JPH113728A - Nonaqueous electrolyte secondary battery - Google Patents

Abstract

PROBLEM TO BE SOLVED: To increase discharge capacity and to enhance charge/discharge cycle characteristics by including at least one kind of organic boron compounds. SOLUTION: Organic boron compounds are characterized by B(R<1> )(R<2> )(R<3> ). R<1> , R<2> , R<3> may be identical, and each of them represents a hydrogen atom, alkyl group, cycloalkyl group, alkoxy group, alkenyl group, alkinyl group, aralkyl group, aryl group, halogen atom, cyano group or a hydroxy group. In the case that the organic boron compound is contained in an electrode active material, a content of 0.01-5 wt.% with respect to the weight of the active material is preferable, and in the case that it is contained in an electrolyte, a content of 0.0001-0.1 mole/l with respect to the volume of the electrolyte solvent is preferable, and a content of 0.001-10 wt.% with respect to the weight of a supporting salt contained in the electrolyte is preferable.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a high-capacity non-aqueous electrolyte secondary battery having excellent charge-discharge cycle characteristics, wherein the negative electrode material is mainly composed of an amorphous chalcogen compound and
Also, the present invention relates to improvement of charge / discharge characteristics such as charge / discharge cycle life of a nonaqueous electrolyte secondary battery having a large discharge capacity, which is an amorphous oxide.

[0002]

2. Description of the Related Art In recent years, the development of portable electronic devices has been accelerated by the practical use of high-voltage, high-capacity lithium secondary batteries.
The demand for lithium secondary batteries is increasing more and more. A high-voltage, high-capacity lithium secondary battery was realized by using a material capable of inserting and releasing lithium for the negative electrode and using a composite oxide of lithium and a transition metal for the positive electrode. Improvements are still desired in this regard.
Attempts to improve the cycle characteristics have been made in various fields for some time.Especially since the reaction involving the electrolyte is observed during the charge / discharge cycle, the solvent composition of the electrolyte and the type of the supporting salt have been studied. . Attempts have also been made to prevent the decomposition of the electrolyte and extend the cycle life by adding a small amount of additives to the electrolyte. For example, JP
JP-A-9-3874, JP-A-63-269461 and JP-A-8-321313 disclose borate esters such as trimethyl borate, and JP-A-3-236169 discloses a silylated borate ester. It is described that these are added to an electrolytic solution and used. However, even with the use of the above-mentioned technology, it has not yet reached a level where both high discharge capacity and excellent cycle characteristics can be achieved.

[0003]

An object of the present invention is to provide a nonaqueous electrolyte secondary battery having a large discharge capacity and excellent charge / discharge cycle characteristics.

[0004]

SUMMARY OF THE INVENTION An object of the present invention is to provide a positive electrode and a negative electrode containing a material capable of reversibly inserting and extracting lithium,
A non-aqueous electrolyte secondary battery comprising a non-aqueous electrolyte containing a lithium salt and a separator, wherein the non-aqueous electrolyte secondary battery comprises at least one organic boron compound.

[0005]

DESCRIPTION OF THE PREFERRED EMBODIMENTS Preferred embodiments of the present invention will be described below, but the present invention is not limited to these.

(1) In a non-aqueous electrolyte secondary battery comprising a positive electrode and a negative electrode containing a material capable of reversibly storing and releasing lithium, a non-aqueous electrolyte containing a lithium salt, and a separator, at least one battery is contained in the battery. A non-aqueous electrolyte secondary battery comprising a kind of organic boron compound. (2) The nonaqueous electrolyte secondary battery according to item 1, wherein the organic boron compound is a compound represented by the following general formula (1). General formula (1)

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In the formula, R ¹ , R ² and R ³ may be the same or different and each represents a hydrogen atom, an alkyl group, a cycloalkyl group, an alkoxy group, an alkenyl group, an alkynyl group, an aralkyl group, an aryl group, a halogen atom. Atom, cyano group, hydroxy group, formyl group, aryloxy group,
Alkylthio group, arylthio group, acyloxy group, sulfonyloxy group, amino group, alkylamino group, arylamino group, carbonamide group, sulfonamide group,
Oxycarbonylamino group, oxysulfonylamino group, ureido group, acyl group, oxycarbonyl group, carbamoyl group, sulfonyl group, sulfinyl group, oxysulfonyl group or sulfamoyl group, carboxylic acid group, sulfonic acid group, phosphonic acid group, heterocyclic ring Group, -B (R ¹¹ )
^{(R 12), - OB (} R 11) (R 12), OSi (R 11)
(R ¹² ) (R ¹³ ) and OSn (R ¹¹ ) (R ¹² ) (R ¹³ ). R ¹¹ , R ¹² and R ¹³ may be the same or different, and each represents a hydrogen atom, an alkyl group, a cycloalkyl group, an alkoxy group, an alkenyl group, an alkynyl group, an aralkyl group, an aryl group, a halogen atom, a cyano group, a nitro group. Group, hydroxy group, formyl group, aryloxy group,
Alkylthio group, arylthio group, acyloxy group, sulfonyloxy group, amino group, alkylamino group, arylamino group, carbonamide group, sulfonamide group,
Oxycarbonylamino group, oxysulfonylamino group, ureido group, acyl group, oxycarbonyl group, carbamoyl group, sulfonyl group, sulfinyl group, oxysulfonyl group or sulfamoyl group, carboxylic acid group, sulfonic acid group, phosphonic acid group, heterocyclic ring Represents a group. In addition, R ¹ , R ² , R ³ , R ¹¹ , R ¹² and R ¹³ may be bonded to each other to form a ring, and this ring may have a substituent. Further, each group may be substituted by a substitutable group. (3) The nonaqueous electrolyte secondary battery according to item 1, wherein the organic boron compound is a compound represented by the following general formula (2). General formula (2)

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In the formula, X ¹ , X ² and X ³ may be the same or different from each other and represent a hetero atom (excluding an oxygen atom). R ²¹ , R ²² and R ²³ may be the same or different and each is a hydrogen atom, an alkyl group, a cycloalkyl group, an alkoxy group, an alkenyl group, an alkynyl group, an aralkyl group, an aryl group, a halogen atom, a cyano group, a hydroxy group A, formyl group, aryloxy group, alkylthio group, arylthio group, acyloxy group, sulfonyloxy group, amino group, alkylamino group, arylamino group, carbonamide group, sulfonamide group, oxycarbonylamino group, oxysulfonylamino group, Ureido group, acyl group, oxycarbonyl group, carbamoyl group,
Sulfonyl group, sulfinyl group, oxysulfonyl group or sulfamoyl group, carboxylic acid group, sulfonic acid group,
Represents a phosphonic acid group or a heterocyclic group. R ²¹ , R ²² and R ²³
May combine with each other to form a ring, and this ring may have a substituent. Further, each group may be substituted by a substitutable group. x, y and z represent an integer of 1 to 5. When x, y and z are 2 or more, a plurality of R ²¹ , R ²² and R ²³ may be the same or different. k, m and n represent 0 or an integer. However, at least one of k, m, and n is 1 or more. (4) The nonaqueous electrolytic secondary battery according to item 1, wherein the organic boron compound is a compound represented by the following general formula (3). General formula (3)

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In the formula, R ³¹ , R ³² and R ³³ each represent an alkyl group or an aryl group. (5) The nonaqueous electrolytic secondary battery according to item 1, wherein the organic boron compound is a compound represented by the following general formula (4). General formula (4)

[0013]

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In the formula, R ⁴¹ , R ⁴² and R ⁴³ each represent an alkyl group or an alkoxy group. (6) The nonaqueous electrolytic secondary battery according to item 1, wherein the organic boron compound is a compound represented by the following general formula (5). General formula (5)

[0015]

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In the formula, Ar ¹ , Ar ² and Ar ³ each represent an aryl group. (7) The composition containing the organic boron compound is a non-aqueous electrolyte containing a lithium salt.
7. The non-aqueous electrolyte secondary battery according to 6. (8) The content of at least one organic boron compound contained in the non-aqueous electrolyte is 0.001% by weight to 10% by weight based on the supporting salt contained in the electrolyte. 3. The non-aqueous electrolyte secondary battery according to 1. (9) The supporting salt according to item 8, wherein at least LiBF ₄
And / or LiPF ₆ . (10) The nonaqueous electrolyte secondary battery according to any one of Items 1 to 9, wherein the solvent of the nonaqueous electrolyte comprises at least one kind of cyclic carbonate and at least one kind of chain carbonate. (11) The nonaqueous electrolyte secondary battery according to any one of items 1 to 10, wherein the negative electrode is a carbonaceous material capable of inserting and extracting lithium. (12) The negative electrode comprises a negative electrode material mainly composed of an amorphous chalcogen compound and / or an amorphous oxide containing three or more types of atoms selected from Group 1, 2, 13, 14, and 15 atoms of the periodic table. Item 10. The non-aqueous electrolyte secondary battery according to any one of Items 1 to 10. (13) The non-aqueous electrolyte secondary battery according to item 12, wherein at least one of the negative electrode materials is represented by the general formula (6). M ¹ M ² pM ⁴ qM ⁶ r General formula (6) (where M ¹ and M ² are different from each other, Si, Ge, Sn, P
at least one selected from b, P, B, Al, and Sb;
M ⁴ is Li, Na, K, Rb, Cs, Mg, Ca, S
at least one selected from r and Ba, M ⁶ is O, S,
At least one selected from Te, p and q are each 0.0
01 to 10, r represents a number of 1.00 to 50. )

The organic boron compound used in the present invention is described, for example, in H. Steinberg, "Organoboron Chemis".
try, Vol 1-3, Wiley & Sons Inc., New York (1964).

Hereinafter, the compound represented by formula (1) will be described in detail. In the general formula (1), R ¹ , R ² , and R ³ may be the same or different from each other;
Alkyl group (preferably having 1 to 16 carbon atoms, for example, methyl, ethyl, propyl, dodecyl) cycloalkyl group (preferably having 3 to 9 carbon atoms, for example, cyclopropyl, cyclohexyl), and alkoxy group (preferably, Those having 1 to 16 carbon atoms, for example, methoxy, ethoxy, 2-methoxyethoxy), alkenyl groups (preferably having 2 to 16 carbon atoms, for example, vinyl, allyl, cyclohexenyl), and alkynyl groups (preferably, carbon number 2
~ 16 things. For example, ethynyl, 2-propenyl, hexadecynyl), an aralkyl group (preferably having 7 to 7 carbon atoms)
16 things. For example, benzyl, diphenylmethyl, naphthylmethyl), an aryl group (preferably having 6 to 1 carbon atoms)
6 things. For example, phenyl, naphthyl, anthryl), halogen atom (for example, chlorine atom, bromine atom, and fluorine atom), cyano group, nitro group, hydroxy group, formyl group, aryloxy group (preferably having 6 to 16 carbon atoms)
Stuff. For example, phenoxy), an alkylthio group (preferably having 1 to 16 carbon atoms; for example, methylthio, octylthio-2-phenoxyoctylthio), an arylthio group (preferably having 6 to 16 carbon atoms, for example, phenylthio), acyloxy Group (preferably having 1 to
12 things. For example, acetoxy), a sulfonyloxy group (preferably having 1 to 12 carbon atoms; for example, methanesulfonyloxy, benzenesulfonyloxy), an amino group, an alkylamino group (preferably having 1 to 32 carbon atoms, for example, methyl) Amino, butylamino), an arylamino group (preferably having 6 to 32 carbon atoms, for example, phenylamino), a carbonamide group (for example, acetylamino, propanoylamino), a sulfonamide group (for example, methanesulfonamide, Benzenesulfonamide), oxycarbonylamino group (eg, methoxycarbonylamino), oxysulfonylamino group (eg, ethoxysulfonylamino), ureido group (eg, phenylureido, methylureido), acyl group (preferably having 1 to 1 carbon atoms) 12 things For example, acetyl, benzoyl, pivaloyl), oxycarbonyl group (eg, methoxycarbonyl), carbamoyl group (eg, N-ethylcarbamoyl, N-benzylcarbamoyl), sulfonyl group (eg, methanesulfonyl, benzenesulfonyl), sulfinyl group ( For example, methanesulfinyl), oxysulfonyl group (for example, methoxysulfonyl) or sulfamoyl group (N-ethylsulfamoyl), carboxylic acid group or salt thereof, sulfonic acid group or salt thereof, phosphonic acid group or salt thereof, heterocyclic ring Group (preferably of 5 or 6 members), -B (R ¹¹ ) (R
^{12), - OB (R 11} ) (R 12), OSi (R 11)
(R ¹² ) (R ¹³ ) and OSn (R ¹¹ ) (R ¹² ) (R ¹³ ) [R ¹¹ , R ¹² and R ¹³ may be the same or different from each other, and each represents a hydrogen atom or an alkyl group (preferably Is a group having 1 to 16 carbon atoms, a cycloalkyl group (preferably having 3 to 9 carbon atoms), an alkoxy group (preferably having 1 carbon atom)
To 16), an alkenyl group (preferably having 2 to 2 carbon atoms)
16), an alkynyl group (preferably having 2 to 1 carbon atoms)
6), an aralkyl group (preferably having 7 to 16 carbon atoms)
Group), an aryl group (preferably having 6 to 16 carbon atoms), a halogen atom, a cyano group, a nitro group, a hydroxy group, a formyl group, an aryloxy group (preferably having 6 to 16 carbon atoms), an alkylthio group (Preferably having 1 to 16 carbon atoms), an arylthio group (preferably having 6 to 16 carbon atoms), an acyloxy group (preferably having 1 to 12 carbon atoms), a sulfonyloxy group (preferably having 1 to 16 carbon atoms) 12), amino group, alkylamino group (preferably having 1 to 32 carbon atoms), arylamino group (preferably having 6 to 32 carbon atoms), carbonamido group, sulfonamido group, oxycarbonylamino group ,
An oxysulfonylamino group, a ureido group, an acyl group (preferably having 1 to 12 carbon atoms), an oxycarbonyl group, a carbamoyl group, a sulfonyl group, a sulfinyl group,
An oxysulfonyl group or a sulfamoyl group, a carboxylic acid group, a sulfonic acid group, a phosphonic acid group, or a heterocyclic group (preferably having 5 or 6 members)]. Also, R ¹ , R
² , R ³ , R ¹¹ , R ¹² and R ¹³ may combine with each other to form a ring, and this ring may have a substituent. Unless otherwise specified, each group in the present specification may be substituted with a substituent when it can be substituted.

Further, R ¹ , R ² and R ³ may be the same or different, and each is an alkyl group, a cycloalkyl group, an aralkyl group, an aryl group, an alkylthio group, an arylthio group, an alkylamino group, an arylamino group, An aryloxy group or an alkoxy group is more preferable, and an aryl group, an arylthio group, an arylamino group,
Particularly preferred is an aryloxy group or an alkoxy group.

Hereinafter, the compound represented by formula (2) will be described in detail. In the general formula (2), X ¹ , X ² and X
³ may be the same or different, and represents a hetero atom (excluding an oxygen atom). R ²¹ , R ²² and R ²³ may be the same or different and each represents a hydrogen atom or an alkyl group (preferably having 1 to 16 carbon atoms, for example, methyl,
Ethyl, propyl, dodecyl) cycloalkyl group (preferably having 3 to 9 carbon atoms, for example, cyclopropyl,
Cyclohexyl), an alkoxy group (preferably having 1 carbon atom)
~ 16 things. For example, methoxy, ethoxy, 2-methoxyethoxy), alkenyl group (preferably having 2 to 2 carbon atoms)
16 things. For example, vinyl, allyl, cyclohexenyl), alkynyl group (preferably having 2 to 16 carbon atoms, for example, ethynyl, 2-propenyl, hexadecynyl), aralkyl group (preferably having 7 to 16 carbon atoms, for example, benzyl, Diphenylmethyl, naphthylmethyl), aryl group (preferably having 6 to 16 carbon atoms, for example, phenyl, naphthyl, anthryl), halogen atom (for example, chlorine atom, bromine atom, and fluorine atom), cyano group, nitro group, Hydroxy group, formyl group, aryloxy group (preferably having 6 to 16 carbon atoms, for example, phenoxy), alkylthio group (preferably having 1 to 16 carbon atoms, for example, methylthio, octylthio-2-phenoxyoctylthio) And an arylthio group (preferably having 6 to 16 carbon atoms. , Phenylthio), an acyloxy group (preferably having 1 to 12 carbon atoms
Stuff. For example, acetoxy), a sulfonyloxy group (preferably having 1 to 12 carbon atoms; for example, methanesulfonyloxy, benzenesulfonyloxy), an amino group, an alkylamino group (preferably having 1 to 32 carbon atoms, for example, methyl) Amino, butylamino) and arylamino groups (preferably having 6 to 32 carbon atoms. For example,
Phenylamino), a carbonamide group (eg, acetylamino, propanoylamino), a sulfonamide group (eg, methanesulfonamide, benzenesulfonamide), an oxycarbonylamino group (eg, methoxycarbonylamino), an oxysulfonylamino group ( For example, ethoxysulfonylamino), ureido group (for example, phenylureide, methylureide), acyl group (preferably having 1 to 12 carbon atoms, for example, acetyl, benzoyl, pivaloyl), oxycarbonyl group (for example, methoxycarbonyl) Carbamoyl group (eg, N-ethylcarbamoyl, N-benzylcarbamoyl), sulfonyl group (eg, methanesulfonyl, benzenesulfonyl), sulfinyl group (eg, methanesulfinyl), oxysulfur A carboxylate group or a salt thereof, a sulfonic acid group or a salt thereof, a phosphonic acid group or a salt thereof, a heterocyclic group (preferably 5 or 6) or a phenyl group (for example, methoxysulfonyl) or a sulfamoyl group (N-ethylsulfamoyl). Member's). R ²¹ , R ²²
And R ²³ may combine with each other to form a ring, and this ring may have a substituent. Further, each group may be substituted by a substitutable group. x, y and z represent an integer of 1 to 5. when x, y and z are 2 or more,
²¹ , R ²² and R ²³ may be the same or different.
k, m and n represent 0 or an integer. Where k,
At least one of m and n is 1 or more.

Further, X ¹ , X ² and X ³ may be the same or different from each other, and are each sulfur, nitrogen, phosphorus, silicon,
Tin and boron are more preferable, and sulfur, nitrogen, phosphorus and boron are particularly preferable. R ²¹ , R ²² and R ²³ may be the same or different, and each is preferably an alkyl group or an aryl group. Most preferably, X ¹ , X ² and X ³ are sulfur, nitrogen, phosphorus, boron and R ²¹ ,
This is the case where R ²² and R ²³ are an alkyl group or an aryl group.

The compound represented by formula (3) will be described in more detail. In the general formula (3), R ³¹ and R ³²
And R ³³ is an alkyl group (preferably having 1 to 16 carbon atoms, such as methyl, ethyl, butyl, dodecyl, cyclohexyl, trifluoromethyl, etc.) or a substituted or unsubstituted aryl group (preferably having 6 to 16 carbon atoms).
16 things. For example, a phenyl group, a naphthyl group, an anthryl group, etc.). Of these, a substituted or unsubstituted phenyl group is preferred. Examples of the substituent include an alkyl group (eg, methyl, ethyl, butyl, dodecyl, cyclohexyl, trifluoromethyl, etc.), an aryl group (eg, phenyl, naphthyl, anthryl, etc.), an alkoxy group (eg, methoxy, ethoxy, dodecyloxy, benzyl) Oxy, phenoxy, etc.), halogen atoms (eg, chlorine atom, bromine atom, fluorine atom, etc.), cyano group, nitro group and the like.

The compound represented by formula (4) will be described in more detail. In the general formula (4), R ⁴¹ and R ⁴²
And R ⁴³ is an alkyl group (preferably having 1 to 16 carbon atoms, such as methyl, ethyl, butyl, dodecyl, cyclohexyl, trifluoromethyl and the like), an alkoxy group [preferably having 1 to 16 carbon atoms. Methoxy, ethoxy, dodecyloxy, benzyloxy group, substituted or unsubstituted phenoxy and the like. Examples of the substituent include an alkyl group (for example, methyl, ethyl, butyl, dodecyloxy,
Cyclohexyl, trifluoromethyl, etc.), aryl group (eg, phenyl, naphthyl, anthryl, etc.), alkoxy group (eg, methoxy, ethoxy, dodecyloxy, benzyloxy, phenoxy, etc.), halogen atom (eg, chlorine atom, bromine atom, fluorine atom) ), A cyano group, a nitro group and the like. ].

The compound represented by formula (5) will be described in more detail. In the general formula (5), Ar ¹ and A
r ² and Ar ³ may be the same or different, and each represents a substituted or unsubstituted aryl group (preferably having 6 to 1 carbon atoms).
6 things. For example, a phenyl group, a naphthyl group, an anthryl group, etc.). Of these, a substituted or unsubstituted phenyl group is preferred. Examples of the substituent include an alkyl group (for example, methyl, ethyl, butyl, dodecyl, cyclohexyl, trifluoromethyl and the like), an aryl group (for example,
Phenyl, naphthyl, anthryl, etc.), alkoxy group (eg, methoxy, ethoxy, dodecyloxy, benzyloxy, phenoxy, etc.), halogen atom (eg, chlorine atom, bromine atom, fluorine atom, etc.), cyano group, nitro group, etc. .

Specific examples of the compound of the present invention are shown below, but the scope of the present invention is not limited only to these.

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[0030]

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[0031]

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[0032]

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[0033]

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[0034]

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[0035]

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[0036]

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[0037]

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[0038]

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The organoboron compound of the present invention may be contained in any part of the battery. Preferably, it is in the electrode active material or in the electrolytic solution. When contained in the electrode, the content is preferably 0.01 to 5% by weight, more preferably 0.1 to 2% by weight, based on the active material of the electrode. When contained in the electrolytic solution, the content of the compound is preferably from 0.0001 to 0.1 mol / l, more preferably from 0.001 to 0.1 mol / l, based on the solvent of the electrolytic solution.
The content of the compound with respect to the supporting salt contained in the electrolytic solution is preferably from 0.001% by weight to 10% by weight,
0.01 to 5% by weight is more preferred.

The electrolyte generally comprises a solvent and a supporting salt dissolved in the solvent, and is preferably a lithium salt (anion and lithium cation). Examples of the solvent for the electrolytic solution that can be used in the present invention include propylene carbonate, ethylene carbonate, butylene carbonate, dimethyl carbonate, diethyl carbonate, methyl ethyl carbonate, γ-butyrolactone, methyl formate, methyl acetate, and methyl acetate.
1,2-dimethoxyethane, tetrahydrofuran, 2-
Methyltetrahydrofuran, dimethylsulfoxide,
1,3-dioxolan, formamide, dimethylformamide, dioxolan, dioxane, acetonitrile,
Aprotic such as nitromethane, ethyl monoglyme, phosphoric acid triester, trimethoxymethane, dioxolane derivative, sulfolane, 3-methyl-2-oxazolidinone, propylene carbonate derivative, tetrahydrofuran derivative, ethyl ether, 1,3-propane sultone Organic solvents can be mentioned, and one kind or a mixture of two or more kinds can be used. Of these, carbonate-based solvents are preferred, and those containing cyclic carbonate and / or non-cyclic carbonate are preferred. As the cyclic carbonate, ethylene carbonate and propylene carbonate are preferable. In addition, the non-cyclic carbonate preferably contains diethyl carbonate, dimethyl carbonate, and methyl ethyl carbonate. Examples of lithium salts soluble in these solvents that can be used in the present invention include LiClO ₄ , LiBF ₄ , L
iPF ₆ , LiCF ₃ SO ₃ , LiCF ₃ CO ₂ , Li
AsF ₆ , LiSbF ₆ , LiB ₁₀ Cl ₁₀ , lithium lower aliphatic carboxylate, LiAlCl ₄ , LiCl, Li
Li salts such as Br, LiI, lithium chloroborane and lithium tetraphenylborate can be used, and one or more of these can be used in combination.
Among them, those in which LiBF ₄ and / or LiPF ₆ are dissolved are preferable. The concentration of the supporting salt is not particularly limited, but is preferably 0.2 to 3 mol per liter of the electrolytic solution. Examples of the electrolyte that can be used in the present invention include LiCF ₃ SO ₃ , L in an electrolyte obtained by appropriately mixing ethylene carbonate, propylene carbonate, 1,2-dimethoxyethane, dimethyl carbonate, or diethyl carbonate.
An electrolyte containing iClO ₄ , LiBF ₄ and / or LiPF ₆ is preferred. Particularly, a mixed solvent of propylene carbonate or ethylene carbonate with 1,2-dimethoxyethane and / or diethyl carbonate is used to prepare LiCF ₃ SO ₃ , LiClO ₄ , LiBF ₄ and / or LiCF ₃ SO ₃ .
Alternatively, an electrolyte containing LiPF ₆ is preferable, and particularly, an electrolyte containing at least ethylene carbonate and LiPF ₆ is preferable. The amount of these electrolytes to be added to the battery is not particularly limited, but can be used in a required amount depending on the amounts of the positive electrode active material and the negative electrode material and the size of the battery.

Hereinafter, other materials and a method of manufacturing the non-aqueous electrolyte secondary battery of the present invention will be described in detail. The positive and negative electrodes used in the non-aqueous electrolyte secondary battery of the present invention can be prepared by applying a positive electrode mixture or a negative electrode mixture on a current collector. The positive electrode or negative electrode mixture can contain a conductive agent, a binder, a dispersant, a filler, an ionic conductive agent, a pressure enhancer, and various additives, respectively, in addition to the positive electrode active material or the negative electrode material.

One of the negative electrode materials used in the present invention is a carbonaceous material capable of inserting and extracting lithium. The carbonaceous material is a material substantially composed of carbon, such as petroleum pitch, natural graphite, artificial graphite, non-graphitizable carbon, mesocarbon microbeads, PAN-based carbon fiber, cellulose-based carbon fiber, and pitch-based carbon fiber. , Vapor-grown carbon fiber, dehydrated PVA-based carbon fiber, lignin carbon fiber, glassy carbon fiber, activated carbon fiber and the like.

Another negative electrode material used in the present invention is an oxide of a metal or semi-metal group or chalcogen, and it is preferable that the material is mainly amorphous when the battery is incorporated. The term “amorphous” as used herein refers to a substance having a broad scattering band having a peak at 20 ° to 40 ° in 2θ value by X-ray diffraction using CuKα ray, and having a crystalline diffraction line. Is also good. Preferably 40 ° or more and 70 ° in 2θ value
Among the crystalline diffraction lines shown below, the strongest intensity is 2
It is preferably 500 times or less, more preferably 100 times or less, particularly preferably 5 times or less, the diffraction line intensity of the peak of the broad scattering band seen at 20 ° or more and 40 ° or less in θ value, Most preferably, it has no crystalline diffraction lines.

The negative electrode material used in the present invention is preferably represented by the following general formula (6). M ¹ M ² pM ⁴ qM ⁶ r General formula (6) In the formula, M ¹ and M ² are different from each other, Si, Ge, Sn, Pb,
It is at least one selected from P, B, Al, and Sb, preferably Si, Ge, Sn, P, B, and Al, and particularly preferably Si, Sn, P, B, and Al.
M ⁴ is Li, Na, K, Rb, Cs, Mg, Ca, S
at least one selected from r and Ba, preferably K, Cs, Mg and Ca, particularly preferably Cs and Mg
It is. M ⁶ is at least one selected from O, S and Te, preferably O and S, and particularly preferably O
It is. p and q are each 0.001 to 10, preferably 0.01 to 5, and particularly preferably 0.01 to 2;
It is. r is 1.00 to 50, preferably 1.0
0 to 26, and particularly preferably 1.02 to 6.
The valences of M ¹ and M ² are not particularly limited, and may be a single valence or a mixture of each valence. Also M
^1, M ^2, the ratio of M ⁴ can be continuously changed in a range M ² and M ⁴ are from 0.001 to 10 molar equivalents relative to M ^1, the amount of M ⁶ accordingly (formula ( 1)
, The value of r) also changes continuously.

Among the compounds mentioned above, in the present invention, it is preferable that M ¹ is Sn, and the compound represented by the general formula (7)
It is represented by SnM ³ pM ⁵ qM ⁷ r General formula (7) In the formula, M ³ is at least one selected from Si, Ge, Pb, P, B, and Al, preferably Si, Ge,
P, B, Al, particularly preferably Si, P, B, A
l. M ⁵ is Li, Na, K, Rb, Cs, Mg,
At least one selected from Ca, Sr, and Ba;
Preferably, it is Cs or Mg, particularly preferably Mg.
M ⁷ is at least one selected from O and S, and is preferably O. p and q are each 0.001 to 10, preferably 0.01 to 5, more preferably 0.01 to 1.5, and particularly preferably 0.7 to 1.0.
5 r is 1.00 to 50, preferably 1.r
00 to 26, particularly preferably 1.02 to 6.

Examples of the negative electrode material of the present invention are shown below, but the present invention is not limited to these. SnAl _{0.4
B 0.5 P 0.5 K 0.1 O 3.65} , SnAl 0.4 B 0.5 P 0.5
Na _0.2 O _3.7 , SnAl _0.4 B _0.3 P _0.5 Rb _0.2 O
_{3.4, SnAl 0.4 B 0.5 P 0.5} Cs 0.1 O 3.65, Sn
Al _0.4 B _0.5 P _0.5 K _0.1 Ge _0.05 O _3.85 , SnAl
_0.4 B _0.5 P _0.5 K _0.1 Mg _0.1 Ge _0.02 O _3.83 , Sn
Al _0.4 B _0.4 P _0.4 O _3.2 , SnAl _0.3 B _0.5 P
_0.2 O _2.7 , SnAl _0.3 B _0.5 P _0.2 O _2.7 , SnA
l _0.4 B _0.5 P _0.3 Ba _0.08 Mg _0.08 O _3.26 , SnAl
_0.4 B _0.4 P _0.4 Ba _0.08 O _3.28 , SnAl _0.4 B _0.5
P _0.5 O _3.6 , SnAl _0.4 B _0.5 P _0.5 Mg _0.1 O
_3.7 .

SnAl _0.5 B _0.4 P _0.5 Mg _0.1 F _0.2
O _3.65 , SnB _0.5 P _0.5 Li _0.1 Mg _0.1 F _0.2 O
_{3.05, SnB 0.5 P 0.5 K 0.1} Mg 0.1 F 0.2 O 3.05,
SnB _0.5 P _0.5 K _0.05 Mg _0.05 F _0.1 O _3.03 , SnB
_0.5 P _0.5 K _0.05 Mg _0.1 F _0.2 O _3.03 , SnAl _{0.4
B 0.5 P 0.5 Cs 0.1 Mg 0.1} F 0.2 O 3.65, SnB
_0.5 P _0.5 Cs _0.05 Mg _0.05 F _0.1 O _3.03 , SnB _{0.5
P 0.5 Mg 0.1 F 0.1 O 3.05} , SnB 0.5 P 0.5 Mg
_0.1 F _0.2 O ₃ , SnB _0.5 P _0.5 Mg _0.1 F _0.06 O
_3.07 , SnB _0.5 P _0.5 Mg _0.1 F _0.14 O _3.03 , SnP
Ba _0.08 O _3.58 , SnPK _0.1 O _3.55 , SnPK _0.05 M
g _0.05 O _3.58 , SnPCs _0.1 O _3.55 , SnPBa _0.08
F _0.08 O _3.54 , SnPK _0.1 Mg _0.1 F _0.2 O _3.55 , S
nPK _0.05 Mg _0.05 F _0.1 O _3.53 , SnPCs _0.1 Mg
_0.1 F _0.2 O _3.55 , SnPCs _0.05 Mg _0.05 F _0.1 O
_3.53 .

Sn _1.1 Al _0.4 B _0.2 P _0.6 Ba _0.08 F
_0.08 O _3.54 , Sn _1.1 Al _0.4 B _0.2 P _0.6 Li _0.1 K
_{0.1 Ba 0.1 F 0.1 O 3.65,} Sn 1.1 Al 0.4 B 0.4 P
_0.4 Ba _0.08 O _3.34 , Sn _1.1 Al _0.4 PCs _0.05 O
_4.23 , Sn _1.1 Al _0.4 PK _0.05 O _4.23 , Sn _1.2 Al
_0.5 B _0.3 P _0.4 Cs _0.2 O _3.5 , Sn _1.2 Al _0.4 B
_0.2 P _0.6 Ba _0.08 O _3.68 , Sn _1.2 Al _0.4 B _0.2 P
_0.6 Ba _0.08 F _0.08 O _3.64 , Sn _1.2 Al _0.4 B _0.2 P
_0.6 Mg _0.04 Ba _0.04 O _3.68 , Sn _1.2 Al _0.4 B _0.3
P _0.5 Ba _0.08 O _3.58 , Sn _1.3 Al _0.3 B _0.3 P _0.4
Na _0.2 O _3.3 , Sn _1.3 Al _0.2 B _0.4 P _0.4 Ca
_0.2 O _3.4 , Sn _1.3 Al _0.4 B _0.4 P _0.4 Ba _0.2 O
_3.6 , Sn _1.4 Al _0.4 PK _0.2 O _4.6 , Sn _1.4 Al
_0.2 Ba _0.1 PK _0.2 O _4.45 , Sn _1.4 Al _0.2 Ba
_0.2 PK _0.2 O _4.6 , Sn _1.4 Al _0.4 Ba _0.2 PK
_0.2 Ba _0.1 F _0.2 O _4.9 , Sn _1.4 Al _0.4 PK _0.3
O _4.65 , Sn _1.5 Al _0.2 PK _0.2 O _4.4 , Sn _1.5 A
l _0.4 PK _0.1 O _4.65 , Sn _1.5 Al _0.4 PCs _0.05 O
_4.63 , Sn _1.5 Al _0.4 PCs _0.05 Mg _0.1 F _0.2 O
_4.63 .

SnSi _0.5 Al _0.1 B _0.2 P _0.1 Ca
_0.4 O _3.1 , SnSi _0.4 Al _0.2 B _0.4 O _2.7 , Sn
Si _0.5 Al _0.2 B _0.1 P _0.1 Mg _0.1 O _2.8 , SnS
i _0.6 Al _0.2 B _0.2 O _2.8 , SnSi _0.5 Al _0.3 B
_0.4 P _0.2 O _3.55 , SnSi _0.5 Al _0.3 B _0.4 P _0.5
O _4.30 , SnSi _0.6 Al _0.1 B _0.1 P _0.3 O _3.25 , S
nSi _0.6 Al _0.1 B _0.1 P _0.1 Ba _0.2 O _2.95 , Sn
Si _0.6 Al _0.1 B _0.1 P _0.1 Ca _0.2 O _2.95 , SnS
i _0.6 Al _0.4 B _0.2 Mg _0.1 O _3.2 , SnSi _0.6 A
l _0.1 B _0.3 P _0.1 O _3.05 , SnSi _0.6 Al _0.2 Mg
_0.2 O _2.7 , SnSi _0.6 Al _0.2 Ca _0.2 O _2.7 , S
nSi _0.6 Al _0.2 P _0.2 O ₃ , SnSi _0.6 B _0.2 P
_0.2 O ₃ , SnSi _0.8 Al _0.2 O _2.9 , SnSi _0.8
Al _0.3 B _0.2 P _0.2 O _3.85 , SnSi _0.8 B _0.2 O
_2.9 , SnSi _0.8 Ba _0.2 O _2.8 , SnSi _0.8 Mg
_0.2 O _2.8 , SnSi _0.8 Ca _0.2 O _2.8 , SnSi
_0.8 P _0.2 O _3.1 .

Sn _0.9 Mn _0.3 B _0.4 P _0.4 Ca _0.1 R
b _0.1 O _2.95 , Sn _0.9 Fe _0.3 B _0.4 P _0.4 Ca _0.1
Rb _0.1 O _2.95 , Sn _0.8 Pb _0.2 Ca _0.1 P _0.9 O
_3.35 , Sn _0.3 Ge _0.7 Ba _0.1 P _0.9 O _3.35 , Sn
_0.9 Mn _0.1 Mg _0.1 P _0.9 O _3.35 , Sn _0.2 Mn _0.8
Mg _0.1 P _0.9 O _3.35 , Sn _0.7 Pb _0.3 Ca _0.1 P
_0.9 O _3.35 , Sn _0.2 Ge _0.8 Ba _0.1 P _0.9 O _3.35 .

The chemical formula of the compound obtained by calcination can be calculated by inductively coupled plasma (ICP) emission spectroscopy as a measuring method, and from the difference in weight of powder before and after calcination as a simple method.

The lithium ion can be inserted into the negative electrode material of the present invention before and / or after assembling the battery. The insertion amount may be up to approximation of the deposition potential of lithium. For example, it is preferably from 50 to 700 mol%, more preferably from 100 to 600 mol%, per negative electrode material. It is preferable that the release amount be larger than the insertion amount. The method of inserting the light metal is preferably an electrochemical, chemical or thermal method. As the electrochemical method, a method of electrochemically inserting a light metal contained in the positive electrode active material or a method of directly electrochemically inserting a light metal or an alloy thereof from a light metal is preferable. Chemical methods include mixing or contacting with light metals, or organic metals,
For example, there is a method of reacting with butyllithium or the like. Electrochemical and chemical methods are preferred.

In the present invention, by using the compounds represented by the general formulas (6) and (7) as described above mainly as a negative electrode material, the charge / discharge cycle characteristics are further improved, the discharge voltage and the discharge voltage are increased. A non-aqueous electrolyte secondary battery having high capacity, high safety, and excellent high current characteristics can be obtained. In the present invention, a particularly excellent effect can be obtained by using a compound containing Sn and having a divalent Sn valence as the negative electrode material. The valence of Sn can be determined by a chemical titration operation. For example, Phys
ics and Chemistry of Glasses Vol.8 No.4 (1967)
It can be analyzed by the method described on page 65. Also, S
It is also possible to determine from the night shift by solid state nuclear magnetic resonance (NMR) measurement of n. For example, in the wide measurement, metal Sn (zero-valent Sn) has a peak in an extremely low magnetic field at around 7000 ppm relative to Sn (CH ₃ ) ₄ , whereas SnO (= bivalent) has a peak around 100 ppm.
In SnO ₂ (= tetravalent), it appears near −600 ppm. Since the case Knight shift having the same ligand depends largely on the valency of Sn, which is the center metal, ¹¹⁹
The valence can be determined at the peak position determined by Sn-NMR measurement. Various compounds can be included in the negative electrode material of the present invention. For example, transition metals (Sc, Ti, V,
Cr, Mn, Fe, Co, Ni, Cu, Zn, Y, Z
r, Nb, Mo, Tc, Ru, Rh, Pd, Ag, C
d, lanthanoid metal, Hf, Ta, W, Re, O
s, Ir, Pt, Au, Hg) and Group 17 elements of the periodic table (F, Cl). Further, it may contain dopants of various compounds (for example, compounds of Sb, In, and Nb) that increase electron conductivity. The amount of the compound to be added is preferably 0 to 20 mol%.

In the present invention, the method of synthesizing the composite oxide mainly composed of the oxides represented by the general formulas (6) and (7) is a firing method,
Any of the solution methods can be employed. For example, the firing method will be described in detail. M ¹ compound, M ² compound and M ⁴ compound (M ¹ and M ² are different from Si, Ge, S
n, Pb, P, B, Al, Sb and M ⁴ are Mg, Ca, S
r, Ba) may be mixed and fired. Examples of the Sn compound include SnO, SnO ₂ , Sn ₂ O ₃ , and Sn.
₃ O ₄ , Sn ₇ O ₁₃ .H ₂ O, Sn ₈ O ₁₅ , stannous hydroxide, stannic oxyhydroxide, stannic acid, stannous oxalate, stannous phosphate, orthostannic acid, meta Stannic acid, parastannic acid, stannous fluoride,
Examples thereof include stannic fluoride, stannous chloride, stannic chloride, stannous pyrophosphate, tin phosphide, stannous sulfide, and stannic sulfide. Examples of the Si compound include SiO ₂ , S
Organic silicon compounds such as iO, tetramethylsilane and tetraethylsilane, alkoxysilane compounds such as tetramethoxysilane and tetraethoxysilane, and hydrosilane compounds such as trichlorohydrosilane can be exemplified. Examples of the Ge compound include GeO ₂ , GeO, alkoxy germanium compounds such as germanium tetramethoxide and germanium tetraethoxide. Pb compounds include, for example, PbO ₂ , P
bO, Pb ₂ O ₃ , Pb ₃ O ₄ , lead nitrate, lead carbonate, lead formate, lead acetate, lead tetraacetate, lead tartrate, lead diethoxide, lead di (isopropoxide) and the like can be mentioned. Examples of the P compound include phosphorus pentoxide, phosphorus oxychloride, phosphorus pentachloride, phosphorus trichloride, phosphorus tribromide, trimethyl phosphate, triethyl phosphate, tripropyl phosphate, stannous pyrophosphate, boron phosphate and the like. Can be mentioned. As the B compound, for example, boron trioxide, boron trichloride,
Examples thereof include boron tribromide, boron carbide, boric acid, trimethyl borate, triethyl borate, tripropyl borate, tributyl borate, boron phosphide, and boron phosphate. Examples of the Al compound include aluminum oxide (α-alumina, β-alumina), aluminum silicate, aluminum tri-iso-propoxide, aluminum tellurite, aluminum chloride, aluminum boride, aluminum phosphide, aluminum phosphate, and lactic acid. Examples include aluminum, aluminum borate, aluminum sulfide, aluminum sulfate, and aluminum boride. Examples of the Sb compound include diantimony trioxide and triphenylantimony.

As the Mg, Ca, Sr and Ba compounds,
Each oxide, hydroxide, carbonate, phosphate, sulfate,
Nitrate, aluminum compound and the like can be mentioned.

The firing conditions are preferably a heating rate of 4 ° C. or more and 2000 ° C. or less per minute.
More preferably, it is 6 ° C. or more and 2000 ° C. or less. It is particularly preferably 10 ° C or more and 2000 ° C or less, and the firing temperature is preferably 250 ° C or more and 1500 ° C or less, more preferably 350 ° C or more and 1500 ° C or less.
Or less, particularly preferably 500 ° C. or more and 1500 ° C.
Or less, and the firing time is 0.01 hour or more and 1
00 hours or less, more preferably 0.5 hours or more and 70 hours or less, particularly preferably 1 hour or more and 20 hours or less, and the temperature decreasing rate is 2 ° C. or more and 107 ° C. or less per minute. The temperature is more preferably from 4 ° C to 107 ° C, particularly preferably from 6 ° C to 107 ° C, particularly preferably from 1 ° C to 107 ° C.
0 ° C or more and 107 ° C or less. The rate of temperature rise in the present invention is an average rate of temperature rise from “50% of firing temperature (displayed in ° C)” to “80% of firing temperature (displayed in ° C)”. "Firing temperature (℃
80% of the display) to “50% of the firing temperature (° C)”
Is the average rate of temperature drop to reach. The temperature may be cooled in a firing furnace, or may be taken out of the firing furnace and put into, for example, water for cooling. In addition, the gun method, Hammer-Anvil method, slap method, and the like described in page 217 of ceramics processing (Gihodo Shuppan 1987).
Gas atomizing method, plasma spray method, centrifugal quenching method,
An ultra-quenching method such as a melt drag method can also be used. Also New Glass Handbook (Maruzen 199
1) Cooling may be performed using a single roller method or a twin roller method described on page 172. In the case of a material that melts during firing, a fired product may be continuously taken out while supplying raw materials during firing. In the case of a material that melts during firing, it is preferable to stir the melt.

The firing gas atmosphere is preferably an atmosphere having an oxygen content of 5% by volume or less, and more preferably an inert gas atmosphere. Examples of the inert gas include nitrogen, argon, helium, krypton, xenon, and the like.

The average particle size of the compounds represented by formulas (6) and (7) used in the present invention is preferably 0.1 to 60 μm, particularly preferably 1.0 to 30 μm, and more preferably 2.0 to 30 μm.
20 μm is more preferred. In order to obtain a predetermined particle size, a well-known pulverizer or classifier is used. For example, mortar, ball mill, sand mill, vibrating ball mill,
A satellite ball mill, a planetary ball mill, a swirling air jet mill, a sieve, and the like are used. At the time of pulverization, wet pulverization in the presence of water or an organic solvent such as methanol can also be performed as necessary. Classification is preferably performed to obtain a desired particle size. The classification method is not particularly limited, and a sieve, an air classifier, a drainage, and the like can be used as necessary. Classification can be performed both in a dry type and a wet type.

More preferred lithium-containing transition metal oxide cathode materials used in the present invention include lithium compounds / transition metal compounds (where transition metals are Ti, V, C
It is preferable to mix and synthesize so that the total molar ratio of r, Mn, Fe, Co, Ni, Mo, and W) is 0.3 to 2.2. Particularly preferred lithium-containing transition metal oxide cathode materials used in the present invention include lithium compounds / transition metal compounds (where transition metals are V, Cr, Mn, Fe, Co, Ni
At least one selected from the group consisting of
It is preferable to synthesize them by mixing them so as to be 2.2. Particularly preferred lithium-containing transition metal oxide cathode materials used in the present invention are Li _x QO _y (where Q is mainly, at least one of which is Co, Mn, Ni,
V, transition metal containing Fe), x = 0.2 to 1.2, y =
1.4 to 3) are preferable. As Q, other than transition metals, Al, Ga, In, Ge, Sn, Pb, Sb,
Bi, Si, P, B, etc. may be mixed. The mixing amount is preferably 0 to 30 mol% based on the transition metal.

More preferable lithium-containing metal oxide cathode materials used in the present invention include Li _x CoO ₂ ,
Li _x NiO ₂ , Li _x MnO ₂ , Li _x Co _a Ni
_1-a O ₂ , Li _x Co _b V _1-b O _z , Li _x Co _b Fe
_{1-b O 2, Li x} Mn 2 O 4, Li x Mn c Co 2-c O
_{4, Li x Mn c Ni 2} -c O 4, Li x Mn c V 2-c O
₄ , Li _x Mn _c Fe _2-c O ₄ (where x = 0.7-
1.2, a = 0.1-0.9, b = 0.8-0.98,
c = 1.6-1.96, z = 2.01-2.3). The most preferred lithium-containing transition metal oxide cathode materials used in the present invention include Li _x CoO ₂ , L
_{i x NiO 2, Li x MnO} 2, Li x Co a Ni 1-a
_{O 2, Li x Mn 2 O} 4, Li x Co b V 1-b O z ( wherein x = 0.7~1.2, a = 0.1~0.9, b =
0.9 to 0.98, z = 2.01 to 2.3). Here, the above x value is a value before the start of charging and discharging,
It increases or decreases due to charge and discharge.

The conductive carbon compound that can be used in the present invention is not particularly limited as long as it is an electron conductive material that does not cause a chemical change in the constructed battery. Specific examples include flake graphite, flake graphite, natural graphite such as earthy graphite, petroleum coke, coal coke, celluloses, sugars, high-temperature fired bodies such as mesophase pitch, and graphite such as artificial graphite such as vapor-grown graphite. Carbon blacks such as acetylene black, furnace black, ketjen black, channel black, lamp black and thermal black, asphalt pitch, coal tar, activated carbon, meso fuse pitch, polyacene and the like. Among these, graphite and carbon black are preferred. Non-carbon conductive agents include conductive fibers such as metal fibers, metal powders such as copper, nickel, aluminum, and silver; conductive whiskers such as zinc oxide and potassium titanate; and conductive metals such as titanium oxide. An oxide or the like may be included alone or a mixture thereof as necessary.

The amount of the conductive agent to be added to the mixture layer is preferably from 6 to 50% by weight, more preferably from 6 to 30% by weight, based on the negative electrode material or the positive electrode material. In the case of carbon or graphite, the content is particularly preferably 6 to 20% by weight.

As the binder for holding the electrode mixture used in the present invention, a polysaccharide, a thermoplastic resin and a polymer having rubber elasticity or a mixture thereof can be used. Preferred binders are starch, carboxymethylcellulose, cellulose, diacetylcellulose, methylcellulose, hydroxyethylcellulose, hydroxypropylcellulose, sodium alginate,
Water-soluble polymers such as polyacrylic acid, sodium polyacrylate, polyvinylphenol, polyvinylmethylether, polyvinylalcohol, polyvinylpyrrolidone, polyacrylamide, polyhydroxy (meth) acrylate, styrene-maleic acid copolymer, polyvinyl chloride, polytetra Fluoroethylene, polyvinylidene fluoride, tetrafluoroethylene-hexafluoropropylene copolymer, vinylidene fluoride-tetrafluoroethylene-hexafluoropropylene copolymer, polyethylene, polypropylene, ethylene-propylene-diene terpolymer (EPDM), sulfone (Meth) acrylates containing (meth) acrylic acid esters such as activated EPDM, polyvinyl acetal resin, methyl methacrylate, 2-ethylhexyl acrylate, etc. Acrylic acid ester copolymer, (meth) acrylic acid ester - acrylonitrile copolymer,
Polyvinyl ester copolymer containing vinyl ester such as vinyl acetate, styrene butadiene copolymer, acrylonitrile butadiene copolymer, polybutadiene, neoprene rubber, fluoro rubber, polyethylene oxide, polyester polyurethane resin, polyether polyurethane resin, polycarbonate Emulsions (latex) or suspensions of polyurethane resins, polyester resins, phenol resins, epoxy resins and the like can be given. In particular, polyacrylate latex, carboxymethyl cellulose, polytetrafluoroethylene, and polyvinylidene fluoride are preferred. These binders can be used alone or as a mixture. If the amount of the binder added is small, the holding power and cohesive force of the electrode mixture is weak and the cycleability is poor, and if too large, the electrode volume increases and the volume per electrode unit volume or unit weight decreases, and further, The conductivity decreases and the capacity decreases. The amount of the binder added is not particularly limited, but is 1 to 30.
% By weight, and particularly preferably 2 to 10% by weight.

The preparation of the negative electrode mixture or the positive electrode mixture paste of the present invention is preferably carried out in an aqueous system. The mixture paste is prepared by first mixing the active material and the conductive agent, adding a binder (resin powder suspension or emulsion (latex)) and water and kneading and mixing. The dispersion can be carried out by using a homogenizer, a dissolver, a planetary mixer, a paint shaker, a stirring mixer such as a sand mill, or a disperser. The prepared mixture paste of the positive electrode active material and the negative electrode active material is mainly used after being coated (coated) on a current collector, dried, and compressed. Coating can be performed by various methods, for example, a reverse roll method, a direct roll method, a blade method, a knife method, an extrusion method, a curtain method, a gravure method, a bar method, a dip method, and a squeeze method. I can do it. The blade method, the knife method and the extrusion method are preferred. The coating is preferably performed at a speed of 0.1 to 100 m / min. At this time, by selecting the above-mentioned coating method in accordance with the liquid physical properties and drying properties of the mixture paste, a good surface state of the coating layer can be obtained. The thickness, length and width of the coating layer are determined depending on the size of the battery. The thickness of the coating layer is particularly preferably 1 to 2000 μm in a compressed state after drying.

As a drying or dehydrating method for removing water from the pellets and sheets, generally employed methods can be used, and hot air, vacuum, infrared rays, far infrared rays, electron beams and low humidity air can be used alone or in combination. Can be used. The temperature is preferably in the range of 80 to 350C, particularly preferably in the range of 100 to 250C. The water content is preferably 2000 ppm or less for the whole battery, and is preferably 500 ppm or less for each of the positive electrode mixture, the negative electrode mixture and the electrolyte from the viewpoint of charge / discharge cycle characteristics.

The compression of the sheet-shaped electrode mixture can be performed by a commonly used pressing method, but a die pressing method and a calender pressing method are particularly preferable. The pressing pressure is not particularly limited, but is 10 kg / cm ^{2 to 3} t / c.
m ² is preferred. The press speed of the calendar press method is
0.1 to 50 m / min is preferred. Press temperature is from room temperature
200 ° C. is preferred.

The support or current collector for the positive electrode and the negative electrode that can be used in the present invention is made of aluminum, stainless steel, nickel, titanium, or an alloy thereof for the positive electrode, and copper, stainless steel, or the like for the negative electrode. Nickel, titanium,
Or, these are alloys, and are in the form of foil, expanded metal, punching metal, or wire mesh. Especially,
Aluminum foil is preferable for the positive electrode, and copper foil is preferable for the negative electrode.

The separator which can be used in the present invention is not limited as long as it has a high ion permeability, a predetermined mechanical strength, and an insulating thin film.
Fluorine polymer, cellulose polymer, polyimide, nylon, glass fiber, alumina fiber is used,
As the form, a nonwoven fabric, a woven fabric, or a microporous film is used. In particular, the material is preferably polypropylene, polyethylene, a mixture of polypropylene and polyethylene, a mixture of polypropylene and Teflon, a mixture of polyethylene and Teflon, and the form is preferably a microporous film. In particular, a microporous film having a pore size of 0.01 to 1 μm and a thickness of 5 to 50 μm is preferable.

The shape of the battery can be applied to any of buttons, coins, sheets, cylinders, corners and the like. A battery is formed by inserting an electrode wound with a pellet, a sheet, or a separator into a battery can, electrically connecting the can and the electrode, injecting an electrolyte, and sealing the battery. At this time, a safety valve can be used as a sealing plate. Further, it is preferable to use a PTC element in order to guarantee the safety of the battery.

The bottomed battery outer can that can be used in the present invention is made of nickel-plated iron steel plate or stainless steel plate (SUS304, SUS304L, SUS304N, S).
US316, SUS316L, SUS430, SUS4
44, etc.), a nickel-plated stainless steel plate (same as above), aluminum or its alloy, nickel, titanium, and copper.
It has a square tubular shape and a rectangular tubular shape. In particular, when the outer can also serves as the negative electrode terminal, a stainless steel plate or a nickel-plated iron steel plate is preferable, and when the outer can also serves as the positive electrode terminal, a stainless steel plate, aluminum or an alloy thereof is preferable.

The sheet-shaped mixture electrode is wound or folded and inserted into a can, the can and the sheet are electrically connected, an electrolytic solution is injected, and a battery can is formed using a sealing plate. . At this time, a safety valve can be used as a sealing plate. In addition to the safety valve, various conventionally known safety elements may be provided. For example, a fuse, a bimetal, a PTC element, or the like is used as the overcurrent prevention element. In addition to the safety valve, as a countermeasure against an increase in the internal pressure of the battery can, a method of making a cut in the battery can, a gasket cracking method or a sealing plate cracking method can be used. Further, the charger may be provided with a circuit incorporating measures for overcharging and overdischarging.

The entire amount of the electrolytic solution may be injected at one time, but it is preferable to perform it in two or more steps. In the case of injecting in two or more steps, each liquid may have the same composition but different compositions (for example, after injecting a non-aqueous solvent or a solution in which a lithium salt is dissolved in a non-aqueous solvent, a non-aqueous solution having a higher viscosity than the solvent). A solution in which a lithium salt is dissolved in a solvent or a nonaqueous solvent is injected). Further, in order to shorten the injection time of the electrolyte solution, the pressure of the battery can is reduced (preferably 500 to 1).
torr, more preferably 400 to 10 torr) or
Centrifugal force or ultrasonic waves may be applied to the battery can.

For the can or the lead plate, a metal or alloy having electrical conductivity can be used. For example, metals such as iron, nickel, titanium, chromium, molybdenum, copper, and aluminum or alloys thereof are used. As a method for welding the cap, the can, the sheet, and the lead plate, a known method (eg, DC or AC electric welding, laser welding, ultrasonic welding) can be used. A conventionally known compound or mixture such as asphalt can be used as the sealing agent for sealing.

The gasket that can be used in the present invention is made of olefin polymer, fluorine polymer, cellulose polymer, polyimide, or polyamide. Olefin polymer is preferable in view of organic solvent resistance and low moisture permeability. Propylene-based polymers are preferred. Further, it is preferably a block copolymer of propylene and ethylene.

[0075] The battery of the present invention is covered with an exterior material if necessary. Examples of the exterior material include a heat-shrinkable tube, an adhesive tape, a metal film, paper, cloth, paint, a plastic case, and the like. Further, at least a part of the exterior may be provided with a portion that changes color by heat so that the heat history during use can be recognized. The battery of the present invention is assembled in a battery pack in a plural number in series and / or parallel as required. In addition to safety elements such as positive temperature coefficient resistors, thermal fuses, fuses and / or current interrupting elements, battery packs have safety circuits (voltage, temperature, current, etc. of each battery and / or assembled battery as a whole, Then, a circuit having a function of interrupting the current may be provided. In addition to the positive and negative terminals of the whole battery pack, the positive and negative terminals of each battery, the temperature detection terminals of the whole battery pack and each battery, the current detection terminals of the whole battery pack, etc. shall be provided as external terminals on the battery pack. Can also. The battery pack may have a built-in voltage conversion circuit (such as a DC-DC converter). The connection of each battery may be fixed by welding a lead plate, or may be fixed by a socket or the like so that it can be easily detached. Further, the battery pack may be provided with a display function of the remaining battery capacity, the presence or absence of charging, the number of times of use, and the like.

[0076] The battery of the present invention is used for various devices.
In particular, video movies, portable VCRs with built-in monitors, movie cameras with built-in monitors, compact cameras,
It is preferably used for a single-lens reflex camera, a film with a lens, a notebook computer, a notebook word processor, an electronic organizer, a mobile phone, a cordless phone, a razor, a power tool, a power mixer, a car, and the like.

[0077]

The present invention will be described in more detail with reference to specific examples, but the present invention is not limited to the examples unless it exceeds the gist of the invention.

Example-1 [Example of preparing positive electrode mixture paste] Positive electrode active material: LiCoO ₂ (a mixture of lithium carbonate and tricobalt tetroxide at a molar ratio of 3: 2 was placed in an alumina crucible, and placed in air. After heating to 750 ° C. at 2 ° C. per minute and calcining for 4 hours, the temperature is further raised to 900 ° C. at a rate of 2 ° C. per minute, followed by baking at that temperature for 8 hours, and crushed. When 50 g of the product is dispersed in 100 ml of water, the conductivity of the dispersion is 0.6 mS / m, the pH is 10.1, and the specific surface area by the nitrogen adsorption method is 0.42 m ² / g).
g and 10 g of acetylene black are mixed with a homogenizer, followed by 8 g of an aqueous dispersion of a copolymer of 2-ethylhexyl acrylate, acrylic acid and acrylonitrile (solids concentration: 50% by weight) as a binder, and a concentration of 2% by weight. %
Of carboxymethylcellulose aqueous solution was added, kneaded and mixed, 50 g of water was further added, and the mixture was stirred and mixed with a homogenizer to prepare a positive electrode mixture paste. [Example of preparing negative electrode mixture paste] Negative electrode active material: SnGe _0.1 B _0.5 P _0.58 Mg _0.1 K _0.1
O _3.35 (6.7 g of tin monoxide, 10.3 g of tin pyrophosphate,
1.7 g of boron trioxide, 0.7 g of potassium carbonate, 0.4 g of magnesium oxide, and 1.0 g of germanium dioxide are dry-mixed, placed in an alumina crucible, and heated to 1000 ° C. at 15 ° C./min in an argon atmosphere. 12 at 1100 ° C
After firing for 10 hours, the temperature was lowered to room temperature at a rate of 10 ° C./min, and the products taken out of the firing furnace were collected, pulverized by a jet mill, average particle size of 4.5 μm, and 2θ value in X-ray diffraction using CuKα ray. Is a substance having a broad peak having an apex at around 28 °, and a 2θ value of 40 ° or more and 70 °
No crystalline diffraction lines were observed below. ) To 200
g, 30 g of a conductive agent (artificial graphite) with a homogenizer, and 50 g of a 2% by weight aqueous solution of carboxymethyl cellulose as a binder, and polyvinylidene fluoride 10 g.
g and 30 g of water were further added and kneaded and mixed to prepare a negative electrode mixture paste. [Preparation of Positive and Negative Electrode Sheets] The positive electrode mixture paste prepared above was coated on both sides of a 30 μm-thick aluminum foil current collector with a blade coater at an application amount of 400 g / m ² ,
The sheet was compressed so as to have a thickness of 280 μm, dried, and then compression-molded by a roller press and cut into a predetermined size to prepare a belt-shaped positive electrode sheet. Further, it was sufficiently dehydrated and dried with a far-infrared heater in a dry box (dew point: dry air having a temperature of -50 ° C. or less) to prepare a positive electrode sheet. Similarly, a negative electrode mixture paste is applied to a 20 μm copper foil current collector, and in the same manner as in the preparation of the positive electrode sheet,
Application amount 70 g / m ² , compressed sheet thickness 90 μm
Was prepared. [Example of electrolytic solution adjustment] In an argon atmosphere, 65.3 g of diethyl carbonate was placed in a 200-cc narrow-mouth polypropylene container, and a small amount of 22.2 g of ethylene carbonate was added thereto while taking care that the solution temperature did not exceed 30 ° C. Each was dissolved. Next, 0.4 g of LiBF ₄ and 12.1 g of LiPF ₆ were dissolved little by little in the polypropylene container in order, respectively, while being careful not to exceed a liquid temperature of 30 ° C.
The obtained electrolyte was a colorless and transparent liquid having a specific gravity of 1.135. The water content is 18 ppm (MKC-
The content of free acid was 24 ppm (measured by neutralization titration with a 0.1 N NaOH aqueous solution using bromthymol blue as an indicator). Further, the compounds of the present invention described in Table 1 were each dissolved in this electrolytic solution at a predetermined concentration to prepare an electrolytic solution. [Example of Making a Cylinder Battery] A positive electrode sheet, a separator made of a microporous polypropylene film, a negative electrode sheet and a separator were laminated in this order, and this was spirally wound.
The wound body was housed in a nickel-plated iron bottomed cylindrical battery can also serving as a negative electrode terminal. Further, an electrolytic solution to which an additive shown in Table 1 was added as an electrolytic solution was injected into the battery can. A battery cover having a positive electrode terminal was caulked via a gasket to produce a cylindrical battery.

Thus, sample batteries 101 to 115 were prepared.

Comparative Example 1 In the same manner as in Example 1, a cylindrical battery was prepared by using an electrolyte solution to which no additives were added. Comparative Example 2 Instead of an oxide-based negative electrode active material, a carbon-based active material (graphite powder) was used.
Was used to prepare a negative electrode sheet in the same manner as in the preparation of the negative electrode sheet, and a cylindrical battery was prepared using an electrolyte solution without adding additives. Further, sample batteries 116 and 117 were prepared using an electrolytic solution to which the compound of the present invention was added. Comparative Examples 3 and 4 Cylindrical batteries were prepared in the same manner as in Example 1, except that the amount of the additive was greatly changed and the added electrolyte was used.

The battery prepared by the above method was charged and discharged under the conditions of a current density of 5 mA / cm ² , a charge end voltage of 4.1 V, and a discharge end voltage of 2.8 V, and the discharge capacity and cycle life were determined. The ratio of the capacity (Wh) of each battery,
Table 1 shows the cyclability (the ratio of the 300th capacity to the first charge / discharge). In addition, as a storage test,
The capacity retention after the battery was charged at 4.1 V and stored at 60 ° C. for one month was similarly measured. The results are also shown in Table 1.

[0082]

[Table 1]

Example 2 Example 1 was repeated except that the additive was changed from the electrolytic solution to the positive electrode active material, and similar results were obtained.

Example 3 120 mg of a lithium metal foil per 1 g of the negative electrode material was stuck on the negative electrode mixture in a strip shape to make electrical contact therewith.
Examples 1 and 2 were repeated except that the coating amount of the positive electrode mixture was 240 g / m ² on one side, and similar results were obtained.

A battery using the compound of the present invention and an oxide for the negative electrode has greatly improved cycleability. Batteries using a carbonaceous material for the negative electrode have improved capacity and cycleability, but the rate of improvement is smaller than that of the oxide negative electrode.

[0086]

By using the compound of the present invention, it is possible to obtain a non-aqueous electrolyte secondary battery having excellent charge / discharge characteristics and further having little deterioration in discharge capacity due to repeated charge / discharge.

[Brief description of the drawings]

FIG. 1 is a sectional view of a cylinder type battery used in Examples.

[Description of sign]

 Reference Signs List 1 gasket made of polypropylene 2 negative electrode can (battery can) also serving as negative electrode terminal 3 separator 4 negative electrode sheet 5 positive electrode sheet 6 nonaqueous electrolyte solution 7 explosion-proof valve 8 positive electrode cap also serving as positive electrode terminal 9 PTC element 10 inner lid 11 ring

Claims (12)

[Claims] 1. A non-aqueous electrolyte secondary battery comprising a positive electrode and a negative electrode containing a material capable of reversibly storing and releasing lithium, a non-aqueous electrolyte containing a lithium salt, and a separator. A non-aqueous electrolyte secondary battery comprising a predetermined amount of the organoboron compound. 2. The non-aqueous electrolyte secondary battery according to claim 1, wherein the organic boron compound is a compound represented by the following general formula (1). General formula (1) In the formula, R ¹ , R ² and R ³ may be the same or different, and each represents a hydrogen atom, an alkyl group, a cycloalkyl group, an alkoxy group, an alkenyl group, an alkynyl group, an aralkyl group, an aryl group, a halogen atom, a cyano atom. Group, hydroxy group, formyl group, aryloxy group, alkylthio group, arylthio group, acyloxy group, sulfonyloxy group, amino group, alkylamino group, arylamino group, carbonamide group, sulfonamide group, oxycarbonylamino group, oxy Sulfonylamino group, ureido group, acyl group, oxycarbonyl group, carbamoyl group,
Sulfonyl group, sulfinyl group, oxysulfonyl group or sulfamoyl group, carboxylic acid group, sulfonic acid group,
Phosphonic acid group, heterocyclic group, -B (R ¹¹ ) (R ¹² ), -O
B (R ¹¹ ) (R ¹² ), OSi (R ¹¹ ) (R ¹² )
(R ¹³ ) and OSn (R ¹¹ ) (R ¹² ) (R ¹³ ). R
¹¹ , R ¹² and R ¹³ may be the same or different from each other;
A hydrogen atom, an alkyl group, a cycloalkyl group, an alkoxy group, an alkenyl group, an alkynyl group, an aralkyl group,
Aryl group, halogen atom, cyano group, nitro group, hydroxy group, formyl group, aryloxy group, alkylthio group, arylthio group, acyloxy group, sulfonyloxy group, amino group, alkylamino group, arylamino group, carbonamide group, Sulfonamide group, oxycarbonylamino group, oxysulfonylamino group, ureido group, acyl group, oxycarbonyl group, carbamoyl group,
Sulfonyl group, sulfinyl group, oxysulfonyl group or sulfamoyl group, carboxylic acid group, sulfonic acid group,
Represents a phosphonic acid group or a heterocyclic group. Note that R ¹ ,
R ² , R ³ , R ¹¹ , R ¹² and R ¹³ may combine with each other to form a ring, and this ring may have a substituent. Further, each group may be substituted by a substitutable group. 3. The organic boron compound represented by the following general formula (2)
The non-aqueous electrolyte secondary battery according to claim 1, which is a compound represented by the following formula: General formula (2) In the formula, X ¹ , X ² and X ³ may be the same or different and represent a hetero atom (however, excluding an oxygen atom).
R ²¹ , R ²² and R ²³ may be the same or different and each is a hydrogen atom, an alkyl group, a cycloalkyl group, an alkoxy group, an alkenyl group, an alkynyl group, an aralkyl group, an aryl group, a halogen atom, a cyano group, a hydroxy group A, formyl group, aryloxy group, alkylthio group, arylthio group, acyloxy group, sulfonyloxy group, amino group, alkylamino group, arylamino group, carbonamide group, sulfonamide group, oxycarbonylamino group, oxysulfonylamino group, It represents a ureido group, an acyl group, an oxycarbonyl group, a carbamoyl group, a sulfonyl group, a sulfinyl group, an oxysulfonyl group or a sulfamoyl group, a carboxylic acid group, a sulfonic acid group, a phosphonic acid group, and a heterocyclic group. R ²¹ , R ²² and R ²³ may combine with each other to form a ring, and this ring may have a substituent. Further, each group may be substituted by a substitutable group. x, y and z represent an integer of 1 to 5. x,
When y and z are 2 or more, a plurality of R ²¹ , R ²² and R ²³ may be the same or different. k, m and n represent 0 or an integer. However, at least one of k, m, and n
One is one or more. 4. The organic boron compound represented by the following general formula (3)
The non-aqueous electrolyte secondary battery according to claim 1, which is a compound represented by the following formula: General formula (3) In the formula, R ³¹ , R ³² and R ³³ each represent an alkyl group or an aryl group. 5. The organic boron compound represented by the following general formula (4)
The non-aqueous electrolyte secondary battery according to claim 1, which is a compound represented by the following formula: General formula (4) In the formula, R ⁴¹ , R ⁴² and R ⁴³ each represent an alkyl group or an alkoxy group. 6. The compound represented by the following general formula (5):
The non-aqueous electrolyte secondary battery according to claim 1, which is a compound represented by the following formula: General formula (5) In the formula, Ar ¹ , Ar ² and Ar ³ each represent an aryl group. 7. The non-aqueous electrolyte secondary battery according to claim 1, wherein the one containing the organic boron compound is a non-aqueous electrolyte containing a lithium salt. 8. The non-aqueous electrolytic solution is characterized in that the content of at least one organoboron compound is 0.001% by weight to 10% by weight based on a supporting salt contained in the electrolytic solution. The non-aqueous electrolyte secondary battery according to claim 7. 9. A non-aqueous electrolyte secondary battery, wherein the supporting salt according to claim 8 is at least LiBF ₄ and / or LiPF ₆ . 10. The non-aqueous electrolyte secondary battery according to claim 1, wherein the negative electrode is a carbonaceous material capable of inserting and extracting lithium. 11. The negative electrode according to any one of the periodic tables 1, 2, 13, 14,
A negative electrode material mainly comprising an amorphous chalcogen compound and / or an amorphous oxide containing three or more kinds of atoms selected from Group 15 atoms.
10. The non-aqueous electrolyte secondary battery according to any one of 9 above. 12. The non-aqueous electrolyte secondary battery according to claim 11, wherein at least one of the negative electrode materials is represented by the general formula (6). M ¹ M ² pM ⁴ qM ⁶ r General formula (6) (where M ¹ and M ² are different from each other, Si, Ge, Sn, P
at least one selected from b, P, B, Al, and Sb;
M ⁴ is Li, Na, K, Rb, Cs, Mg, Ca, S
at least one selected from r and Ba, M ⁶ is O, S,
At least one selected from Te, p and q are each 0.0
01 to 10, r represents a number of 1.00 to 50. )