JPH09330739A - Nonaqueous electrolyte secondary battery - Google Patents

Abstract

PROBLEM TO BE SOLVED: To improve the charge and discharge cycle characteristic of a nonaqueous electrolyte secondary battery having a large discharge capacity by containing at least one disc-like compound in the electrolyte of the nonaqueous electrolyte secondary battery. SOLUTION: This nonaqueous electrolyte secondary battery is formed of a positive electrode containing a material capable of reversibly storing and releasing lithium, a negative electrode mainly consisting of amorphous chalcogen compound and/or amorphous oxide containing three or more kinds of atoms selected from atoms of groups 1, 2, 13, 14, 15 of the periodic table, a nonaqueous electrolyte containing lithium salt, and a separator. At least one disc-like compound is contained in the nonaqueous electrolyte. This disk-like compound contained in the nonaqueous electrolyte has a ring structure represented by either one of the formulas 1-6.

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. The disadvantage of this carbonaceous material is that it has conductivity in itself, so lithium metal may be deposited on the carbonaceous material during overcharging or rapid charging, resulting in the precipitation of dendrites. . In order to avoid this, we have devised a charger or adopted a method of reducing the positive electrode active material to prevent overcharging, but the latter method limits the amount per active material. Therefore, the discharge capacity is also limited. In addition, since the density of the carbonaceous material is relatively small, the discharge capacity is limited in the double sense that the capacity per volume is low. It is disclosed in JP-A-61-54165 and JP-A-2-82447 that a carbon material is used by pressure bonding or laminating a lithium foil.
2-215062, 3-122974, 3-27
2571, the same 5-144471, the same 5-144472,
Although disclosed in JP-A-5-144473 and JP-A-5-151995, the carbon material is used as the negative electrode active material, and the above problems are not essentially solved.

On the other hand, as negative electrode materials other than lithium metal, lithium alloys, and carbonaceous materials, TiS ₂ , LiTiS ₂ (US Pat. No. 983476), WO ₂ , Fe ₂ O ₃ capable of inserting and extracting lithium ions. Lithium compound (JP-A-3-120070), Nb ₂ O ₅ (JP-B-62-59412, JP-A-2-82447), iron oxide,
FeO, Fe ₂ O ₃ , Fe ₃ O ₄ , cobalt oxide, Co
_{O, Co 2 O 3, Co} 3 O 4 ( JP-A-3-29186
2) is known. None of these compounds has a low redox potential, and it has not been possible to realize a non-aqueous electrolyte secondary battery having a high discharge potential of 3V class. Moreover, the discharge capacity is not satisfactory.

In order to improve the above-mentioned drawbacks, a non-aqueous electrolyte secondary battery having a high discharge potential with an average discharge voltage of 3 to 3.6 V class is achieved.
It has been proposed to use oxides such as B and Zr, and composite oxides thereof (Japanese Patent Laid-Open No. 174818/1993).
6-60867, 6-275267, 6-325
765, 6-338324, EP-615296).
Oxides such as Sn, V, Si, B, and Zr, and
By combining these composite oxides with a positive electrode of a transition metal compound containing lithium of a certain kind, the average discharge voltage is 3 to 3.6 V class, the discharge capacity is large, and dendrite generation in the practical range is almost zero. Although a non-aqueous electrolyte secondary battery having extremely high safety is provided, there is a problem that charge / discharge cycle characteristics are not sufficient.

[0005]

An object of the present invention is to improve charge / discharge cycle characteristics of a non-aqueous electrolyte secondary battery having a large discharge capacity.

[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 electrolyte contains at least one discotic compound. Achieved

[0007]

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) A positive electrode containing a material capable of reversibly occluding and releasing lithium, mainly an amorphous chalcogen compound containing three or more kinds of atoms selected from atoms of groups 1, 2, 13, 14, and 15 of the periodic table and / or a non-crystalline chalcogen compound. A non-aqueous electrolyte secondary battery comprising a negative electrode made of a crystalline oxide, a non-aqueous electrolyte containing a lithium salt, and a separator, wherein the non-aqueous electrolyte contains at least one discotic compound. Non-aqueous electrolyte secondary battery. (2) At least one discotic compound contained in the non-aqueous electrolyte is represented by the following general formulas (1), (2), (3), (4),
The non-aqueous electrolyte secondary battery according to item (1), which has a ring structure represented by any one of (5) and (6).

[0008]

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(3) A positive electrode containing a material capable of reversibly occluding and releasing lithium, mainly an amorphous chalcogen compound containing three or more kinds of atoms selected from atoms of the 1, 2, 13, 14, and 15 periodic tables, and A negative electrode made of an amorphous oxide, a non-aqueous electrolyte solution containing a lithium salt, and a non-aqueous electrolyte secondary battery made of a separator, wherein the non-aqueous electrolyte solution has at least one kind of side chain with an ether bond. A non-aqueous electrolyte secondary battery comprising a discotic compound. (4) The non-aqueous electrolyte secondary battery according to item (1), wherein the discotic compound having an ether bond in at least one side chain contained in the non-aqueous electrolyte is a triphenylene derivative. (5) The non-aqueous electrolyte secondary battery according to item (1), wherein at least one discotic compound contained in the non-aqueous electrolyte is a truxene derivative. (6) A discotic compound having an ether bond in at least one side chain contained in the non-aqueous electrolyte is represented by the following general formula (7).
Alternatively, it is represented by the general formula (8) (2)
A non-aqueous electrolyte secondary battery according to item. General formula (7)

[0010]

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In the formula, X ¹¹ represents an oxygen or sulfur atom.
Y represents an alkylene group or an alkyleneoxy group. Z
Represents an alkyl or alkoxy group. R ^{1 s} may be the same or different, and when X ¹¹ is a sulfur atom, at least one group represented by R ¹ has Y as an alkyleneoxy group or Z is an alkoxy group. a represents 0 or 1, and b represents an integer of 0 to 10. General formula (8)

[0012]

[Chemical 6]

In the formula, X ²¹ represents an oxygen or sulfur atom.
J represents a linking group or a chemical bond. c represents 0 or 1. R ¹² has the same meaning as R ^{1 in} formula (7). P represents H, Cl, Br, F, a lower alkyl group or an alkoxy group. R ^{2 s} may be the same or different, and X ²¹
Is a sulfur atom, Y of the group represented by at least one R ² is an alkyleneoxy group or P is an alkoxy group. n represents an integer of 1 to 5. (7) The content of at least one discotic compound contained in the non-aqueous electrolyte is 0.001 wt% to 10 wt% with respect to the supporting salt contained in the electrolyte (1 ) The non-aqueous electrolyte secondary battery according to the item. (8) The supporting salt according to item (4) is at least LiBF
₄ and / or LiPF ₆ is a non-aqueous electrolyte secondary battery. (9) The non-aqueous electrolyte secondary battery according to any one of items (1) to (5), wherein at least one of the negative electrode materials is represented by the general formula (9). M ¹ M ² pM ⁴ qM ⁶ r General formula (9) (wherein 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, 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 0.00
1-10, r represents the number of 1.00-50). (10) At least one of the negative electrode materials has the general formula (1
0) The non-aqueous electrolyte secondary battery according to item (9). SnM ³ pM ⁵ qM ⁷ r General formula (10) (wherein, M ³ is at least one selected from Si, Ge, Pb, P, B, and Al, and M ⁵ is Li, Na, K, R
b, Cs, Mg, Ca, Sr, or at least one selected from Ba, M ⁷ is at least one selected from O and S,
p and q each represent a number of 0.001 to 10, and r represents a number of 1.00 to 50. (11) At least one of the positive electrode materials is Li _x CoO.
_{2, Li x NiO 2, Li} x MnO 2, Li x Co a N
i _(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 C
o _(2-c) O ₄ , Li _x Mn _c Ni _(2-c) O ₄ , Li _x M
n _c V _(2-c) O ₄ , Li _x Mn _c Fe _(2-c) O ₄ (wherein x = 0.02 to 1.2, a = 0.1 to 0.9, b =
0.8-0.98, c = 1.6-1.96, z = 2.0
1 to 2.3) (1) to (1)
The non-aqueous electrolyte secondary battery according to item 0).

By containing at least one discotic compound in the electrolytic solution, the charge / discharge cycle characteristics can be improved without impairing the high capacity of the non-aqueous electrolytic solution secondary battery.

The discotic compound is characterized by having a discotic molecular portion in its mother nucleus. The disk-shaped morphological characteristics of the mother nucleus portion excluding the side chain portion can be expressed as follows for the hydrogen-substituted compound which is the original compound thereof. First, the size of the molecule is determined as follows. 1) Construct a nearly planar, preferably planar, molecular structure for the molecule. In this case, it is preferable to use standard values for the bond distance and bond angle according to the mixture of the orbitals.
You can refer to Chapter 15 of Volume II (Maruzen, 1993). 2) Using the structure obtained in 1) as an initial value, the structure is optimized by the molecular orbital method or the molecular force field method. As the method, for example, Gaussian92, MOPAC93, CHAR
Mm / QUANTA, MM3, and preferably G
aussian92. 3) The center of gravity of the structure obtained by the structure optimization is moved to the origin, and the coordinate axis is taken as the principal axis of inertia (the principal axis of the inertia tensor ellipsoid). 4) Give each atom a sphere defined by the van der Waals radius and describe the shape of the molecule. 5) The length in each coordinate axis direction is measured on the van der Waals surface, and these are designated as a, b, and c, respectively. If a disk-shaped form is defined using a, b, and c obtained by the above procedure, a ≧ b> c and a ≧ b ≧ a /
2, preferably a ≧ b> c and a ≧ b ≧ 0.7a. Further, it is preferable that b / 2> c.

Specific compounds include, for example, Quarterly Chemistry Review No., edited by The Chemical Society of Japan. 22 "Liquid Crystal Chemistry"
Chapter 5, Chapter 10, Section 2 (1994 Academic Publishing Center), C.I. Report of Destrade et al., Mol. C
ryst. Liq. Cryst. 71, 111 pages (1
981), B. Report of Kohne et al., Ange
w. Chem. 96, 70 (1984), J. Am.
M. J. Lehn et al. Chem. Soc. C
hem. Commun. , P. 1794 (1985),
J. Zhang, J .; S. Research report of Moore et al.,
J. Am. Chem. Soc. , 116, 2655 (1994).

For example, benzene derivative, triphenylene derivative, truxene derivative, phthalocyanine derivative, porphyrin derivative, anthracene derivative, azacrown derivative, cyclohexane derivative, β-diketone metal complex derivative, hexaethynylbenzene derivative, dibenzopyrene derivative, coronene derivative and Examples include derivatives of phenylacetylene macrocycle. In addition, “Chemical Review No. 15 New Aromatic Chemistry” edited by the Chemical Society of Japan
(The University of Tokyo Press, 1977) and cyclic compounds and their heteroatom-substituted electronic structures. Further, as in the case of the above-described metal complex, an assembly of a plurality of molecules may be formed by hydrogen bonding, coordination bond, or the like to form a disk-shaped molecule. For example, the above b / a
Are benzene (0.9098), anthraquinone (0.
7249) and triphenylene (0.8936).

A discotic compound is formed by a structure in which a linear alkyl group, an alkoxy group, a substituted benzoyloxy group or the like is radially substituted as a side chain with these as the central nucleus of the molecule. Preferable examples of the mother nucleus compound include triphenylene and truxene. Examples of the side chain include an alkyl group, an alkoxy group, an alkylthio group, an acyloxy group and the like. In addition, C.I. Han
sch, A.A. Leo, R.A. W. Taft, Chemical Review Magazine (Chem. Rev.), 1991, Volume 91,
It may be substituted with the substituents described on pages 165-195 (American Chemical Society), and representative examples thereof include an alkoxy group, an alkyl group, an alkoxycarbonyl group, and a halogen atom. Further, the side chain may have a functional group such as an ether group, an ester group, a carbonyl group, a thioether group, a sulfoxide group, a sulfonyl group, and an amide group. Hereinafter, the side chain will be described in detail.

Examples of the side chain moiety include alkanoyloxy groups (eg, hexanoyloxy, heptanoyloxy, octanoyloxy, nonanoyloxy, decanoyloxy, undecanoyloxy), alkylsulfonyl groups (eg, hexylsulfonyl, heptyl). Sulfonyl, octylsulfonyl, nonylsulfonyl, decylsulfonyl, undecylsulfonyl), alkylthio groups (eg, hexylthio, heptylthio, dodecylthio), alkoxy groups (eg, butoxy, pentyloxy, hexyloxy, heptyloxy, octyloxy, nonyloxy, decyloxy) , Undecyloxy), 2- (4-alkylphenyl) ethynyl group (for example, methyl, ethyl, propyl, butyl, pentyl, hexyl as an alkyl group, Butyl, octyl, nonyl), a terminal vinylalkoxy group (for example, 4-vinylbutoxy, 5-vinylpentyloxy, 6-vinylhexyloxy, 7-vinylheptyloxy, 8-vinyloctyloxy, 9-vinylnonyloxy), 4-alkoxyphenyl group (for example, the alkoxy group mentioned above in the alkoxy group), alkoxymethyl group (for example, the alkoxy group mentioned above in the alkoxy group), alkylthiomethyl group (for example, the alkylthio group mentioned above) Of the alkylthio group), 2-alkylthiomethyl (for example, the alkylthio group mentioned above for the alkylthio group), 2-alkylthioethoxymethyl (for example, the alkylthio group mentioned above for the alkylthio group), 2-alkoxyeth Cimethyl group (for example, the alkoxy group mentioned above as the alkoxy group), 2-alkoxycarbonylethyl group (for example, the alkoxy group mentioned above as the alkoxy group), cholesteryloxycarbonyl, β-sitosteryloxycarbonyl , 4-alkoxyphenoxycarbonyl group (for example, the alkoxy group mentioned above in the alkoxy group), 4-alkoxybenzoyloxy group (for example, the alkoxy group mentioned above in the alkoxy group), 4-alkylbenzoyloxy Examples thereof include a group (for example, the alkyl group mentioned above in the 2- (4-alkylphenyl) ethynyl group) and a 4-alkoxybenzoyl group (for example, an alkoxy group mentioned above in the alkoxy group). In the above description of the group (including the case where it is shown as a substituent), alkanoyl preferably has 2 to 36 carbon atoms, alkyl preferably has 1 to 36 carbon atoms, and alkoxy preferably has 1 to 3 carbon atoms.
6.

Of the above-mentioned groups, the phenyl group may be another aryl group (for example, naphthyl group, phenanthryl group, anthracene group), or may be further substituted in addition to the above-mentioned substituents. The phenyl group is a heteroaromatic ring (preferably a 3- to 10-membered ring containing at least one kind of nitrogen atom, sulfur atom, oxygen atom, silicon atom, phosphorus atom, etc., for example, pyridyl group, pyrimidyl group, triazinyl group. , Thienyl group, furyl group, pyrrolyl group, pyrazolyl group, imidazolyl group, triazolyl group, thiazolyl group, imidazolyl group, oxazolyl group, thiadialyl group, oxadiazolyl group, quinolyl group, isoquinolyl group).

The discotic compound having such a side chain portion is known per se, and it can be synthesized by a usual method starting from the discotic compound. For example, when the side chain is a substituted benzoyloxy group, 2,3,6,7,1
It can be introduced by an esterification procedure in which a hydroxylated discotic compound such as 0,11-hexahydroxytriphenylene is reacted with an acid chloride of a substituted benzoic acid. In addition, the literature Sandler, Karo (Sandler, Kar
o), Organic Functional Group
Preparations Part I (Organic F
unctional Group Preparation
ns Part I), Chapter 10, Academic Press, 1968,
C. Destrade et al., Mol. Cryst. Li
q. Cryst. The side chain portion can be introduced by the method described in Vol. 71, page 111 (1981). The general formula (7) will be described in detail below. X ¹¹ represents an oxygen or sulfur atom. Y is an alkylene group (for example, methylene, ethylene, propylene, butylene, pentylene, hexylene, heptylene, octylene, nonylene) or an alkyleneoxy group (for example, methyleneoxy, ethyleneoxy, propyleneoxy, butyleneoxy, pentyleneoxy, hexyleneoxy). , Heptyleneoxy, octyleneoxy, nonyleneoxy). Y is preferably an alkyleneoxy group. Z is a substituted or unsubstituted alkyl group (for example, methyl, ethyl, n-propyl, isopropyl, n-butyl, pentyl, hexyl, heptyl, octyl, nonyl, 2-chloroethyl, 3-methoxyethyl, methoxyethoxyethyl, 2- Hydroxyethyl, 3-hydroxypropyl) or an alkoxy group (for example, methoxy group, ethoxy group, n-propoxy group or n-butoxy group). R ^{1 s} may be the same or different, and when X ¹¹ is a sulfur atom, at least one group represented by R ¹ has Y as an alkyleneoxy group or Z is an alkoxy group. a represents 0 or 1, and b represents an integer of 0 to 10. The number of carbon atoms in Y is preferably 1 to 12, and more preferably 1 to 6. The number of carbon atoms in Z is preferably 1 to 12, and more preferably 1 to 6.

The general formula (8) will be described in detail below. X ²¹ represents an oxygen or sulfur atom. J represents a linking group or a chemical bond, for example, an alkylene group (preferably having a carbon number of 1 to 12, more preferably 1 to 6. For example, methylene, ethylene, propylene, butylene, pentylene, hexylene, heptylene, octylene, Nonylene), an alkyleneoxy group (preferably having 1 to 12 carbon atoms, more preferably 1 to 6 carbon atoms).
For example, ethyleneoxy, propyleneoxy, butyleneoxy, pentyleneoxy, hexyleneoxy, heptyleneoxy, octyleneoxy, nonyleneoxy), 0
Or a divalent group having up to 25 carbon atoms [eg, -O-, -S-, -C (O)-, -OC (O).
-, -S (C = S)-, -OC (O) -O-, -C
(O) -O-C (O ) -, - C (O) NR 0 -, - NR
⁰ −, —NR ⁰ (O) NR— (R ⁰ is a hydrogen atom or a lower alkyl group). c is 0 or 1. R ¹² has the same meaning as R ^{1 in} formula (7). n represents an integer of 1 to 5. P is H, Cl, Br,
F, a lower alkyl group (eg, methyl, ethyl, n-propyl, isopropyl, n-butyl) or an alkoxy group (eg, methoxy group, ethoxy group, n-propoxy group or n-butoxy group). R ^{2 s} may be the same or different, and when X ²¹ is a sulfur atom, at least one of the groups represented by R ² is an alkyleneoxy group or P is an alkoxy group.

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

[0024]

[Chemical 7]

[0025]

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[0026]

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[0027]

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[0028]

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[0029]

[Chemical 12]

[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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The content of the discotic compound contained in the electrolytic solution is 0.0001 to 0.1 mol / based on the solvent of the electrolytic solution.
L is preferable, and 0.001 to 0.1 mol / l is more preferable. The content of the discotic compound with respect to the supporting salt contained in the electrolytic solution is preferably 0.001% by weight to 10% by weight, and more preferably 0.01-5% by weight.

The electrolytic solution is generally composed of a solvent and a supporting salt dissolved in the solvent, and a lithium salt (anion and lithium cation) is preferable. As the solvent of the electrolytic solution that can be used in the present invention, 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. Further, as the non-cyclic carbonate, diethyl carbonate, dimethyl carbonate,
It is preferable to include methyl ethyl carbonate.
Examples of the lithium salt that can be used in the present invention and are soluble in these solvents include LiClO ₄ , LiBF ₄ , and LiP.
_{F 6, LiCF 3 SO 3,} LiCF 3 CO 2, LiAs
F ₆ , LiSbF ₆ , LiB ₁₀ Cl ₁₀ , lower aliphatic lithium carboxylate, LiAlCl ₄ , LiCl, LiB
Li salts such as r, LiI, lithium chloroborane, and lithium tetraphenylborate can be used, and one kind or a mixture of two or more kinds thereof can be used. 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 an electrolytic solution that can be used in the present invention, ethylene carbonate, propylene carbonate, 1,2-dimethoxyethane, LiCF ₃ SO ₃ dimethyl carbonate or diethyl carbonate appropriately mixed electrolyte, L
An electrolytic solution containing iClO ₄ , LiBF ₄ and / or LiPF ₆ is preferable. Particularly, in a mixed solvent of propylene carbonate or ethylene carbonate and 1,2-dimethoxyethane and / or diethyl carbonate, LiCF ₃ SO ₃ , LiClO ₄ , LiBF ₄ and / or
Alternatively, an electrolytic solution containing LiPF ₆ is preferable, and an electrolytic solution containing at least ethylene carbonate and LiPF ₆ is particularly 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.

Other materials and manufacturing methods for making the non-aqueous electrolyte secondary battery of the present invention will be described in detail below. 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. Each of the positive and negative electrodes may have a single layer or a plurality of layers. As an example of the form consisting of multiple layers,
It may have a surface protective layer or may be composed of a plurality of mixture layers containing an active material. For each mixture, in addition to the positive electrode active material or the negative electrode material, a conductive agent, a binder,
It may contain a dispersant, a filler, an ion conductive agent, a pressure enhancer and various additives.

The negative electrode material used in the present invention is preferably mainly amorphous when incorporated in a battery. 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 is preferably represented by the following general formula (9). M ¹ M ² pM ⁴ qM ⁶ r General formula (9) 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
It is at least one selected from r and Ba, preferably K, Cs, Mg and Ca, and 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 ( 9)
At, the value of r) also changes continuously.

Among the compounds listed above, in the present invention, it is preferable that M ¹ is Sn, and the compound represented by the general formula (1
0). SnM ³ pM ⁵ qM ⁷ r Formula (10) 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.
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 thereto. 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 M
g _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 firing can be calculated from an inductively coupled plasma (ICP) emission spectral analysis method as a measuring method and a weight difference between the powders before and after firing as a simple method.

The amount of the light metal to be inserted into the negative electrode material of the present invention may be close to the deposition potential of the light metal.
The amount 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. How to insert light metal
Electrochemical, chemical and thermal methods are preferred. 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. As a chemical method, there is a method of mixing or contacting with a light metal or a method of reacting with an organic metal such as butyllithium. Electrochemical and chemical methods are preferred. The light metal is particularly preferably lithium or lithium ion.

In the present invention, the compounds represented by the general formulas (9) and (10) as described above are mainly used as the negative electrode material, whereby the charge and discharge cycle characteristics are more excellent, the discharge voltage is high and the discharge voltage is high. It is possible to obtain a non-aqueous electrolyte secondary battery that has high capacity, high safety, and excellent high current characteristics. 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 can also be determined from the night shift by n solid state nuclear magnetic resonance (NMR) measurement. For example, in wide measurement, Sn (zero-valent Sn) has a peak in an extremely low magnetic field of around 7,000 ppm with respect to Sn (CH ₃ ) ₄ , whereas SnO (= 2 valence) has a peak of 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 added is preferably 0 to 20 mol%.

As the method for synthesizing the composite oxide mainly composed of the oxides represented by the general formulas (9) and (10) in the present invention, either a firing method or a solution method can be adopted. For example, the firing method will be described in detail. M ¹ compound, M ² compound and M ⁴ compound (M ¹ , M ² are different from each other in Si, Ge,
Sn, Pb, P, B, Al, Sb, M ⁴ are Mg, Ca,
Sr, Ba) may be mixed and fired. Examples of Sn compounds include SnO, SnO ₂ , Sn ₂ O ₃ , and S.
n 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, Metastannic acid, parastannic acid, stannous fluoride, stannic fluoride, stannous chloride, stannic chloride, stannous pyrophosphate, tin phosphide, stannous sulfide, stannic sulfide, Etc. can be mentioned. Examples of the Si compound include Si
Examples thereof include organic silicon compounds such as O ₂ , SiO, tetramethylsilane and tetraethylsilane, alkoxysilane compounds such as tetramethoxysilane and tetraethoxysilane, and hydrosilane compounds such as trichlorohydrosilane. Examples of the Ge compound include GeO ₂ and G
Examples thereof include alkoxy germanium compounds such as eO, germanium tetramethoxide, and germanium tetraethoxide. Examples of the Pb compound include Pb
O ₂ , PbO, 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. Examples of the B compound include boron trioxide, boron trichloride, boron tribromide, boron carbide, boric acid, trimethyl borate, triethyl borate, tripropyl borate, tributyl borate, boron phosphide, boron phosphate and the like. Examples of the Al compound include aluminum oxide (α-alumina, β-alumina), aluminum silicate, aluminum tri-iso-propoxide,
Examples thereof include aluminum tellurite, aluminum chloride, aluminum boride, aluminum phosphide, aluminum phosphate, aluminum lactate, 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 temperature rising rate of 4 ° C. or more and 2000 ° C. or less per minute.
More preferably, it is 6 ° C. or higher and 2000 ° C. or lower. 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.
And the firing time is 0.01 hours or more 1
The heating time is preferably not more than 00 hours, more preferably not less than 0.5 hours and not more than 70 hours, particularly preferably not less than 1 hour and not more than 20 hours, and the temperature decreasing rate is not less than 2 ° C. and not more than 107 ° C. per minute. The temperature is more preferably 4 ° C to 107 ° C, particularly preferably 6 ° C to 107 ° C, particularly preferably 1 ° C to 107 ° C.
It is above 0 ° C and below 10 7 ° C. 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. See 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.

General formulas (9) and (1 used in the present invention
The average particle size of the compound represented by 0) is 0.1 to 60.
μm is preferable, 1.0 to 30 μm is particularly preferable,
2.0 to 20 μm is more preferable. In order to obtain a predetermined particle size, a well-known pulverizer or classifier is used. For example, a mortar, a ball mill, a sand mill, a vibrating ball mill, a satellite ball mill, a planetary ball mill, a swirling airflow type 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.

A more preferable lithium-containing transition metal oxide positive electrode material used in the present invention is a lithium compound / transition metal compound (wherein the transition metal means 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. As a particularly preferable lithium-containing transition metal oxide positive electrode material used in the present invention, a lithium compound / transition metal compound (wherein the transition metal is at least one selected from V, Cr, Mn, Fe, Co and Ni) The total molar ratio of
It is preferable to synthesize them by mixing them to 2.2.
Particularly preferable lithium-containing transition metal oxide positive electrode material used in the present invention is Li _x QO _y (wherein Q is mainly at least one of Co, Mn, Ni, V and F).
e), x = 0.02 to 1.2, y = 1.
It is preferably 4 to 3). As Q, in addition to transition metals, Al, Ga, In, Ge, Sn, Pb, Sb, B
You may mix i, Si, P, B, etc. The mixing amount is preferably 0 to 30 mol% with respect to the transition metal.

More preferable lithium-containing metal oxide positive electrode materials used in the present invention are Li _x CoO ₂ and
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 ( wherein x = 0.02 to
1.2, a = 0.1 to 0.9, b = 0.8 to 0.98,
c = 1.6 to 1.96 and z = 2.01 to 2.3). The most preferable lithium-containing transition metal oxide positive electrode material used in the present invention is 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 (where x = 0.02 to 1.2, a = 0.1 to 0.9, b =
0.9 to 0.98, z = 2.01 to 2.3). Here, the above-mentioned x value is a value before the start of charging / discharging,
Increases / decreases due to charge / discharge.

The conductive carbon compound that can be used in the present invention may be any electron conductive material that does not undergo 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. Of these, graphite and carbon black are preferable. As non-carbon conductive agents, conductive fibers such as metal fibers, metal powders such as copper, nickel, aluminum and silver, conductive whiskers such as zinc oxide and potassium titanate, conductive metals such as titanium oxide. Oxides and the like can be included alone or as a mixture thereof as required.

The amount of the conductive agent added to the mixture layer is preferably 6 to 50% by weight, 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, a polymer having rubber elasticity, or a mixture thereof can be used. Preferred binders include starch, carboxymethyl cellulose, cellulose, diacetyl cellulose, methyl cellulose, hydroxyethyl cellulose, hydroxypropyl cellulose, 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 esters such as activated EPDM, polyvinyl acetal resin, methyl methacrylate, and 2-ethylhexyl acrylate 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, polyacrylic ester latex, carboxymethyl cellulose, polytetrafluoroethylene, and polyvinylidene fluoride are preferable. These binders can be used alone or as a mixture. When the content of the binder in the mixture is small, the holding power / cohesion of the electrode mixture is weak and the cycleability is poor, and when the content is too large, the electrode volume increases and the capacity per unit weight or unit weight of the electrode increases. It decreases, the conductivity decreases, and the capacity decreases. The content of the binder is not particularly limited,
It is preferably 1 to 30% by weight, and particularly preferably 2 to 10% by weight in the electrode mixture.

The negative electrode mixture or the positive electrode mixture paste of the present invention is preferably prepared in an aqueous system. The mixture paste is prepared by first mixing the active material and the conductive agent, adding a binder (suspension of resin powder or emulsion (latex), preferably 1 μm or less) and water and kneading and mixing. Then, the mixture can be dispersed by using a mixer, 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 applied (coated) on the current collector,
Mainly used after being 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 according to the size of the battery, but the thickness of the coating layer is 1 to 2000 when compressed after drying.
μm is particularly preferred.

As a drying or dehydrating method for removing water from the pellets or sheets, a generally adopted method can be used. 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.

For compression of the sheet-shaped electrode mixture, a generally adopted pressing method can be used, 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 room temperature ~
200 ° C. is preferred.

The positive electrode and negative electrode supports, ie, current collectors, which can be used in the present invention, are made of aluminum, stainless steel, nickel, titanium, or an alloy thereof for the positive electrode and copper, stainless steel 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 has a large ion permeability, has a predetermined mechanical strength, and is an insulating thin film.
Fluorine-based polymer, cellulose-based 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 steel plate, 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 rolled 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 total amount of the electrolytic solution may be injected once, but it is preferable to perform the injection in two or more stages. In the case of injecting in two or more stages, even if each solution has the same composition, different compositions (for example, after injecting a non-aqueous solvent or a solution of a lithium salt dissolved in a non-aqueous solvent, a non-aqueous solvent having a higher viscosity than the solvent) A solution of a lithium salt dissolved in a solvent or a non-aqueous solvent may be 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 and 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 which can be used in the present invention is made of an olefin polymer, a fluorine polymer, a cellulosic polymer, a polyimide or a polyamide as a material, and the olefin polymer is preferable from the viewpoint of organic solvent resistance and low water permeability, and particularly, Polymers based on propylene are preferred. Further, it is preferably a block copolymer of propylene and ethylene.

The battery of the present invention is optionally covered with an exterior material. 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. A plurality of batteries of the present invention are assembled in series and / or in parallel and stored in a battery pack as needed. 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 / absence of charging, the number of times of use, and the like.

The battery of the present invention is used in various devices.
In particular, video movies, portable VCRs with monitors, movie cameras with 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.

[0073]

EXAMPLES The present invention will be described in more detail with reference to specific examples below, but the present invention is not limited to the examples as long as the gist of the invention is not exceeded.

Example 1 [Example of Preparation of Positive Electrode Mixture Paste] Positive electrode active material; LiCoO ₂ (a mixture of lithium carbonate and tricobalt tetroxide in a molar ratio of 3: 2 was placed in an alumina crucible, and the mixture was placed in air every time. After calcination for 4 hours by raising the temperature to 750 ° C. at 2 ° C. for 2 minutes, then raising to 900 ° C. at a rate of 2 ° C./minute and firing for 8 hours at that temperature for crushing. When 50 g was dispersed in 100 ml of water, the electric conductivity of the dispersion was 0.6 mS / m, pH was 10.1, and the specific surface area by the nitrogen adsorption method was 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. %
60 g of the carboxymethyl cellulose 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 Preparation of 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,
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 10 ° C / min, and the ones taken out from the firing furnace were collected and pulverized with a jet mill. The average particle diameter was 4.5 μm. It has a broad peak with a peak at around 28 °, and it is 40 ° or more and 70 ° at 2θ value.
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.
30 g of water and 30 g of water were further mixed and kneaded to prepare a negative electrode mixture paste.

[Preparation of Positive Electrode and Negative Electrode Sheet] The positive electrode mixture paste prepared above was applied by a blade coater on both sides of an aluminum foil current collector having a thickness of 30 μm to give an application amount of 40.
A strip-shaped positive electrode sheet was prepared by applying 0 g / m ² so that the thickness of the sheet after compression was 280 μm, drying and then compression molding with a roller press and cutting into a predetermined size. Further, it was thoroughly dehydrated and dried with a far infrared heater in a dry box (dew point; dry air at -50 ° C or lower) to prepare a positive electrode sheet. Similarly, paste the negative electrode mixture paste into 20
A negative electrode sheet having a coating amount of 70 g / m ² and a compressed sheet thickness of 90 μm was prepared in the same manner as in the preparation of the positive electrode sheet described above.

[Example of Electrolyte Preparation] In an argon atmosphere, 20
Into a 0 cc narrow-neck polypropylene container was placed 65.3 g of diethyl carbonate, and 22.2 g of ethylene carbonate was dissolved little by little while paying attention not to let the liquid temperature exceed 30 ° C. Next, 0.4 g of LiBF ₄ , 12.1 g of L
iPF ₆ was dissolved little by little in the above-mentioned polypropylene container in order, respectively, while taking care that the liquid temperature did not exceed 30 ° C. The obtained electrolyte was a colorless and transparent liquid having a specific gravity of 1.135. Moisture is 18 ppm (measured with a Karl Fischer moisture meter, Model MKC-210, manufactured by Kyoto Electronics Co., Ltd.), and free acid content is 24 ppm (measured by neutralization titration with a 0.1 N NaOH aqueous solution using bromthymol blue as an indicator). )Met. Further, the compounds shown in Table 1 were each dissolved in this electrolytic solution to a predetermined concentration to prepare an electrolytic solution.

[Preparation Example of Cylinder Battery] The cylinder battery shown in the sectional view of FIG. 1 was prepared as follows. The positive electrode sheet (5), the microporous polypropylene film separator (3), the negative electrode sheet (4) and the separator (3) were laminated in this order and spirally wound. This wound body was housed in a bottomed cylindrical battery can (2) made of iron and plated with nickel and also serving as a negative electrode terminal. Further, an electrolytic solution (6) containing the additives shown in Tables 1 to 3 as an electrolytic solution was injected into the battery can (2). A battery lid (8) having a positive electrode terminal was caulked via a gasket (1) to produce a cylindrical battery. In addition, the positive electrode terminal of the battery cover (8) was connected to the positive electrode sheet, and the battery can was connected to the negative electrode sheet by a lead terminal in advance. Also, (7) in the figure is an explosion-proof valve body as a safety valve,
(9) is a PTC element, (10) is an inner lid, and (11) is a ring.

Thus, the sample batteries 101 to 309 of the present invention shown in Tables 1 to 3 were prepared.

Comparative Example Comparative 1 In the same manner as in Example 1, a cylindrical battery of Comparative 1 shown in Tables 1 to 3 was prepared using an electrolyte solution containing no additive.

Comparisons 2 to 4 Carbon-based active material (graphite powder) was used instead of the oxide-based negative electrode active material.
To prepare a negative electrode sheet in the same manner as in the preparation of the negative electrode sheet, using the electrolytic solutions of Tables 1 to 3 respectively.
The cylindrical batteries of Comparative 2 to 4 shown in 3 were prepared.

Comparative Examples 5 to 6 The same method as in Example 1 was used, except that electrolytic solutions added as shown in Tables 1 to 3 were used in which the amounts of additives were changed significantly.
The cylindrical batteries of Comparatives 5 to 6 shown in 3 were prepared.

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,
Tables 1 to 3 show the cycle characteristics (the ratio of the capacity at the 300th time to the first time at the charge and discharge).

[0084]

[Table 1]

[0085]

[Table 2]

[0086]

[Table 3]

Example 2 A cylindrical battery was prepared in the same manner as in Example 1 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 attached in a strip shape on the negative electrode mixture and electrically contacted,
A cylindrical battery was prepared in the same manner as in Example 1 or 2 except that the amount of the positive electrode mixture applied 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 discotic compound has improved cycleability. The improvement rate is higher than that using the carbon-based negative electrode active material.

[0090]

EFFECTS OF THE INVENTION By using an electrolytic solution containing a discotic compound as in the present invention, a non-aqueous electrolytic solution secondary battery having excellent charge / discharge characteristics and less deterioration in discharge capacity due to repeated charge / discharge is provided. Can be obtained.

[Brief description of drawings]

FIG. 1 shows a cross-sectional view of a cylinder type battery manufactured according to an example.

[Explanation of symbols]

 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

─────────────────────────────────────────────────── ─── Continuation of the front page (51) Int.Cl. ⁶ Identification number Internal reference number FI Technical indication C07C 15/56 9734-4H C07C 15/56 15/62 9734-4H 15/62

Claims (9)

[Claims] 1. A positive electrode containing a material capable of reversibly occluding and releasing lithium, a predominantly amorphous chalcogen compound containing three or more kinds of atoms selected from the atoms of groups 1, 2, 13, 14, and 15 of the periodic table, and / or Or a negative electrode made of an amorphous oxide,
A non-aqueous electrolyte secondary battery comprising a non-aqueous electrolyte containing a lithium salt and a separator, wherein the non-aqueous electrolyte contains at least one discotic compound. . 2. At least one discotic compound contained in the non-aqueous electrolyte is represented by the following general formulas (1), (2), (3),
The non-aqueous electrolyte secondary battery according to claim 1, which has a ring structure represented by any one of (4), (5), and (6). Embedded image 3. A positive electrode containing a material capable of reversibly occluding and releasing lithium, mainly an amorphous chalcogen compound containing three or more kinds of atoms selected from the atoms of groups 1, 2, 13, 14, and 15 of the periodic table, and / or Or a negative electrode made of an amorphous oxide,
A non-aqueous electrolyte secondary battery comprising a lithium salt-containing non-aqueous electrolyte and a separator, characterized in that the non-aqueous electrolyte contains at least one discotic compound having an ether bond in a side chain. Non-aqueous electrolyte secondary battery. 4. The non-aqueous electrolyte secondary battery according to claim 1, wherein the discotic compound having an ether bond in at least one side chain contained in the non-aqueous electrolyte is a triphenylene derivative. 5. The non-aqueous electrolyte secondary battery according to claim 1, wherein at least one discotic compound contained in the non-aqueous electrolyte is a truxene derivative. 6. The discotic compound having an ether bond in at least one side chain contained in the non-aqueous electrolyte is represented by the following general formula (7) or general formula (8). 2. The non-aqueous electrolyte secondary battery according to 2. General formula (7) In the formula, X ¹¹ represents an oxygen or sulfur atom. Y represents an alkylene group or an alkyleneoxy group. Z represents an alkyl or alkoxy group. R ^{1 s} may be the same or different, and when X ¹¹ is a sulfur atom, at least one group represented by R ¹ has Y as an alkyleneoxy group or Z is an alkoxy group. a represents 0 or 1, and b represents an integer of 0 to 10. General formula (8) In the formula, X ²¹ represents an oxygen or sulfur atom. J represents a linking group or a chemical bond. c represents 0 or 1. R ¹² has the same meaning as R ^{1 in} formula (7). P is H, Cl, B
It represents r, F, a lower alkyl group or an alkoxy group. R ^{2 s} may be the same or different, and when X ²¹ is a sulfur atom, Y of at least one group represented by R ² is an alkyleneoxy group or P is an alkoxy group. n is 1
Represents an integer from 5 to 5. 7. The content of the discotic compound having an ether bond in the side chain, which is contained in at least one kind of the non-aqueous electrolytic solution,
The non-aqueous electrolyte secondary battery according to any one of claims 1 to 6, wherein the content is 0.001% by weight to 10% by weight with respect to the supporting salt contained in the electrolytic solution. 8. A non-aqueous electrolyte secondary battery, wherein the supporting salt according to claim 4 is at least LiBF ₄ and / or LiPF ₆ . 9. The non-aqueous electrolyte secondary battery according to claim 1, wherein at least one of the negative electrode materials is represented by the general formula (9). M ¹ M ² pM ⁴ qM ⁶ r General formula (9) (wherein 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. )