JPH07201318A - Nonaqueous secondary battery - Google Patents

Abstract

PURPOSE:To provide a safe nonaqueous secondary battery having high discharging operation voltage, high discharging capacity, and excellent charging- discharging cycle properties by using at least one kind of specified lithium compounded oxide as a negative electrode active material. CONSTITUTION:A nonaqueous secondary battery is a battery composed of a positive electrode active material, a negative electrode active material, and a nonaqueous electrolyte containing a lithium salt and at least one substance for the negative electrode active material is a lithium compounded oxide having a formula LipMqOr wherein M stands for at least one element selected from Si, Ge, Sn, Pb, Bi, Sb, Zn, In, and Mg; p=0.1-8; q=1-7; and r=1-20.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION The present invention improves charge / discharge characteristics,
The present invention also relates to a non-aqueous secondary battery with improved safety.

[0002]

2. Description of the Related Art Lithium metal and lithium alloys are typical as negative electrode active materials for non-aqueous secondary batteries. When they are used, lithium metal grows in a dendritic form during charge / discharge, causing internal short circuit. , The activity of the dendritic metal itself is high,
There is a risk of ignition. On the other hand, recently, a calcined carbonaceous material capable of inserting and releasing lithium has come into practical use. The disadvantage of this carbonaceous material is that it has conductivity, so that lithium metal may be deposited on the carbonaceous material during overcharging or rapid charging, resulting in the deposition of dendritic metal. It will be. In order to avoid this, we have devised a charger or adopted a method of reducing the amount of positive electrode active material to prevent overcharge, but the latter method limits the amount of active material. Therefore, the discharge capacity is also limited. Also,
Since the carbonaceous material has a relatively low density, the discharge capacity is limited by the double meaning that the capacity per volume is low.

On the other hand, as negative electrode active material other than lithium metal, lithium alloy or carbonaceous material, TiS ₂ and LiTiS ₂ capable of absorbing and desorbing lithium.
(US Pat. No. 3,983,476), transition metal oxides having a rutile structure, such as WO ₂ (US Pat.
476), a spinel compound such as Li _x Fe (Fe ₂ ) O ₄ (JP-A-58-220362), and an electrochemically synthesized lithium compound of Fe ₂ O ₃ (US Pat.
464, 447), a lithium compound of Fe ₂ O ₃ (JP-A-3-112,070), Nb ₂ O ₅ (Japanese Patent Publication No. 62-5).
9, 412, JP-A-2-82,447), iron oxide, Fe
O, Fe ₂ O ₃ , Fe ₃ O ₄ , cobalt oxide, CoO,
_{Co 2 O 3, Co 3 O} 4 ( JP-A-3-291,862)
It has been known. Since all of these compounds have a high redox potential, a non-aqueous secondary battery having a high discharge potential of 3 V class and a high capacity has not been realized.

As an example of using SnO ₂ or a Sn compound as an active material of a lithium battery, Li as a positive electrode active material of a secondary battery is used.
_1.03 Co _0.95 Sn _0.04 O ₂ (EP86-106, 30
1), the addition of SnO ₂ to V ₂ O ₅ of the secondary battery positive electrode active material (JP-A-2-158,056), the addition of SnO ₂ to α-Fe ₂ O ₃ of the secondary battery negative electrode active material (SnO ₂ Of 0.5 to 10 mol%) (JP-A-62-219,
465), SnO _{2 as a} positive electrode active material for primary batteries (electrochemistry and industrial physical chemistry, vol. 46, No. 7, page 407, 197).
8 years) is known. In addition, as an example of using SnO ₂ or a Sn compound for an electrochromic electrode, SnO ₂ is used.
₂ can reversibly insert Li ions (Journal of Electrochemical Society, Vol. 140, No. 5, L81 1993), 8 mol% Sn in InO _2.
-Doped film (ITO) can reversibly insert Li ions (Solid State Ionics 2
8-30, page 1733, published in 1988). However, in the electrochromic system, since the electrode is made transparent to be used as a thin film by a vapor deposition method or the like, it is generally operated at a considerably low current unlike the practical range of the battery. In the “solid state ionics” of the above-mentioned document, 1 μA to
An experimental example of 30 μA / cm ² is shown.

As an example of using a Ge oxide as an active material of a lithium battery, a positive electrode active material of a secondary battery, V ₂ O ₅ containing G
It is known to add eO ₂ (JP-A-2-158,056) and use GeO or GeO ₂ (JP-A-55-96,567) as a positive electrode active material for primary batteries. As an example of using Pb oxide as an active material of a lithium battery, use of PbO _x as a positive electrode active material of a primary battery (x = 1.4 to 1.
8) (British Patent 78-6,271), as a cathode active material for primary _{cells, PbO, PbO 2, Pb 2} O 3, Pb 3
Use of O ₄ (Materials Chemistry and Physics Vol. 25, No. 2, p. 207, 1990
Year) is known. As an example of using Sb oxide as an active material of a lithium battery, use of Sb oxide as a positive electrode active material of a primary battery (German Patent 2,516,70
3) is known. As an example of using a Bi oxide as an active material of a lithium battery, use of Bi ₂ O ₃ as a positive electrode active material of a primary battery (Japanese Patent Laid-Open No. 52-12425).
A composite oxide of Bi and Pb (Japanese Patent Laid-Open No. 59-151,761) is known as a positive electrode active material for primary batteries.

As a positive electrode active material, LiMn₂ O_Four , L
i₂ MnO₃ , Γ-βMnO₂ And LiMn₂ O_Four Composite of
Oxide, γ-βMnO₂ And Li₂ MnO₃ Complex oxidation of
Thing, LiCoO₂ , LiCo_0.5 Ni_0.5 O₂ , LiN
iO₂ , V₂ O_Five , Amorphous V₂O_Five , V₆ O₁₃, LiV₃
 O₈ , VO₂ , Ti compound TiS₂ , Mo compounds
MoS₂ , MoO₃ , LiMo₂ O_Four Are known
It Both are negative electrode active materials that are metal chalcogenides.
As a combination with a polar active material, TiS₂ And LiTiS₂ 
(US Pat. No. 983,476), chemically synthesized L
i_0.1 V₂ O_Five And LiMn_1-sMe_sO₂ (0.1 <s
<1 Me = transition metal JP-A-63-210,028),
Same Li_0.1 V₂ O_Five And LiCo_1-sFe_sO ₂ (S =
0.05-0.3, 63-211, 564), and Li
_0.1 V₂ O_Five And LiCo_1-sNi_sO₂ (S = 0.5 ~
0.9 JP-A-1-294,364), V₂ O_Five And Nb
₂ O_Five + Lithium metal (JP-A-2-82447), V₂ 
O_Five And TiS₂ Li electrochemically synthesized with_xFe₂ 
O₃ (US Pat. No. 4,464,447 Journal
Boupower Sources Vol. 8 289 1982
Year), LiNi for positive electrode active material and negative electrode active material_xCo_1-xO
₂ (0 ≦ x <1 in Japanese Patent Laid-Open No. 1-120,765
Then, from the examples, the positive electrode active material and the negative electrode active material are the same compound.
Is described. ), LiCoO₂ Or LiMn
₂ O_Four And iron oxide, FeO, Fe₂ O₃ , Fe₃ O_Four ,acid
Cobalt oxide, CoO, Co₂ O₃ Or Co₃O_Four 
(Japanese Patent Laid-Open No. 3-291,862) and the like are known. Well
Also, any of these combinations has a discharge potential lower than 3V class.
It is a non-aqueous secondary battery with a low capacity and a low capacity. The above S
The oxide mainly composed of n is used as the negative electrode active material, and
High discharge potential and high volume by combining with substances
Capacity, good charge / discharge cycle characteristics, and safety
Water secondary battery can be obtained, but charge / discharge cycle characteristics
As described above, this is not satisfactory, and
Further improvement in discharge cycle characteristics is strongly desired.

[0007]

An object of the present invention is to obtain a non-aqueous secondary battery with improved charge / discharge cycle characteristics, high discharge voltage, high capacity and enhanced safety.

[0008]

The object of the present invention relates to a non-aqueous secondary battery comprising a positive electrode active material, a negative electrode active material, and a non-aqueous electrolyte containing a lithium salt, wherein at least one of the negative electrode active materials has a general formula. (1), Li _p M _q O _r General formula (1) (where M is Si, Ge, Sn, Pb, Bi, Sb, Z
at least one selected from n, In and Mg, p = 0.
The numbers 1 to 8, q = 1 to 7, and r = 1 to 20 are represented. ) Can be achieved by a non-aqueous secondary battery characterized by being a lithium composite oxide represented by (4).

The lithium composite oxide referred to in the present invention is generally
Formula (1), Li_pM_qO_r General formula (1) (where M is Si, Ge, Sn, Pb, Bi, Sb, Z
at least one selected from n, In and Mg, p = 0.
The numbers 1 to 8, q = 1 to 7, and r = 1 to 20 are represented. )so
A lithium composite oxide shown, for example Li₂Si O
₃ , Li_FourSi O_Four , Li₂Si₃O₇ , Li₂Si₂O_Five , Li₈
Si O₆ , Li₆Si₂O₇ , Li_FourGe₉O₂ , Li₆Ge
₈O₁₉, Li_FourGe_FiveO₁₂, Li₆Ge₂O₇ , Α-Li_FourGe O_Four
 , Li_FourGe O_Four , Β-Li₈Ge O₆ , Li₂Ge₇O₁₅,
Li₂Ge O₃ , Li₂Ge_FourO₉ , Li₂Sn O₃, Li₈Sn
O₆ , Li₂Pb O₃ , Β-Li₂Pb O₃ , Li₈Pb O
₆ , Li_FourPb O _Four , Li₇Sb O₆ , Li Sb O₃ , Li₃
Sb O_Four , Li₃Bi O_Four , Li₇Bi O₆, Li_FiveBi O
_Five , Li Bi O₂ , Li_FourBi₆O₁₁, Li₆Zn O_Four , Li_Four
Zn O₃ , Li₂Zn O₂ , Li In O₂ , Li₃In O
₃ , Li_FourMg Sn₂O₇ , Li₂Mg Sn₂O₆ , Li₂Mg S
n₃O₆ , Li₂Mg₃Sn O₆ , Li_FourMg₂Sn O₆ , Li₂Z
n Sn₂O₆ , Li In Ge₂O₆ , Li In Ge O_Four , L
i₂Mg Ge O_Four , Li₂Zn GeO_Four , Li₃Zn_0.5Ge O_Four
 , Li₂Zn Ge₃O₈ Or these non-stoichiometric compounds
However, the present invention is not limited to these. Also general
The valence of M in the formula (1) is not particularly limited.
It may be a single valence or a mixture of each valence.
Yes. In addition, lithium of the lithium composite oxide in the present invention
The amount can be varied continuously, at which time the compound
It can be a mixture of physical examples, or a single-phase compound.
In the case of light, either a mixture or a single-phase compound may be used. Also
When the amount of lithium is small,
In some cases, it may be a mixture with a non-containing oxide.
Is also effective for the mixture.

In the present invention, the general formula (2), Li _s SnO _t general formula (2) (in the formula, s = 0.1 to 8 and t = 1 to 6 are represented).
It is more preferable to use the lithium composite oxide represented by as the negative electrode active material. For example Li _0.1 Sn O _2.05 , L
i _0.5 Sn O _2.25 , Li Sn O _2.5 , Li _1.5 SnO _2.75 ,
Li ₂ Sn O ₃ , Li ₃ Sn O _3.5 , Li ₄ Sn O ₄ , Li ₅ S
_{n O 4.5, Li 6 Sn O} 5, Li 7 Sn O 5.5, Li 8 Sn O
_{6, Li 0.1 Sn O 1.05,} Li 0.5 Sn O 1. 25, Li Sn O
_1.5 , Li _1.5 Sn O _1.75 , Li ₂ Sn O ₂ , Li ₃ Sn O
_2.5 , Li ₄ Sn O ₃ , Li ₄ Sn O _3.5 , Li ₆ Sn O ₄ ,
Examples thereof include Li ₇ Sn O _4.5 , Li ₈ Sn O ₅ , and the like, but are not limited thereto. The valence of Sn is not particularly limited and may be a single valence or a mixture of each valence. Further, the amount of lithium in the lithium composite oxide represented by the general formula (2) can be continuously changed between 0.1 and 6, and at that time, a mixture of the above compound examples or a single-phase compound can be obtained. In the present invention, either a mixture or a single phase compound may be used. If the lithium amount is small also, and the compound examples, lithium-free oxides (e.g. Sn O, Sn O _2, etc.) they may have a mixture of, it is effective in the mixture in the present invention.

In the present invention, by using the lithium composite oxide represented by the general formula (1) or the general formula (2) as the negative electrode active material, the charge and discharge cycle characteristics are more excellent and It is possible to obtain a non-aqueous secondary battery having high discharge voltage, high capacity and high safety. Various compounds can be included in the negative electrode active material precursor of the present invention. For example, transition metals (elements of the fourth, fifth, and sixth periods of the Periodic Table belonging to groups IIIA to IB)
And Group IIIB elements of the Periodic Table and P, Cl, Br, I, F
Can be included. It may also contain a dopant of various compounds (for example, compounds of Sb, In, and Nb) that enhance electron conductivity. The amount of the compound added is preferably 0 to 20 mol%.

The general formula (1) or (2) in the present invention
For the synthesis of the lithium composite oxide represented by, either a firing method or a solution method can be adopted. For example, the lithium composite oxide represented by the general formula (2) will be described in detail. A lithium compound and a tin compound may be mixed and fired. Examples of the lithium compound include lithium hydroxide, lithium carbonate, lithium nitrate, lithium sulfate, lithium sulfite, lithium phosphate, lithium tetraborate, lithium chlorate, lithium perchlorate, lithium thiocyanate, lithium formate, lithium acetate, lithium oxalate, Examples thereof include lithium citrate, lithium lactate, lithium tartrate, lithium pyruvate, lithium trifluoromethanesulfonate, lithium fluoride, lithium chloride, lithium bromide and lithium iodide. The tin compound for example _{Sn O, Sn O 2, Sn} 2 O 3, Sn 3 O
₄ , Sn ₇ O ₁₃ · H ₂ O, Sn ₈ O ₁₅ , stannous hydroxide, stannic oxyhydroxide, stannic acid, stannous oxalate, stannous phosphate, orthostannic acid, metastannic acid , Parastannic acid, stannous fluoride, stannic fluoride, stannous chloride, stannic chloride, stannous bromide, stannic bromide, stannous iodide, stannous iodide Etc. can be mentioned.
The firing temperature may be a temperature at which a part of the mixed compound used in the present invention is decomposed and melted, and particularly 250 to
2000 ° C. is preferable, and 250 to 1500 ° C. is particularly preferable. The calcination gas atmosphere is not particularly limited, and the calcination gas atmosphere is synthesized in air, a gas having an oxygen concentration adjusted to an arbitrary ratio, or an inert gas. Other lithium composite oxides represented by the general formula (1) can be easily synthesized by the same method as above.

In the present invention, the lithium composite oxide represented by the general formula (1) or (2) synthesized as described above is heat-treated in an atmosphere having an oxygen concentration of less than 20% or a reduced pressure of 2 torr or less. The performance can be further improved by using the lithium composite oxide heat-treated in the atmosphere (hereinafter referred to as “reduction-treated lithium composite oxide”) as the negative electrode active material. In particular, it is possible to further increase the capacity while maintaining the charge / discharge cycle characteristics.

The shape of the lithium composite oxide represented by the general formula (1) or (2) to be treated under the above atmosphere is not particularly limited, and may be a synthesized lump as it is,
It may be pulverized by a pulverizer, but it is preferably about 200 μm or less. Examples of the atmosphere include hydrogen, carbon monoxide, nitrogen, argon, helium, krypton, xenon, air, water vapor, carbon dioxide, etc., but preferably an oxygen concentration of at least one of hydrogen, carbon monoxide, and argon is less than 20%. Or an atmosphere of reduced pressure of 2 torr or less. Examples of means for realizing a reduced pressure atmosphere of 2 torr or less include a method using an oil rotary pump, an oil diffusion pump, a turbo molecular pump, an ion pump, etc., but are not particularly limited. The heating temperature is not particularly limited, but is preferably 100 to 1000 ° C, more preferably 100 to 700 ° C. The heat treatment time is preferably 10 minutes or longer, more preferably 30 minutes or longer. The lithium composite oxide represented by the general formula (1) or (2) at the time of heat treatment may be in a stationary state or a stirring state. As described above, the “reduction-treated lithium composite oxide” used in the present invention can be obtained.

In the "reduction-treated lithium composite oxide" obtained as described above, Si, Ge, and Li of the lithium composite oxide represented by the general formula (1) or (2),
The valence of Sn, Pb, Bi, Sb, Zn, In, or Mg becomes lower. Taking Sn as an example, L
By subjecting i ₂ Sn O ₃ to the reduction treatment by the above method,
Li ⁺ is not reduced, and some or all of Sn ⁴⁺ is Sn.
It will be reduced to ²⁺ . The ratio of Sn ⁴⁺ to Sn ²⁺ is not particularly limited, and any ratio is effective in the present invention. The lithium composite oxide represented by the general formula (1) or (2) used in the present invention, and “reduction-treated lithium composite oxide” (hereinafter, these are generically referred to as “lithium composite oxide used in the present invention”) The average particle size of () is preferably 0.1 to 60 μm. A well-known crusher or classifier is used to obtain a predetermined particle size. For example, mortar, ball mill, vibrating ball mill,
A satellite ball mill, a planetary ball mill, a swirling airflow type jet mill, a sieve, etc. are used.

The positive electrode active material used in the present invention may be a transition metal oxide capable of reversibly inserting and releasing lithium ions, but a lithium-containing transition metal oxide is particularly preferable.
Preferred lithium-containing transition metal oxide positive electrode active materials used in the present invention include lithium-containing Ti, V, Cr,
Examples thereof include oxides containing Mn, Fe, Co, Ni, Cu, Mo and W. Alkali metals other than lithium (elements IA and IIA of the Periodic Table), semimetals Al, Ga,
In, Ge, Sn, Pb, Sb, Bi and the like may be mixed. The mixing amount is preferably 0 to 10 mol%. As a more preferable lithium-containing transition metal oxide positive electrode active material used in the present invention, a lithium compound / transition metal compound (wherein the transition metal is Ti, V, Cr, Mn, Fe, C
It is preferable to mix and synthesize such that the total molar ratio of at least one selected from o, Ni, Mo, and W) is 0.3 to 2.2.

Particularly preferred Lithiu used in the present invention
Lithium-containing transition metal oxide positive electrode active material
Compound / transition metal compound (where transition metal means V, C
At least 1 selected from r, Mn, Fe, Co, and Ni
The total molar ratio of the seeds) is 0.3 to 2.2.
It is preferable to synthesize them together. When used in the present invention
Particularly preferred lithium-containing transition metal oxide positive electrode active material
Is Lix MOz (where M = Co, Mn, Ni, V,
Transition metal containing at least one selected from Fe), x
= 0.3-1.2, z = 1.4-3)
Good More preferred lithium content used in the present invention
As the metal oxide positive electrode active material, Li_xCoO₂ , Li
_xNiO₂ , Li_xCo_aNi_1-aO₂ , Li_zCo _b
V_1-bO_z, Li_xCo_bFe_1-bO₂ , Li_xMn₂ 
O_Four , Li_xMn_cCo_2-cO_Four , Li_xMn_cNi
_2-cO_Four , Li_xMn_cV_2-cO_z, Li_xMn _cFe
_2-cO_Four , Li_xMn₂ O_Four And MnO₂ Mixture of Li
_2xMnO₃ And MnO₂ Mixture of Li_xMn₂ O_Four , L
i_2xMnO₃ And MnO₂ (Where x = 0.6-
1.2, a = 0.1 to 0.9, b = 0.8 to 0.98,
c = 1.6-1.96, z = 2.01-5)
It

Further preferred Lithiu used in the present invention
The lithium-containing metal oxide positive electrode active material may be Li_xCoO
₂ , Li_xNiO₂ , Li_xCo_aNi_1-aO₂ , Li
_xCo _bV_1-bO_z, Li_xCo_bFe_1-bO₂ , Li
_xMn₂ O_Four , Li_xMn_cCo_2-cO_Four , Li_xMn
_cNi_2-cO_Four , Li_xMn_cV_2-cO_Four , Li_xMn
_cFe_2-cO_Four (Where x = 0.7 to 1.04, a =
0.1 to 0.9, b = 0.8 to 0.98, c = 1.6 to
1.96, z = 2.01 to 2.3). Starting
Most Preferred Lithium-Containing Transition Metal Oxides Used in Ming
As the positive electrode active material, Li_xCoO₂ , Li_xNiO
₂ , Li_xCo_aNi_1-aO₂ , Li_xMn₂ O_Four , L
i_xCo_bV_1-bO_z(Where x = 0.7 to 1.1, a
= 0.1 to 0.9, b = 0.9 to 0.98, z = 2.0
1 to 2.3). Most preferred for use in the present invention
As a positive electrode active material for transition metal oxide containing lithium
Is Li_xCoO₂ , Li_xNiO₂ , Li_xCo_aN
i_1-aO₂ , Li_xMn₂ O_Four , Li_xCo_bV_1-bO
_z(Here, x = 0.7 to 1.04, a = 0.1 to 0.
9, b = 0.9-0.98, z = 2.02-2.3)
can give. Here, the above x value is the value before the start of charge / discharge.
And increases or decreases due to charge and discharge.

The positive electrode active material can be synthesized by a method of mixing and firing a lithium compound and a transition metal compound or by a solution reaction, but a firing method is particularly preferable. The firing temperature used in the present invention may be a temperature at which a part of the mixed compound used in the present invention is decomposed and melted, and is preferably 250 to 2000 ° C, particularly 350 to 1500.
C is preferred. The firing gas atmosphere used in the present invention is not particularly limited, but in the positive electrode active material, air or a gas having a large proportion of oxygen (for example, about 30% or more), and in the negative electrode active material, the proportion of air or oxygen is set. A small amount of gas (for example, about 10% or less) or an inert gas (nitrogen gas, argon gas) is preferable.

When synthesizing the positive electrode active material of the present invention, a method of chemically inserting lithium ions into the transition metal oxide is to synthesize lithium metal, lithium alloy or butyllithium with the transition metal oxide. The method is preferred. The average particle size of the positive electrode active material used in the present invention is not particularly limited, but is preferably 0.1 to 50 μm.
A well-known crusher or classifier is used to obtain a predetermined particle size. For example, a mortar, a ball 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.

The equivalent amount of lithium inserted into the "lithium composite oxide used in the present invention" is 3 to 10 equivalents, and the ratio of the amount used with the positive electrode active material is determined according to this equivalent amount.
It is preferable to multiply the usage ratio based on this equivalent by a coefficient of 0.5 to 2 to use. When the lithium source is other than the positive electrode active material (for example, lithium metal, alloy, butyl lithium, etc.), the amount of the positive electrode active material used is determined according to the lithium release equivalent of the negative electrode active material. Also at this time, it is preferable to multiply the usage ratio based on this equivalent by a coefficient of 0.5 to 2 times. The "lithium composite oxide used in the present invention" has a crystal structure, but as lithium is inserted, the crystallinity decreases and the crystallinity changes. Therefore, the structure in which reversible redox is performed as the negative electrode active material is presumed to be a compound having high amorphousness. Therefore,
The “lithium composite oxide used in the present invention” may have a crystalline structure, an amorphous structure, or a mixed structure thereof.

As the negative electrode active material that can be used in combination with the present invention, lithium metal, lithium alloy (Al, A
1-Mn (U.S. Pat. No. 4,820,599), Al-
Mg (JP-A-57-98,977), Al-Sn (JP-A-63-6,742), Al-In, Al-Cd (JP-A-1-144,573), lithium ion or lithium metal Calcined carbonaceous compounds capable of occluding and releasing (for example, JP-A-58-209,864 and 61-21).
4,417, ibid. 62-88,269, ibid. 62-21
6,170, 63-1,282, 63-2
4,555, the same 63-121,247, the same 63-1
21,257, 63-155,568, 63-2
76, 873, 63-314, 821, JP-A-1-.
204,361, 1-221,859, 1-2
74, 360). The purpose of the combined use of the above-mentioned lithium metal and lithium alloy is to insert lithium into the "lithium composite oxide used in the present invention" in the battery, and as a battery reaction, dissolution of lithium metal, etc.
It does not utilize the precipitation reaction.

A conductive agent, a binder, a filler and the like can be added to the electrode mixture. The conductive agent may be any electron-conductive material that does not cause a chemical change in the constructed battery. Usually, natural graphite (scaly graphite, flake graphite, earthy graphite, etc.), artificial graphite, carbon black, acetylene black, Ketjen black, carbon fibers and metals (copper, nickel, aluminum, silver (JP-A-63) -1
48, 554), powders, metal fibers, or polyphenylene derivatives (Japanese Patent Laid-Open No. 59-20971) can be included as one kind or a mixture thereof. The combined use of graphite and acetylene black is particularly preferred. The amount added is not particularly limited, but is preferably 1 to 50% by weight, and particularly preferably 2 to 30% by weight. For carbon and graphite, 2 to 15% by weight is particularly preferable.

The binder is usually starch, polyvinyl alcohol, carboxymethyl cellulose, hydroxypropyl cellulose, regenerated cellulose, diacetyl cellulose, polyvinyl chloride, polyvinylpyrrolidone,
Tetrafluoroethylene, polyvinylidene fluoride, polyethylene, polypropylene, ethylene-propylene-diene terpolymer (EPDM), sulfonated EPDM, styrene butadiene rubber, polybutadiene, fluororubber,
Polysaccharides such as polyethylene oxide, thermoplastic resins, polymers having rubber elasticity and the like are used alone or as a mixture thereof. When a compound containing a functional group that reacts with lithium, such as a polysaccharide, is used, it is preferable to add a compound such as an isocyanate group to deactivate the functional group. The amount of the binder added is not particularly limited, but is preferably 1 to 50% by weight, and particularly preferably 2 to 30% by weight. As the filler, any fibrous material that does not cause a chemical change in the constructed battery can be used. Generally, olefin polymers such as polypropylene and polyethylene, fibers such as glass and carbon are used. The amount of the filler added is not particularly limited, but is preferably 0 to 30% by weight.

As the electrolyte, propylene is used as an organic solvent.
Len carbonate, ethylene carbonate, butylene car
Carbonate, dimethyl carbonate, diethyl carbonate
, Γ-butyrolactone, 1,2-dimethoxyethane
Amine, tetrahydrofuran, 2-methyltetrahydrofuran
Amine, dimethyl sulfoxide, 1,3-dioxolane,
Formamide, dimethylformamide, dioxolane,
Acetonitrile, nitromethane, methyl formate, methyl acetate
, Methyl propionate, ethyl propionate, phosphoric acid
Triester (JP-A-60-23,973), Trimeth
Xymethane (JP-A-61-4,170), dioxolane
Derivatives (JP-A-62-15,771, JP-A-62-22,3)
72, 62-108, 474), sulfolane (Japanese Patent Application Laid-Open No. Sho 62-187).
62-31,959), 3-methyl-2-oxazolidi
Non (JP-A-62-44,961), propylene carbon
Net derivatives (Japanese Patent Laid-Open Nos. 62-290,069, 62-
290,071), a tetrahydrofuran derivative
63-32, 872), diethyl ether (JP-A-63-63)
-62,166), 1,3-propanesarton
63-102, 173) and other aprotic organic solvents
Solvents mixed with at least one kind and soluble in the solvents
Lithium salt, eg LiClO_Four , LiBF ₆ , Li
PF₆ , LiCF₃ SO₃ , LiCF₃ CO₂ , LiA
sF₆ , LiSbF₆ , LiB_TenCl_Ten(JP-A-57-
74,974), lower aliphatic lithium carboxylate (JP
60-41,773), LiAlCl_Four , LiCl,
LiBr, LiI (JP-A-60-247,265),
Loloborane lithium (JP-A-61-165,957),
Lithium tetraphenylborate (JP-A-61-214,37)
6) and the like. in
Also, propylene carbonate or ethylene carbonate
And 1,2-dimethoxyethane and / or diethyl
LiCF in the carbonate mixture₃ SO₃ , LiClO
_Four , LiBF_Four And / or LiPF₆ Electrolysis including
Quality is preferred.

The amount of these electrolytes to be added to the battery is not particularly limited, but a necessary amount can be used depending on the amount of the positive electrode active material or the negative electrode active material and the size of the battery. The volume ratio of the solvent is not particularly limited, but it is propylene carbonate.
In the case of a mixed solution of ethylene carbonate or ethylene carbonate, butylene carbonate and 1,2-dimethoxyethane and / or diethyl carbonate, 0.4 / 0.6 to
0.6 / 0.4 (mixing ratio of both ethylene carbonate and butylene carbonate is 0.4 / 0.6-
0.6 / 0.4, and the mixing ratio when 1,2-dimethoxyethane and diethyl carbonate are both used is 0.4 /
0.6-0.6 / 0.4) is preferable. The concentration of the supporting electrolyte is not particularly limited, but is preferably 0.2 to 3 mol per liter of the electrolytic solution.

In addition to the electrolytic solution, the following solid electrolytes can be used. Solid electrolytes are classified into inorganic solid electrolytes and organic solid electrolytes. Li-nitrides, halides, oxyacid salts, and the like are well known as inorganic solid electrolytes. Among them, Li ₃ N, LiI, Li ₅ N
_{I 2, Li 3 N-LiI} -LiOH, LiSiO 4, L
iSiO ₄ -LiI-LiOH (JP-A-49-81,8)
_{99), xLi 3 PO 4 -} (1-x) Li 4 SiO 4
(JP 59-60,866), Li ₂ SiS ₃ (JP 60-501,731), phosphorus sulfide compound (JP 6
2-82,665) is effective. In the organic solid electrolyte, a polyethylene oxide derivative or a polymer containing the derivative (JP-A-63-135,447), a polypropylene oxide derivative or a polymer containing the derivative, a polymer containing an ion-dissociating group (JP-A-62-135). 254,30
2, ibid. 62-254, 303, ibid. 63-193, 95
4), a mixture of a polymer containing an ionic dissociative group and the above aprotic electrolytic solution (U.S. Pat. Nos. 4,792,504, 4,830,939, JP-A-62-22,375 and JP-A-6-222,375.
2-22, 376, 63-2, 375, 63-2
2,776, JP-A-1-95,117) and phosphoric acid ester polymers (JP-A-61-256,573) are effective. Furthermore, there is also a method of adding polyacrylonitrile to the electrolytic solution (JP-A-62-278,774). Further, a method of using an inorganic and organic solid electrolyte in combination (Japanese Patent Laid-Open No. 60-1,
768) is also known.

As the separator, an insulating thin film having a large ion permeability and a predetermined mechanical strength is used. A sheet or non-woven fabric made of olefin polymer such as polypropylene or glass fiber or polyethylene is used because of its resistance to organic solvent and hydrophobicity. The pore size of the separator is in the range generally used for batteries. For example, 0.01 to 10 μ
m is used. The thickness of the separator is generally within the range for batteries. For example, 5 to 300 μm is used.

It is also known to add the following compounds to the electrolyte for the purpose of improving discharge and charge / discharge characteristics. For example, pyridine (JP-A-49-108,52)
5), triethylphosphite (JP-A-47-4,3)
76), triethanolamine (JP-A-52-72,4).
25), cyclic ether (JP-A-57-152,68)
4), ethylenediamine (JP-A-58-87,77)
7), n-glyme (JP-A-58-87,778), hexaphosphoric acid triamide (JP-A-58-87,779),
Nitrobenzene derivative (JP-A-58-214, 28)
1), sulfur (JP-A-59-8,280), quinoneimine dye (JP-A-59-68,184), N-substituted oxazolidinone and N, N'-substituted imidazolidinone (JP-A-5-280).
9-154,778), ethylene glycol dialkyl ether (JP-A-59-205,167), quaternary ammonium salt (JP-A-60-30,065), polyethylene glycol (JP-A-60-41). , 773), pyrrole (JP-A-60-79,677), 2-methoxyethanol-
Le (JP 60-89,075), AlCl ₃ (JP-61-88,466), conductive polymer - monomer of the electrode active material - (JP 61-161,673), triethylene phosphoramide Amide (JP-A-61-208,758), trialkylphosphine (JP-A-62-80,976), morpholine (JP-A-62-80,977), aryl compound having a carbonyl group 62-86, 67
3), hexamethylphosphoric triamide and 4-alkylmorpholine (JP 62-217,575), bicyclic tertiary amine (JP 62-217,578), oil (JP 62 -287,580), a quaternary phosphonium salt (JP-A-63-121268), a tertiary sulfonium salt (JP-A-63-121269), and the like.

Further, in order to make the electrolytic solution nonflammable, a halogen-containing solvent such as carbon tetrachloride or ethylene trifluoride chloride can be contained in the electrolytic solution. (JP-A-48-36,
632) Further, the electrolytic solution may contain carbon dioxide gas in order to have suitability for high temperature storage. (JP-A-59-1
34, 567) Further, the mixture of the positive electrode and the negative electrode may contain an electrolytic solution or an electrolyte. For example, a method is known in which the ion conductive polymer, nitromethane (JP-A-48-36,633) and an electrolytic solution (JP-A-57-124,870) are included. Further, the surface of the positive electrode active material can be modified. For example, the surface of the metal oxide may be treated with an esterifying agent (JP-A-55-163,779),
Treatment with a photocatalyst (JP-A-55-163,780), conductive polymers (JP-A-58-163,188, 59-14).
274), polyethylene oxide, etc. (JP-A-60-
97, 561). Also, the surface of the negative electrode active material can be modified. For example, an ion conductive polymer or polyacetylene layer is provided (JP-A-58-111276), or LiCl
(JP-A-58-142,771) and the like.

The collector of the electrode active material may be any electron conductor as long as it does not cause a chemical change in the constructed battery. For example, for the positive electrode, in addition to stainless steel, nickel, aluminum, titanium, calcined carbon, etc. as the material, carbon on the surface of aluminum or stainless steel,
Those treated with nickel, titanium or silver, and the negative electrode are made of stainless steel, nickel, copper, titanium,
In addition to aluminum and calcined carbon, copper, stainless steel whose surface is treated with carbon, nickel, titanium or silver), an Al-Cd alloy, or the like is used. It is also used to oxidize the surface of these materials. The shape is
In addition to the foil, a film, a sheet, a net, a punched product, a lath body, a porous body, a foamed body, a molded body of a fiber group and the like are used. The thickness is not particularly limited, but is 1 to 5
Those having a diameter of 00 μm are used.

The shape of the battery can be any of coins, buttons, sheets, cylinders, corners and the like. When the shape of the battery is a coin or a button, the mixture of the positive electrode active material and the negative electrode active material is used by being compressed into a pellet shape. The thickness and diameter of the pellet are determined by the size of the battery. Further, when the battery has a sheet, cylinder, or square shape, the mixture of the positive electrode active material and the negative electrode active material is mainly used after being coated, dried, and compressed on the current collector. The coat thickness, length and width are determined by the size of the battery,
The thickness of the coat is 1-2 in the compressed state after drying.
000 μm is particularly preferable.

The application of the non-aqueous secondary battery of the present invention is not particularly limited. For example, when it is installed in an electronic device, a color notebook computer, a black and white notebook computer, a pen input computer, a pocket (palmtop) computer, a notebook. Type word processor, pocket word processor, e-book player, mobile phone, cordless phone handset, pager, handy terminal, mobile fax, mobile copy, mobile printer, headphone stereo, video movie, LCD TV, handy cleaner, portable CD, mini disk, Electric shaver, electronic translator, car phone,
There are transceivers, power tools, electronic organizers, calculators, memory cards, tape recorders, radios, backup power supplies, memory cards, etc. Other consumer products such as automobiles, electric vehicles, motors, lighting equipment, toys,
Game equipment, road conditioners, irons, watches, strobes, cameras, medical equipment (pacemakers, hearing aids, shoulder massagers, etc.), etc. Furthermore, it can be used for various military purposes and for space. It can also be combined with a solar cell.

[0034]

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.

Synthesis Example-1 7.3 g of lithium carbonate and 15.1 g of tin dioxide are dry-mixed and put in an alumina crucible, and the mixture is dried at 1000 ° C. in air at 1 ° C.
It was baked for 2 hours. After firing, it was cooled to room temperature and taken out of the firing furnace to obtain Li ₂ Sn O ₃ . The compound was pulverized with a jet mill to obtain Li ₂ Sn O ₃ having an average particle size of 3 μm.
(Compound A-1) In the same manner, stoichiometric amounts of raw materials were mixed, fired and pulverized to obtain Li ₂ Ge O ₃ (Compound B-1),
Li ₂ Pb O ₃ (C-1), Li ₃ Bi O ₄ (D-1), L
i ₃ Sb O ₄ (E-1), Li ₂ Zn O ₂ (F-1), Li _{3
In O 3 (G-1)} , Li 2 Zn Sn 2 O 6 (H-1), L
i ₂ Mg Sn ₂ O ₆ (I-1), Li _0.1 SnO _2.05 (J-
1), Li _0.5 Sn O _2.25 (K-1), Li ₄ Sn O ₄ (L
-1), Li ₆ Sn O ₅ (M-1), Li ₈ Sn O ₆ (N
-1) was obtained.

Synthesis Example-2 10.2 g of lithium acetate dihydrate and 13.5 g of tin monoxide
Dry mixed, put in a porcelain crucible, and under argon atmosphere,
It was baked at 350 ° C. for 24 hours. After firing, cool to room temperature
Then, remove it from the firing furnace and₂Sn O₂ Got Conversion
The compound was crushed with a jet mill to obtain L with an average particle size of 2.5 μm.
i₂Sn O₂ Got (Compound P-1) In the same manner, the stoichiometric raw materials are mixed and baked.
Cultivated, crushed, Li respectively_0.1Sn O_1.05(Compound Q-
1), Li_0.5Sn O_1.25(R-1), Li Sn O _2.5 
(S-1), Li_FourSn O_Four (T-1), Li₆Sn O_Four 
(U-1), Li₈SnO_Five (V-1) was obtained.

Synthesis Example-3 The compound A-1 synthesized in Synthesis Example-1 was put in a boat crucible and inserted into a quartz reaction tube having a diameter of about 40 mm at both ends and a diameter of about 120 mm at the center. Then, nitrogen gas was caused to flow from a part of the reaction tube for 10 minutes to replace the inside of the reaction tube with nitrogen gas. afterwards,
While flowing hydrogen gas at 2 liters / minute, the heating rate is 25 ° C /
The temperature rose to 300 ° C in minutes. The mixture was heat-treated at this temperature for 2 hours, then cooled to room temperature, replaced with nitrogen gas, and taken out to obtain "reduction-treated lithium composite oxide". (Compound A
-2) Compounds synthesized in Synthesis Example-1, B-1, C-1, D-
1, G-1, H-1, I-1, L-1, M-1, N-1
Is also subjected to reduction heat treatment in the same manner as in “reduction-treated lithium composite oxide”, B-2, C-2, and D, respectively.
-2, G-2, H-2, I-2, L-2, M-2, N-
Got 2.

Synthesis Example-4 The compound A-1 synthesized in Synthesis Example-1 was placed in a magnetic crucible and introduced into a vacuum electric furnace. Then, set the pressure in the furnace to 1 x 1
40 ° C at a heating rate of 20 ° C / min in a reduced pressure of 0 ^-3 torr
The temperature was raised to 0 ° C., and vacuum heat treatment was performed at this temperature for 10 hours. Then cool to room temperature, air leak,
Take it out into the atmosphere and use "reduction treatment lithium composite oxide"
Got (Compound A-3) Compounds synthesized in Synthesis Example-1, B-1, C-1, D-
1, G-1, H-1, I-1, L-1, M-1, N-1
Is also subjected to vacuum heat treatment in the same manner as in “reduction-treated lithium composite oxide”, B-3, C-3, and D, respectively.
-3, G-3, H-3, I-3, L-3, M-3, N-
Got 3.

Example 1 As a method for preparing a mixture, in the negative electrode material, 82% by weight of the compound A-1 synthesized in Synthesis Example-1, 8% by weight of scaly graphite as a conductive agent, and 4% by weight of acetylene black were used. %, Polyvinylidene fluoride as a binder was mixed at a mixing ratio of 6% by weight, and a mixture was compression molded into pellets (13 mmΦ, 22
(mg) was used after drying with a far infrared heater (150 ° C. for 3 hours) in a dry box (dew point −40 to −70 ° C., dry air). For the positive electrode material, the positive electrode active material LiCoO 2
82% by weight of ₂ , ₂ % by weight of flake graphite as a conductive agent,
A mixture of 4% by weight of acetylene black and 6% by weight of tetrafluoroethylene as a binder was compression molded into a positive electrode pellet (13 mmΦ, compound A-
It was adjusted to a lithium insertion capacity of 1. The charge capacity of LiCoO ₂ was 170 mAh / g. ) Was dried with a far infrared heater (150 ° C. for 3 hours) in the same dry box as above and then used. 80 μm for both positive and negative electrode cans
A thick SUS316 net was used by welding to a coin can. 200 μl of 1 mol / liter LiPF ₆ (a 2: 2: 6 volume mixture of ethylene carbonate, butylene carbonate and dimethyl carbonate) was used as an electrolyte, and a microporous polypropylene sheet and a polypropylene non-woven fabric were used as a separator. Was used by impregnating a non-woven fabric. Then, a coin type non-aqueous secondary battery as shown in FIG. 1 was produced in the same dry box as above.

This non-aqueous secondary battery was charged with 0.75 mA / cm ²
The charge and discharge test was performed in the range of 4.3 to 2.7 V with the constant current density of. (All tests started with charging.) The results are shown in Table 1. The abbreviations shown in Table 1 are
(A) Negative electrode active material of the present invention, (b) First discharge capacity (mAh per 1 g of negative electrode active material), (c) Average discharge voltage (V), (d) Charge-discharge cycle property (first discharge) The number of cycles at which the capacity reaches 60% of the capacity is shown. Compounds B-1, C-1, D-1, and E synthesized in Synthesis Example-1
-1, F-1, G-1, H-1, I-1, J-1, K-
With respect to 1, L-1, M-1, and N-1, coin-type nonaqueous secondary batteries were prepared by the same method, and a charge / discharge test was conducted. The results are shown in Table 1. From these results, it can be seen that the negative electrode active material used in the present invention provides a non-aqueous secondary battery having excellent charge / discharge cycle property, high discharge voltage, and high capacity.

[0041]

[Table 1]

Example-2 Example-2 except that the compound P-1 synthesized in Synthesis Example-2 was used in place of the negative electrode active material A-1 in Example-1.
A coin-type non-aqueous secondary battery was produced by the same method as in 1 and a charge / discharge test was conducted. The results are shown in Table 2. The abbreviations shown in Table 2 are the same as in Example-1 (a), (b), (c), and (d). A coin type non-aqueous secondary battery was prepared by the same method for the compounds Q-1, R-1, S-1, T-1, U-1, and V-1 synthesized in Synthesis Example-2.
A charge / discharge test was performed. The results are shown in Table 2.
From these results, it can be seen that the negative electrode active material used in the present invention provides a non-aqueous secondary battery having excellent charge / discharge cycle property, high discharge voltage, and high capacity.

[0043]

[Table 2]

Example 3 A coin type non-aqueous secondary battery was prepared in the same manner as in Example 1 except that the compound A-2 synthesized in Synthesis Example 3 was used instead of the negative electrode active material A-1. It was produced and a charge / discharge test was performed. The results are shown in Table 3. The abbreviations shown in Table 3 are the same as in Example-1 (a), (b), (c) and (d). Compound B synthesized in Synthesis Example-3
-2, C-2, D-2, G-2, H-2, I-2, L-
For 2, M-2 and N-2, coin-type non-aqueous secondary batteries were prepared by the same method and a charge / discharge test was conducted. The results are shown in Table 3. From this result, when the "reduction-treated lithium composite oxide" used in the present invention is used as the negative electrode active material, the charge-discharge cycle property is excellent, and the high discharge voltage,
It can be seen that it gives a higher capacity non-aqueous secondary battery.

[0045]

[Table 3]

Example-4 Example-4 except that the compound A-3 synthesized in Synthesis Example-4 was used in place of the negative electrode active material A-1 in Example-1.
A coin-type non-aqueous secondary battery was produced by the same method as in 1 and a charge / discharge test was conducted. The results are shown in Table 4. The abbreviations shown in Table 4 are the same as in Example-1 (a), (b), (c) and (d). Compounds B-3, C-3, D-3, G-3, H-3, I-3 synthesized in Synthesis Example-3,
With respect to L-3, M-3, and N-3, coin-type nonaqueous secondary batteries were produced by the same method, and a charge / discharge test was conducted. The results are shown in Table 4. From these results, it can be seen that when the “reduction-treated lithium composite oxide” used in the present invention is used as a negative electrode active material, a charge / discharge cycle property is excellent, and a high discharge voltage and a higher capacity non-aqueous secondary battery are provided. .

[0047]

[Table 4]

Comparative Example 1 In Example 1, Sn 2 O 3 was used instead of the negative electrode active material A-1.
_A coin type non-aqueous secondary battery was prepared in the same manner as in Example 1 except that ₂ was used, and a charge / discharge test was performed. The results are shown in Table 5. A coin type non-aqueous secondary battery was prepared by the same method using Sn 2 O 3 as the negative electrode active material, and a charge / discharge test was conducted. The results are shown in Table 5. The abbreviations shown in Table 5 are the same as in Example 1 for (a), (b), (c) and (d). The result from the case of using the "lithium composite oxide used in the present invention" as a negative electrode active material, are excellent especially charge-discharge cycle characteristics compared to the Sn O _2, Sn O.

[0049]

[Table 5]

Comparative Example-2 In Example-1, WO was used instead of the negative electrode active material A-1.
_A coin-type non-aqueous secondary battery was produced in the same manner as in Example 1 except that ₂ was used, and a charge / discharge test was performed. The results are shown in Table 6. The abbreviations shown in Table 6 are (a),
(B), (c), and (d) are the same as in Example-1. Using Fe ₂ O ₃ as the negative electrode active material, a coin-type non-aqueous secondary battery was prepared by the same method, and a charge / discharge test was conducted. The results are shown in Table 6. From these results, when the “lithium composite oxide used in the present invention” is used as the negative electrode active material, it is superior to WO ₂ and Fe ₂ O ₃ in terms of charge / discharge cycle characteristics, discharge voltage, and discharge capacity. I understand.

[0051]

[Table 6]

[0052] In Example -6 Example -1 but using Li Ni O ₂ in place of Li Co O ₂ as the positive electrode active material to prepare a coin-type nonaqueous secondary battery in the same manner as in Example 1 , A charge / discharge test was performed. The results are shown in Table 7. The abbreviations shown in Table 7 are the same as in Example-1 (a), (b), (c), and (d). Li Co _0.95 V as the positive electrode active material
_A coin type non-aqueous secondary battery was prepared in the same manner for _0.05 O _2.07 and Li Mn ₂ O ₄ , and a charge / discharge test was conducted.
The results are shown in Table 7. From these results, using any positive electrode active material, charge / discharge cycle characteristics, discharge voltage,
It can be seen that the discharge capacity is excellent in all respects.

[0053]

[Table 7]

Example-7 Compound A-1 synthesized in Synthesis Example-1 as a negative electrode active material
86% by weight, scaly graphite 6% by weight, acetylene black 3% by weight, and 4% by weight of an aqueous dispersion of styrene-butadiene rubber as a binder.
And 1% by weight of carboxymethyl cellulose were added and kneaded with water as a medium to prepare a slurry. The slurry was applied on both sides of a copper foil having a thickness of 18 μm by an extrusion method, dried, compression-molded by a calender press, and cut into a predetermined width and length to prepare a strip-shaped negative electrode sheet. The thickness of the negative electrode sheet was 124 μm. As a positive electrode active material, 87% by weight of LiCoO ₂ , 6% by weight of scaly graphite, 3% by weight of acetylene black, and 3% by weight of an aqueous dispersion of polytetrafluoroethylene and 1% by weight of sodium polyacrylate as a binder were added. The slurry obtained by kneading with water as a medium was applied, dried, pressed and cut on both sides of an aluminum foil having a thickness of 20 μm in the same manner as above. Then, a 220 μm band-shaped positive electrode sheet was produced. After spot-welding nickel and aluminum lead plates to the ends of the negative electrode sheet and the positive electrode sheet, respectively, in a dry air with a dew point of -40 ° C or less, 1
It was dehydrated and dried at 50 ° C. for 2 hours. Further, the dehydrated and dried positive electrode sheet (8), the microporous polypropylene film separator (Celgard 2400), the dehydrated and dried negative electrode sheet (9) and the separator (10) were laminated in this order, and wound in a spiral shape with a winding machine. Turned

This wound body is used also as a negative electrode terminal, nickel
Stored in a plated steel bottomed cylindrical battery can (11)
did. Furthermore, as an electrolyte, 1 mol / liter Li
PF ₆ (Ethylene carbonate, butylene carbonate
And 2: 2: 6 volume mixture of dimethyl carbonate)
I poured it into a pond can. Install the battery cover (12) with the positive terminal.
A caulking through a sket (13) to produce a cylindrical battery
It was The positive electrode terminal (12) and the positive electrode sheet (8) are electrically connected to each other.
The pond can (11) has a lead sheet and a negative electrode sheet (9) in advance.
Connected by the child. FIG. 2 shows a cross section of the cylindrical battery.
Incidentally, (14) is a safety valve. Charge / discharge conditions are 4.3
~ 2.7V, 1mA / cm² And The result is the 8th
Shown in the table. The abbreviations shown in Table 8 are (b), (c),
Both (d) are the same as in Example-1. (E) is AA
The discharge capacity per ml of pond is shown.

[0056]

[Table 8]

Example-8 A coin type non-aqueous secondary battery of the compound A-1 synthesized in Synthesis Example-1 was prepared according to Example-1 and the following safety test was carried out. 5 mA / c for each 50 coin-type non-aqueous secondary batteries
After repeating 20 cycles of charge and discharge under the condition of m ² , the battery was disassembled and the negative electrode pellet was taken out in 60% RH air to test whether or not to spontaneously ignite. As a result, the number of coin batteries that ignited was 0.

Comparative Example-3 A negative electrode active material made of Li-Al alloy (80% -20% weight ratio, 15 mmΦ, 100 mg) was used in Example-7.
The same experiment was performed. As a result, 32 fired. From these results, it can be seen that the non-aqueous secondary battery of the present invention is extremely safe.

[0059]

INDUSTRIAL APPLICABILITY As in the present invention, the positive electrode active material contains at least one lithium-containing transition metal oxide and the negative electrode active material contains at least 1
By using a specific lithium composite oxide of a certain kind, it is possible to obtain a safe non-aqueous secondary battery having a high discharge operating voltage, a large discharge capacity, and excellent charge / discharge cycle characteristics.

[Brief description of drawings]

FIG. 1 is a cross-sectional view of a coin battery used in an example.

FIG. 2 is a cross-sectional view of a cylindrical battery used in an example.

[Explanation of symbols]

 1 Negative Electrode Sealing Plate 2 Negative Electrode Mixture Pellets 3 Separator 4 Positive Electrode Mixture Pellets 5 Current Collector 6 Positive Electrode Case 7 Gasket 8 Positive Electrode Sheet 9 Negative Electrode Sheet 10 Separator 11 Battery Can 12 Battery Lid 13 Gasket 14 Safety Valve

 ─────────────────────────────────────────────────── ─── Continuation of the front page (72) Kensuke Goda 210 Nakanisha, Minamiashigara-shi, Kanagawa Fuji Photo Film Co., Ltd. (72) Kokatsu Kagawa 210, Nakanuma, Minamiashigara-shi, Kanagawa Fuji Photo Film Co., Ltd. (72) ) Inventor Riki Miyasaka 210 Nakanuma, Minamiashigara City, Kanagawa Prefecture Fuji Photo Film Co., Ltd.

Claims (9)

[Claims] 1. A positive electrode active material, negative electrode active material, it relates to non-aqueous secondary battery comprising a nonaqueous electrolyte containing a lithium salt, at least one general formula of the negative electrode active material _{(1) Li p M q O} r General Formula (1) (where M is Si, Ge, Sn, Pb, Bi, Sb, Z
at least one selected from n, In and Mg, p = 0.
The numbers 1 to 8, q = 1 to 7, and r = 1 to 20 are represented. ) A non-aqueous secondary battery, which is a lithium composite oxide represented by 2. At least one kind of the negative electrode active material is represented by the general formula (2) Li _s SnO _t general formula (2) (in the formula, s = 0.1 to 8 and t = 1 to 6 are represented).
The non-aqueous secondary battery according to claim 1, which is a lithium composite oxide represented by. 3. A lithium composite oxide obtained by heat-treating at least one of the negative electrode active materials, the lithium composite oxide represented by the general formula (1) according to claim 1 in an atmosphere having an oxygen concentration of less than 20%. The non-aqueous secondary battery according to claim 1, wherein 4. A lithium composite oxide in which at least one of the negative electrode active materials is a lithium composite oxide represented by the general formula (2) according to claim 2 which is heat-treated in an atmosphere having an oxygen concentration of less than 20%. The non-aqueous secondary battery according to claim 2, wherein 5. At least one of the negative electrode active materials is a lithium composite oxide obtained by heat-treating the lithium composite oxide represented by the general formula (1) according to claim 1 under a reduced pressure atmosphere of 2 torr or less. The non-aqueous secondary battery according to claim 1, wherein 6. At least one of the negative electrode active materials is a lithium composite oxide obtained by heat-treating the lithium composite oxide represented by the general formula (2) according to claim 2 under a reduced pressure atmosphere of 2 torr or less. The non-aqueous secondary battery according to claim 2, wherein 7. The non-aqueous secondary battery according to claim 1, wherein the positive electrode active material is a lithium-containing transition metal oxide. 8. At least one of the positive electrode active materials comprises Li
_x MO _z (where M is at least one of Co and M
transition metals including n, Ni, V, and Fe), x = 0.2 to
1.2, z = 1.4 to 3), The non-aqueous secondary battery according to any one of claims 1 to 7. 9. At least one of the positive electrode active materials comprises Li
_x CoO ₂ , Li _x NiO 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 , L
i _x Mn _c Ni _2-c O ₄ , Li _x Mn _c V _2-c O ₄ , L
i _x Mn _c Fe _2-c O ₄ (where x = 0.5 to 1.2,
a = 0.1 to 0.9, b = 0.8 to 0.98, c = 1.
6 to 1.96, z = 2.01 to 2.3), The non-aqueous secondary battery according to any one of claims 1 to 8.