JPH10106624A - Nonaqueous electrolyte secondary battery - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a large discharging capacity and an enhanced high- charging-discharging cycle characteristic by containing one kind of specific compound in a battery. SOLUTION: At least one kind of compound represented by the general formula (a), in which an unsaturated bond adjoins to a hetero atom, is contained in a battery. In the general formula, X is either oxygen, sulfur, or nitrogen, atom, and when X is either oxygen or sulfur atom (n) is 0, and, when it is nitrogen atom, (n) is 1. Also, R<1> to R<5> may be the same or different and are hydrogen atom, halogen atom, or various groups. Each of the groups. when it can be substituted, may be substituted with a substuent. Also, R<1> to R<5> may form a ring by bonding to one another, and the ring may have a substituent. Thus, at least one kind of compound in which an unsaturated bond adjoins to the hetero atom is contained in the battery, whereby the charge-discharge cycle characteristic can be enhanced without damaging the high capacity of the battery.

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 As a negative electrode material for a non-aqueous electrolyte secondary battery, lithium metal and lithium alloy are typical, but when they are used, so-called dendrite in which lithium metal grows in a dendritic manner during charge and discharge is generated. However, dangers such as ignition were caused due to the internal short circuit or the high activity of the dendrite itself. On the other hand, fired carbonaceous materials capable of reversibly inserting and releasing lithium have come into practical use. Disadvantages of this carbonaceous material are its relatively low density, low capacity per volume, and its own conductivity, so lithium metal can be deposited on the carbonaceous material during overcharging or rapid charging. That is, it may precipitate.

In order to improve the above drawbacks, a non-aqueous electrolyte secondary battery having a high discharge potential having an average discharge voltage of 3 to 3.6 V class is achieved by using Sn, V, Si,
It has been proposed to use oxides such as B and Zr and composite oxides thereof (Japanese Patent Application Laid-Open No. 5-174818,
6-60867, 6-275267, 6-325
765, 6-338324, EP-615296).
Oxides such as Sn, V, Si, B, and Zr; and
These composite oxides have a large discharge capacity at an average discharge voltage of 3 to 3.6 V class when combined with a positive electrode of a transition metal compound containing a certain kind of lithium, and have almost no dendrite generation in a practical region. Although a highly safe nonaqueous electrolyte secondary battery is provided, further improvement in charge / discharge cycle characteristics has been desired.

On the other hand, attempts have been made to improve the charge / discharge cycle characteristics of a non-aqueous secondary battery by changing the composition of an electrolytic solution.
It has been proposed to use unsaturated cyclic carbonates as electrolyte solvents. However, even when these techniques are used, when a lithium metal, a lithium alloy, or a carbon material is used as the negative electrode material, the level of achieving both high discharge capacity and excellent cycle characteristics has not been achieved.

[0005]

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.

[0006]

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 comprises at least one compound represented by the general formula (1). The following was achieved by batteries.

[0007]

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In the formula, R ¹ , R ² , R ³ , R ⁴ and R ⁵ may be the same or different from each other and each represents a hydrogen atom, an alkyl group, a cycloalkyl group, an alkoxy group, an alkenyl group,
Alkynyl group, 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, carbonamido group,
Sulfonamide group, oxycarbonylamino group, oxysulfonylamino group, ureido group, acyl group, oxycarbonyl group, carbamoyl group, sulfonyl group, sulfinyl group, oxysulfonyl group or sulfamoyl group,
Examples include a carboxylic acid group or a salt thereof, a sulfonic acid group or a salt thereof, a phosphonic acid group or a salt thereof, and a heterocyclic group. Note that R ¹ , R ² , R ³ , R ⁴ and R ⁵ may be bonded to each other to form a ring, and this ring may have a substituent. X represents any of oxygen, sulfur and nitrogen atoms.

[0009]

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 including a positive electrode and a negative electrode containing a material capable of reversibly inserting and extracting lithium, a non-aqueous electrolyte containing a lithium salt, and a separator, at least one kind of general battery A non-aqueous electrolyte secondary battery comprising the compound represented by the formula (1).

[0010]

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In the formula, R ¹ , R ² , R ³ , R ⁴ and R ⁵ may be the same or different and each represents a hydrogen atom, an alkyl group, a cycloalkyl group, an alkoxy group, an alkenyl group,
Alkynyl group, 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, carbonamido group,
Sulfonamide group, oxycarbonylamino group, oxysulfonylamino group, ureido group, acyl group, oxycarbonyl group, carbamoyl group, sulfonyl group, sulfinyl group, oxysulfonyl group or sulfamoyl group,
Examples include a carboxylic acid group or a salt thereof, a sulfonic acid group or a salt thereof, a phosphonic acid group or a salt thereof, and a heterocyclic group. Note that R ¹ , R ² , R ³ , R ⁴ and R ⁵ may be bonded to each other to form a ring, and this ring may have a substituent. X represents any of oxygen, sulfur and nitrogen atoms. n represents an integer of 0 or 1. (2) The nonaqueous electrolyte secondary battery according to item 1, wherein X in the compound represented by the general formula (1) is an oxygen atom. (3) The nonaqueous electrolyte secondary battery according to item 1, wherein the compound represented by the general formula (1) is an unsaturated cyclic carbonate. (4) The non-aqueous electrolyte contains at least one kind of the general formula (1)
Item 2. The non-aqueous electrolyte secondary battery according to Item 1, comprising a compound represented by the following formula: (5) The content of at least one compound represented by the general formula (1) contained in the nonaqueous electrolyte is 0.001% by weight to 10% by weight based on the supporting salt contained in the electrolyte. Item 2. The non-aqueous electrolyte secondary battery according to Item 1. (6) The supporting salt according to item 5, wherein at least LiBF ₄
And / or LiPF ₆ . (7) The negative electrode comprises a negative electrode material mainly containing an amorphous chalcogen compound and / or an amorphous oxide containing three or more kinds of atoms selected from Group 1, 2, 13, 14, and 15 atoms of the periodic table. Item 7. The non-aqueous electrolyte secondary battery according to any one of Items 1 to 6, (8) At least one kind of the negative electrode material has a general formula (2)
8. The non-aqueous electrolyte secondary battery according to item 7, wherein M ¹ M ² pM ⁴ qM ⁶ r General formula (2) (where M ¹ and M ² are different from each other, Si, Ge, Sn, Pb,
At least one selected from P, B, Al and Sb, M ⁴
Is Li, Na, K, Rb, Cs, Mg, Ca, Sr, B
at least one selected from a, M ⁶ is at least one selected from O, S, Te, and p and q are each 0.001 to 1;
0 and r represent numbers of 1.00 to 50. )

In the present invention, at least one battery is installed in the battery.
By including a compound in which an unsaturated bond is adjacent to a kind of hetero atom, charge / discharge cycle characteristics can be improved without impairing the high capacity of the nonaqueous electrolyte secondary battery.

Hereinafter, the compound represented by formula (1) will be described in detail. In the general formula (1), X represents any of oxygen, sulfur and nitrogen atoms. When X is an oxygen atom or a sulfur atom, n is 0, and when X is a nitrogen atom, n is 1. R ¹ , R ² , R ³ , R ⁴ and R ⁵ may be the same or different from each other and are each a hydrogen atom, an alkyl group (eg, methyl, ethyl, propyl, dodecyl) or a cycloalkyl group (eg, cyclopropyl, cyclohexyl) ), Alkoxy groups (eg, methoxy, ethoxy, 2-methoxyethoxy), alkenyl groups (eg, vinyl, allyl, cyclohexenyl), alkynyl groups (eg, ethynyl,
2-propenyl, hexadecynyl), aralkyl group (eg, benzyl, diphenylmethyl, naphthylmethyl), aryl group (eg, phenyl, naphthyl, anthryl), halogen atom (eg, chlorine atom, bromine atom, fluorine atom), cyano group A nitro group, a hydroxy group, a formyl group, an aryloxy group (eg, phenoxy), an alkylthio group (eg, methylthio, octylthio 2-phenoxyoctylthio), an arylthio group (eg, phenylthio), an acyloxy group (eg,
Acetoxy), a sulfonyloxy group (eg, methanesulfonyloxy, benzenesulfonyloxy), an amino group, an alkylamino group (eg, methylamino, butylamino), an arylamino group (eg, phenylamino), a carbonamide group (eg, Acetylamino, propanoylamino), sulfonamide group (eg, methanesulfonamide, benzenesulfonamide), oxycarbonylamino group (eg, methoxycarbonylamino), oxysulfonylamino group (eg, ethoxysulfonylamino), ureido group ( For example, phenylureido, methylureido), acyl group (eg, acetyl, benzoyl, pivaloyl), oxycarbonyl group (eg, methoxycarbonyl), carbamoyl group (eg, N-ethylcarbayl) Yl, N-benzylcarbamoyl), a sulfonyl group (eg, methanesulfonyl, benzenesulfonyl), a sulfinyl group (eg, methanesulfinyl), an oxysulfonyl group (eg, methoxysulfonyl) or a sulfamoyl group (N-ethylsulfamoyl), Examples include a carboxylic acid group or a salt thereof, a sulfonic acid group or a salt thereof, a phosphonic acid group or a salt thereof, and a heterocyclic group. 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 , R ³ , R ⁴ and R ⁵ may be bonded to each other to form a ring, and this ring may have a substituent. 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.

[0014]

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[0015]

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[0016]

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[0017]

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[0018]

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[0019]

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[0020]

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[0021]

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[0022]

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The compound of the general formula (1) 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 of the compound of the general formula (1) is preferably from 0.01% by weight to 5% by weight, more preferably from 0.1% by weight to 2% by weight, based on the active material of the electrode. When contained in the electrolytic solution, the content of the compound of the general formula (1) is preferably 0.0001 to 0.1 mol / l with respect to the electrolytic solution solvent,
0.001 to 0.1 mol / l is more preferred. The content of the compound of the general formula (1) with respect to the supporting salt contained in the electrolytic solution is preferably from 0.001% by weight to 10% by weight, more preferably from 0.01% by weight to 5% by weight.

The electrolytic solution generally comprises a solvent and a supporting salt dissolved in the solvent, and is preferably a lithium salt (anion and lithium cation). Solvents for the electrolyte 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,
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 the lithium salt soluble in these solvents that can be used in the present invention include, for example, LiClO ₄ , LiBF ₄ , Li
PF ₆ , LiCF ₃ SO ₃ , LiCF ₃ CO ₂ , LiAs
F ₆ , LiSbF ₆ , LiB ₁₀ Cl ₁₀ , lithium lower aliphatic carboxylate, LiAlCl ₄ , LiCl, LiBr,
Li salts such as 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. As the electrolytic solution that can be used in the present invention, ethylene carbonate,
Propylene carbonate, 1,2-dimethoxyethane,
LiCF ₃ SO ₃ , LiClO ₄ ,
An electrolyte containing LiBF ₄ and / or LiPF ₆ is preferred. In particular, a mixed solvent of ethylene carbonate and diethyl carbonate and / or dimethyl carbonate,
An electrolyte containing LiBF ₄ and / or LiPF ₆ is preferred. 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.

It is preferable that the negative electrode material used in the present invention is mainly amorphous when the battery is assembled. 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, the strongest intensity of the crystalline diffraction lines observed at 40 ° to 70 ° in 2θ value is 20 ° in 2θ value.
It is preferably 500 times or less, more preferably 100 times or less, particularly preferably 5 times or less, and most preferably the crystallinity of the diffraction line intensity at the peak of the broad scattering band observed at 40 ° or more. Has no diffraction line.

The negative electrode material used in the present invention has the following general formula:
It is preferable to be represented by (2). M¹M^TwopM^FourqM⁶r General formula (2) where M¹, M^TwoAre different from Si, Ge, Sn, Pb,
At least one selected from P, B, Al, and Sb
And preferably Si, Ge, Sn, P, B, and Al.
And particularly preferably Si, Sn, P, B and Al.
M^FourIs Li, Na, K, Rb, Cs, Mg, Ca, S
r, at least one selected from Ba, preferably
Is K, Cs, Mg, Ca, particularly preferably Cs, Mg
It is. M⁶Is at least one selected from O, S, and Te
Species, preferably O, S, particularly preferably O
It is. p and q are each 0.001 to 10, preferably
Is 0.01 to 5, particularly preferably 0.01 to 2.
is there. r is 1.00 to 50, preferably 1.00
To 26, and particularly preferably from 1.02 to 6. M
¹, M^TwoThe valence of is not particularly limited.
Or a mixture of each valence. Also M¹,
M^Two, M^FourThe ratio is M^TwoAnd M^FourIs M¹0.001 for
Continuously changing in the range of 10 to 10 molar equivalents
And M ⁶(In the general formula (1), r
Also changes continuously.

Among the compounds mentioned above, in the present invention, the case where M ¹ is Sn is preferable, and the compound represented by the general formula (3)
It is represented by SnM ³ pM ⁵ qM ⁷ r General formula (3) 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 and Al. M ⁵ is Li, Na, K, Rb, Cs, Mg, Ca,
It is at least one selected from Sr and Ba, preferably Cs and Mg, and 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, and more preferably 0.01 to
1.5, particularly preferably 0.7 to 1.5.
r is 1.00 to 50, preferably 1.00 to 26
And particularly preferably 1.02 to 6.

Examples of the negative electrode material of the present invention are shown below.
The invention is not limited to these. SnAl_0.4B_0.5P_0.5K_0.1O_3.65, SnAl_0.4
B_0.5P_0.5Na_0.2O _3.7, SnAl_0.4B_0.3P
_0.5Rb_0.2O_3.4, SnAl_0.4B_0.5P_0.5Cs
_0.1O_3.65, SnAl_0.4B_0.5P_0.5K_0.1Ge_0.05
O_3.85, SnAl_0.4B_0.5P_0.5K_0.1Mg_0.1Ge
_0.02O_3.83, SnAl_0.4B_0.4P_0.4O_3.2, SnA
l_0.3B_0.5P_0.2O_2.7, SnAl_0.3B_0.5P_0.2
O_2.7, SnAl_0.4B_0.5P_0.3Ba_0.08Mg_0.08O
_3.26, SnAl_0.4B_0.4P_0.4Ba_{0. 08}O_3.28, Sn
Al_0.4B_0.5P_0.5O_3.6, SnAl_0.4B_0.5P
_0.5Mg_{0. 1}O_3.7.

SnAl_0.5B_0.4P_0.5Mg_0.1F_0.2
O_3.65, SnB_0.5P_0.5Li_0.1Mg_0.1F_0.2O
_3.05, SnB_0.5P_0.5K_0.1Mg_0.1F_0.2O_3.05,
SnB_{0. Five}P_0.5K_0.05Mg_0.05F_0.1O_3.03, SnB
_0.5P_0.5K_0.05Mg_0.1F_0.2O_3.03, SnAl_0.4
B_0.5P_0.5Cs_0.1Mg_0.1F_0.2O_3.65, SnB
_0.5P_0.5Cs_0.05Mg_0.05F_0.1O_3.03, SnB_0.5
P_0.5Mg_0.1F_0.1O_3.05, SnB_0.5P_0.5Mg
_0.1F_0.2O_Three , SnB_0.5P_0.5Mg_0.1F_0.06O_3.
07, SnB_0.5P_0.5Mg_0.1F_0.14O_3.03, SnPB
a_0.08O_3.58, SnPK _0.1O_3.55, SnPK_0.05Mg
_0.05O_3.58, SnPCs_0.1O_3.55, SnPBa _0.08F
_0.08O_3.54, SnPK_0.1Mg_0.1F_0.2O_3.55, Sn
PK_0.05Mg_0.05F_0.1O_3.53, SnPCs_0.1Mg
_0.1F_0.2O_3.55, SnPCs_0.05Mg_0.05F_0.1O
_3.53.

Sn_1.1Al_0.4B_0.2P_0.6Ba_0.08F
_0.08O_3.54, Sn_1.1Al_0.4B_0.2P_0.6Li_0.1K
_0.1Ba_0.1F_0.1O_3.65, Sn_1.1Al_0.4B_0.4P
_0.4Ba_0.08O_3.34, Sn_1.1Al_0.4PCs_0.05O
_4.23, Sn_1.1Al_0.4PK_0.05O_4.23, Sn_1.2Al
_0.5B_0.3P_0.4Cs_0.2O_3.5, Sn_1.2Al_0.4B
_{0. Two}P_0.6Ba_0.08O_3.68, Sn_1.2Al_0.4B_0.2P
_0.6Ba_0.08F_0.08O_3.64, Sn_1.2Al_0.4B_0.2P
_0.6Mg_0.04Ba_0.04O_3.68, Sn_1.2Al_0.4B _0.3
P_0.5Ba_0.08O_3.58, Sn_1.3Al_0.3B_0.3P_0.4
Na_0.2O_3.3, Sn_1.3Al_0.2B_0.4P_0.4Ca
_0.2O_3.4, Sn_1.3Al_0.4B_0.4P_0.4Ba_0.2O
_3.6, Sn_1.4Al_0.4PK_0.2O_4.6, Sn_1.4Al
_0.2Ba_0.1PK_0.2O_4.45, Sn_1.4Al_0.2Ba
_0.2PK_0.2O_4.6, Sn_1.4Al_0.4Ba_0.2PK
_0.2Ba_0.1F_0.2O_4.9, Sn_1.4Al_0.4PK_0.3
O_4.65, Sn _1.5Al_0.2PK_0.2O_4.4, Sn_1.5A
l_0.4PK_0.1O_4.65, Sn_1.5Al _0.4PCs_0.05O
_4.63, Sn_1.5Al_0.4PCs_0.05Mg_0.1F_0.2O
_4.63.

SnSi_0.5Al_0.1B_0.2P_0.1Ca
_0.4O_3.1, SnSi_0.4Al_0.2B_{0. Four}O_2.7, Sn
Si_0.5Al_0.2B_0.1P_0.1Mg_0.1O_2.8, SnS
i_0.6Al_0.2B_0.2O_2.8, SnSi_0.5Al_0.3B
_0.4P_0.2O_3.55, SnSi_0.5Al_0.3B_0.4P_0.5
O_4.30, SnSi_0.6Al_0.1B_0.1P_0.3O_3.25, S
nSi_0.6Al_0.1B_0.1P_0.1Ba_0.2O_2.95, Sn
Si_0.6Al_0.1B_0.1P _0.1Ca_0.2O_2.95, SnS
i_0.6Al_0.4B_0.2Mg_0.1O_3.2, SnSi_{0. 6}A
l_0.1B_0.3P_0.1O_3.05, SnSi_0.6Al_0.2Mg
_0.2O_2.7, SnSi_0.6Al_0.2Ca_0.2O_2.7, S
nSi_0.6Al_0.2P_0.2O_Three, SnSi_{0. 6}B_0.2P
_0.2O_Three , SnSi_0.8Al_0.2O_2.9, SnSi_0.8
Al_0.3B_{0. Two}P_0.2O_3.85, SnSi_0.8B_0.2O
_2.9, SnSi_0.8Ba_0.2O_2.8, SnSi_0.8Mg
_0.2O_2.8, SnSi_0.8Ca_0.2O_2.8, SnSi
_0.8P_0.2O_3.1.

[0033] Sn_0.9Mn_0.3B_0.4P_0.4Ca_0.1R
b_0.1O_2.95, Sn_0.9Fe_0.3B_{0. Four}P_0.4Ca_0.1
Rb_0.1O_2.95, Sn_0.8Pb_0.2Ca_0.1P_0.9O
_3.35, Sn_0.3Ge_0.7Ba_0.1P_0.9O_3.35, Sn
_0.9Mn_0.1Mg_0.1P_0.9O_3.35, Sn_0.2Mn_0.8
Mg_0.1P_0.9O_3.35, Sn_0.7Pb_0.3Ca_0.1P
_0.9O _3.35, Sn_0.2Ge_0.8Ba_0.1P_0.9O_3.35.

The chemical formula of the compound obtained by calcining can be calculated by an inductively coupled plasma (ICP) emission spectroscopic analysis method as a measuring method and a weight difference between powder before and after calcining as a simple method.

The lithium ion can be inserted into the negative electrode material of the present invention before and / or after the battery is assembled. 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, the compounds represented by the general formulas (2) and (3) as described above are mainly used as a negative electrode material, so that the charge / discharge cycle characteristics are more excellent, the discharge voltage and the discharge voltage are higher. 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 (2) and (3) 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 and Ba) may be mixed and fired. Examples of the Sn compound include SnO, SnO ₂ , Sn ₂ O ₃ , Sn ₃ O
₄ , Sn ₇ O ₁₃ .H ₂ O, Sn ₈ O ₁₅ , stannous hydroxide, stannic oxyhydroxide, stannous acid, stannous oxalate, stannous phosphate, orthostannic acid, metastannic acid , Parastannic acid, stannous fluoride, stannic fluoride, stannous chloride, stannic chloride, stannous pyrophosphate, tin phosphide, stannous sulfide, stannic sulfide, etc. be able to. Examples of the Si compound include organic silicon compounds such as SiO ₂ , SiO, tetramethylsilane and tetraethylsilane, alkoxysilane compounds such as tetramethoxysilane and tetraethoxysilane, and hydrosilane compounds such as trichlorohydrosilane. Ge
Examples of the compound include alkoxy germanium compounds such as GeO ₂ , GeO, germanium tetramethoxide, and germanium tetraethoxide. Examples of the Pb compound include PbO ₂ , PbO, Pb
b ₂ O ₃ , Pb ₃ O ₄ , lead nitrate, lead carbonate, lead formate, lead acetate,
Examples include lead tetraacetate, lead tartrate, lead diethoxide, and lead di (isopropoxide). 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, boron tribromide,
Examples thereof include 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. aluminum,
Examples thereof include aluminum borate, aluminum sulfide, aluminum sulfate, and aluminum boride. S
Examples of the compound b 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.

As the firing conditions, the heating rate is preferably 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, more preferably an inert gas atmosphere. Examples of the inert gas include nitrogen, argon, helium, krypton, xenon, and the like.

The compound represented by the general formula (2) or (3) used in the present invention has an average particle size of 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 the transition metal is at least one selected from V, Cr, Mn, Fe, Co, and Ni). Is a total molar ratio of 0.3 to
It is preferable to synthesize them by mixing them to 2.2.
Particularly preferred lithium-containing transition metal oxide cathode material used in the present invention is Li _x QO _y (where Q is mainly, at least one of which is Co, Mn, Ni, V, F
e), x = 0.2-1.2, y = 1.4
To 3). As Q, besides 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 preferred Lithium used in the present invention
Li-containing metal oxide cathode materials include Li_xCoO_Two, L
i_xNiO_Two, Li_xMnO_Two, Li_xCo_aNi_1-aO_Two,
Li_xCo_bV_1-bO_z, Li_xCo_bFe_1-bO_Two, Li_x
Mn_TwoO_Four, Li_xMn_cCo_2-c O_Four, Li_xMn_cNi_2-c
O_Four, Li_xMn_cV_2-cO_Four, Li_xMn_cFe_2-cO
_Four(Where x = 0.02 to 1.2, a = 0.1 to 0.
9, b = 0.8 to 0.98, c = 1.6 to 1.96, z
= 2.01-2.3). Used in the present invention
Most preferred lithium-containing transition metal oxide cathode material
And Li_xCoO_Two, Li_xNiO_Two, Li_xMnO_Two,
Li_xCo_aNi_1-aO_Two, Li_xMn_TwoO_Four, Li_xCo_bV
_1-bO_z(Where x = 0.02 to 1.2, a = 0.1 to
0.9, b = 0.9-0.98, z = 2.01-2.
3). Here, the above-mentioned x value indicates the start of charging and discharging.
This is the previous value and increases or decreases due to charging and discharging.

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 added to the mixture layer is preferably 6 to 50% by weight, and more preferably 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. The particle size of these particles is preferably 0.05 μm to 5 μm. 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 may be 1 to 3
0% by weight is preferable, and 2 to 10% by weight is particularly preferable.

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 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 calendar 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 that 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 non-aqueous 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 applying a centrifugal force or an ultrasonic wave 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 gaskets usable in the present invention are olefin polymers, fluorine polymers, cellulose polymers, polyimides and polyamides, and olefin polymers are preferred from the viewpoint of organic solvent resistance and low moisture permeability. Propylene-based polymers are preferred. Further, it is preferably a block copolymer of propylene and ethylene.

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.

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.

[0060]

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, heated in air at 2 ° C./minute to 750 ° C., calcined for 4 hours, and then further The product was heated to 900 ° C. at a rate of 2 ° C., baked at that temperature for 8 hours, and crushed, and the conductivity of the dispersion when the central particle size was 5 μm and 50 g of the washed product was dispersed in 100 ml of water was 0.6.
200 g of mS / m, pH of 10.1, specific surface area by nitrogen adsorption method of 0.42 m ² / g) and 10 g of acetylene black were mixed with a homogenizer, followed by 2-ethylhexyl acrylate and acrylic as a binder. Aqueous dispersion of copolymer of acid and acrylonitrile (solids concentration 50
8%) and 60 g of a 2% by weight aqueous solution of carboxymethylcellulose, kneaded and mixed.
Then, 0 g was 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 (tin monoxide 6.
7 g, tin pyrophosphate 10.3 g, diboron trioxide 1.7
g, potassium carbonate 0.7 g, magnesium oxide 0.4
g and 1.0 g of germanium dioxide were dry-mixed, placed in an alumina crucible, and placed in an argon atmosphere at 15 ° C./min.
After heating to 00 ° C and baking at 1100 ° C for 12 hours,
The temperature was lowered to room temperature at a rate of 10 ° C./min.
5 μm, a substance having a broad peak having an apex in the vicinity of 28 ° in 2θ value by X-ray diffraction using CuKα ray, and a crystalline diffraction line is observed in 40 ° to 70 ° in 2θ value. Did not. ), 30 g of a conductive agent (artificial graphite) and 30 g of a carboxymethylcellulose aqueous solution having a concentration of 2% by weight as a binder, and 10 g of polyvinylidene fluoride, and 30 g of water, and further kneading and mixing. Then, a negative electrode mixture paste was prepared. [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 preparation] In an argon atmosphere, put 65.3 g of diethyl carbonate in a 200 cc narrow-necked polypropylene container, and add a small amount of 22.2 g of ethylene carbonate to this solution while taking care that the solution temperature does 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. Moisture is 18 ppm (MKC-2 manufactured by Kyoto Electronics)
10 Karl Fischer moisture meter), the free acid content is 24 ppm (using bromthymol blue as an indicator,
Neutralization titration with 0.1N NaOH aqueous solution for measurement)
Met. Further, the compounds described in Tables 1 to 5 were respectively dissolved in this electrolyte solution so as to have a predetermined concentration to prepare an electrolyte 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 114 were prepared.

[Comparative Example 1] A cylindrical battery was prepared in the same manner as in Example 1, except that an electrolytic solution containing no additive was used. [Comparative Examples 2 to 4] Instead of the oxide-based negative electrode active material, a negative electrode sheet was prepared in the same manner as the negative electrode sheet using a carbon-based active material (graphite powder), and the electrolytes shown in Table 1 were used. Thus, a cylindrical battery was prepared. [Comparative Examples 5 to 6] In the same manner as in Example 1, a cylindrical battery was prepared by using an electrolyte solution which was greatly changed in the amount of additives.

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).

Table 1 Experimental results No. 1 Sample Additive Additive concentration (mol / liter) Initial capacity Cycleability (%) ──────────────────────── １０１ 101 A-8 0.01 0.99 83 102 A-15 0.001 1.00 82 103 A-15 0.01 0.98 83 104 A-15 0. 05 0.97 82 105 A-29 0.01 0.98 83 106 106 A-29 0.001 1.083 107 A-29 0.01 0.98 82 108 A-30 0.01 0.97 81 109 A-31 0.01 0.99 82 110 A-32 0.01 0.98 81 111 A-45 0.01 0.97 83 112 B-10 0.01 0.98 82 113 B-18 0.01 0.98 84 114 B-20 0. 01 0.97 83 115 C-2 0.01 0.98 82 113 C-6 0.01 0.98 84 114 C-19 0.01 0.9783 Comparative Example 1 None 0 1.0 70 Comparative Example 2 None 0 0.80 76 Comparative Example 3 A-15 0.01 0.82 82 Comparative Example 4 A-29 0.01 0.82 82 Comparative Example 5 A-29 0.0001 1.0 71 Comparative Example 6 A- 29 1.0 0.78 69

Example 2 Example 1 was repeated except that the additive was changed from the electrolytic solution to the positive electrode active material, and the same 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 and brought into electrical contact with each other.
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.

The battery using the oxide-based negative electrode active material of the present invention has a larger capacity than the battery using the carbon-based negative electrode active material, and the battery containing the compound of the present invention has improved cycleability. Therefore, the improvement rate is larger than that using the carbon-based negative electrode active material.

[0069]

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 (8)

[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 compound represented by the general formula (1): General formula (1) In the formula, R ¹ , R ² , R ³ , R ⁴ and R ⁵ may be the same or different from each other, 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. 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, sulfone Amide group, oxycarbonylamino group, oxysulfonylamino group, ureido group, acyl group, oxycarbonyl group, carbamoyl group, sulfonyl group, sulfinyl group,
Examples include an oxysulfonyl group or a sulfamoyl group, a carboxylic acid group or a salt thereof, a sulfonic acid group or a salt thereof, a phosphonic acid group or a salt thereof, and a heterocyclic group. Note that R
¹ , R ² , R ³ , R ⁴ and R ⁵ may combine with each other to form a ring, and this ring may have a substituent. X represents any of oxygen, sulfur and nitrogen atoms. n is 0 or 1
Represents an integer. 2. The non-aqueous electrolyte secondary battery according to claim 1, wherein X in the compound represented by the general formula (1) is an oxygen atom. 3. The non-aqueous electrolyte secondary battery according to claim 1, wherein the compound represented by the general formula (1) is an unsaturated cyclic carbonate. 4. The non-aqueous electrolyte secondary battery according to claim 1, wherein the non-aqueous electrolyte contains at least one compound represented by the general formula (1). 5. The content of at least one compound represented by the general formula (1) contained in the non-aqueous electrolytic solution 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 1, wherein 6. A non-aqueous electrolyte secondary battery, wherein the supporting salt according to claim 5 is at least LiBF ₄ and / or LiPF ₆ . 7. The method according to claim 1, wherein the negative electrode is a periodic table.
7. 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 V atoms.
The non-aqueous electrolyte secondary battery according to any one of the above. 8. The non-aqueous electrolyte secondary battery according to claim 7, wherein at least one of the negative electrode materials is represented by the general formula (2). M ¹ M ² pM ⁴ qM ⁶ r General formula (2) (where M ¹ and M ² are different from each other, Si, Ge, Sn, Pb,
At least one selected from P, B, Al and Sb, M ⁴
Is Li, Na, K, Rb, Cs, Mg, Ca, Sr, B
at least one selected from a, M ⁶ is at least one selected from O, S, Te, and p and q are each 0.001 to 1;
0 and r represent numbers of 1.00 to 50. )