positive electrode was produced and this electrode was used as a positive electrode.

The battery thus prepared was charged and discharged in the same manner as in Example 1. As a result, a flat voltage portion was not observed during discharge and the voltage dropped rapidly, and the battery did not operate sufficiently.

When a constant current of 0.1 mA was applied to this battery to try to charge it, the voltage instantaneously rose and exceeded 4.5 V. When it was further discharged, the voltage was No flat portion was observed in the curve, confirming that this battery did not operate as a secondary battery.

(Comparative Example 2) 25 mg of the diazine N, N'-dioxide compound represented by the formula (5), 200 mg of graphite powder and 25 mg of polytetrafluoroethylene resin binder as a binder were measured and mixed in an agate mortar. did. The mixture obtained by dry mixing for about 10 minutes,
Rolling was performed under pressure to obtain a thin electrode plate having a thickness of 215 μm. This thin electrode plate was dried in vacuum at 80 ° C. overnight and then punched into a circular shape having a diameter of 12 mm to obtain an electrode.

Next, the obtained electrode was dipped in an electrolytic solution so that the voids in the electrode were impregnated with the electrolytic solution. As the electrolyte,
Ethylene carbonate / diethyl carbonate mixed solution containing 1 mol / l LiPF ₆ electrolyte salt (mixing ratio 3:
7 (volume ratio) was used.

The electrode impregnated with the electrolytic solution was placed on the positive electrode current collector (aluminum foil), and the porous film separator impregnated with the electrolytic solution was laminated thereon. Further, a lithium metal plate serving as a negative electrode was laminated, and a negative electrode current collector provided with a frame-shaped insulating packing was laminated. A pressure was applied to the obtained laminated body by a caulking machine to obtain a sealed coin-type battery.

To the battery produced as described above, an electrode layer containing a diazine N, N'-dioxide compound represented by the formula (5) formed on an aluminum foil was laminated on a positive electrode and a copper foil. Using a lithium metal plate as a negative electrode, 0.
Charging was performed at a constant current of 1 mA, and discharging was performed immediately after the voltage increased to 4.5V. The discharge current was 0.1 mA, which was the same as during charging. As a result, a voltage flat portion was recognized around 4.0 V, and it was confirmed that the battery was operating as a battery. Calculated capacity per active material 140 mAh
/ G, and the capacity per electrode of the positive electrode (excluding the current collector) was 14 mAh / g.

Comparative Example 3 A positive electrode was prepared in the same manner as in Example 1 except that 25 mg of LiCoO ₂ was used instead of the diazine N, N′-dioxide compound represented by the formula (5) used in Comparative Example 2. A battery was prepared in the same manner as in Example 1 except that an electrode for forming the electrode was prepared and this electrode was used as the positive electrode.

The battery produced as described above was charged and discharged in the same manner as in Example 1 and the capacity per active material was calculated to be 96 mAh / g.

[0122]

According to the present invention, the capacity density is high by using the diazine N, N'-dioxide compound as the active material of the electrode and the styrene-butadiene latex as the main component of the binder, and A battery having excellent charge / discharge stability can be obtained.

[Brief description of drawings]

FIG. 1 is an explanatory diagram showing an example of the configuration of a battery of the present invention.

[Explanation of symbols]

1 Negative electrode current collector 2 Insulating packing 3 Negative electrode 4 separator 5 Positive electrode 6 Positive electrode current collector

   ─────────────────────────────────────────────────── ─── Continued front page    (72) Inventor Jiro Iriyama             5-7 Shiba 5-1, Minato-ku, Tokyo NEC Corporation             Inside the company (72) Inventor Kentaro Nakahara             5-7 Shiba 5-1, Minato-ku, Tokyo NEC Corporation             Inside the company (72) Inventor Masahiro Suguro             5-7 Shiba 5-1, Minato-ku, Tokyo NEC Corporation             Inside the company (72) Inventor Masaharu Sato             5-7 Shiba 5-1, Minato-ku, Tokyo NEC Corporation             Inside the company F term (reference) 5H029 AJ02 AJ03 AK02 AK03 AK15                       AK16 AK18 AL06 AL07 AL08                       AL12 AL15 AL16 AL18 AM02                       AM03 AM07 AM16 BJ03 DJ08                       EJ14                 5H050 AA02 AA08 BA06 BA07 BA16                       BA17 BA18 CA05 CA08 CA09                       CA19 CA20 CB07 CB08 CB09                       CB12 DA11 EA23 EA26 EA28

Claims (7)

[Claims] 1. A compound containing a compound represented by the following general formula (1) having a diazine N, N′-dioxide structure as an electrode active material, and the electrode active material containing styrene-butadiene latex as a main component. An electrode characterized by being bound by a binder. [Chemical 1] [In the formula, n, m, n ′ and m ′ each independently represent an integer of 0 or more. The order of condensation of the diazine ring and the benzene ring may be alternating or random. Further, the substituents R ₁ , R ₂ , R ₃ , R ₄ , R ^a , R ^b , R ^c and R ^d.
Are each independently a hydrogen atom, halogen atom, hydroxyl group, nitro group, nitroso group, cyano group, carboxyl group, substituted or unsubstituted alkyl group, substituted or unsubstituted alkenyl group, substituted or unsubstituted cycloalkyl A group, a substituted or unsubstituted aromatic hydrocarbon group,
A substituted or unsubstituted aromatic heterocyclic group, a substituted or unsubstituted aralkyl group, a substituted or unsubstituted amino group,
A substituted or unsubstituted alkoxy group, a substituted or unsubstituted aryloxy group, a substituted or unsubstituted alkoxycarbonyl group, a substituted or unsubstituted aryloxycarbonyl group, or a substituted or unsubstituted acyl group is shown. However, when n is 2 or more, R ^a and R ^b may be the same or different, and when n ′ is 2 or more, R ^c and R ^d are the same or different. Good. In addition, one or more atoms of these substituents may be substituted with a sulfur atom, a silicon atom, a phosphorus atom, or a boron atom, and the substituents may form a ring structure. ] 2. Substituents R ₁ , R ₂ , R ₃ , R ₄ , R ^a , R ^b , R ^{c of} a compound represented by the following general formula (1) having a diazine N, N′-dioxide structure and instead of the two substituents contain oligomeric or polymeric compounds having a divalent group having two bonds as a structural unit as an electrode active material, and the electrode active material is a styrene-butadiene latex mainly composed of R ^d An electrode characterized by being bound by a binding agent of [Chemical 2] [In the formula, n, m, n ′ and m ′ each independently represent an integer of 0 or more. The order of condensation of the diazine ring and the benzene ring may be alternating or random. Further, the substituents R ₁ , R ₂ , R ₃ , R ₄ , R ^a , R ^b , R ^c and R ^d.
Are each independently a hydrogen atom, halogen atom, hydroxyl group, nitro group, nitroso group, cyano group, carboxyl group, substituted or unsubstituted alkyl group, substituted or unsubstituted alkenyl group, substituted or unsubstituted cycloalkyl A group, a substituted or unsubstituted aromatic hydrocarbon group,
A substituted or unsubstituted aromatic heterocyclic group, a substituted or unsubstituted aralkyl group, a substituted or unsubstituted amino group,
A substituted or unsubstituted alkoxy group, a substituted or unsubstituted aryloxy group, a substituted or unsubstituted alkoxycarbonyl group, a substituted or unsubstituted aryloxycarbonyl group, or a substituted or unsubstituted acyl group is shown. However, when n is 2 or more, R ^a and R ^b may be the same or different, and when n ′ is 2 or more, R ^c and R ^d are the same or different. Good. In addition, one or more atoms of these substituents may be substituted with a sulfur atom, a silicon atom, a phosphorus atom, or a boron atom, and the substituents may form a ring structure. ] 3. The compound having a diazine N, N′-dioxide structure according to claim 1 or the oligomer or polymer compound according to claim 2 is used as a reaction starting material, a product or at least a discharge reaction in an electrode reaction. An electrode characterized by being contained as an intermediate product. 4. A battery comprising the electrode according to claim 1, 2 or 3 as a positive electrode and / or a negative electrode. 5. A battery comprising the electrode according to claim 1, 2 or 3 as a positive electrode. 6. A battery comprising the electrode according to claim 1, 2 or 3 as a positive electrode and / or a negative electrode. 7. The battery according to claim 6, wherein the secondary battery is a lithium secondary battery.