JP3498380B2 - Non-aqueous secondary battery - Google Patents

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 typically used as a negative electrode active material 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 drawback of this carbonaceous material is
Since it has conductivity by itself, lithium metal may be deposited on the carbonaceous material during overcharging or rapid charging,
Eventually, the dendritic metal will be deposited. 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. Further, since the carbonaceous material has a relatively small density, the discharge capacity is limited in the double sense that the capacity per volume is low.

On the other hand, as negative electrode active materials other than lithium metal, lithium alloys, and carbonaceous materials, TiS ₂ , LiTiS ₂ , and transition metal oxides having a rutile structure, such as WO ₂ , capable of occluding and releasing lithium. Li _x Fe (F
e ₂₎ O ₄ spinel compounds such as, electrochemically synthesized Fe ₂ O ₃ of a lithium compound, lithium compound of _{Fe 2 O 3, Nb 2 O} 5, iron _{oxide, FeO, Fe 2 O 3,} Fe 3 O ₄ ,
It is known to use cobalt oxide, CoO, Co ₂ O ₃ , Co ₃ O ₄ , amorphous V ₂ O ₅ , or a transition metal oxide whose crystal basic structure is changed by inserting lithium ions as the negative electrode active material. ing. 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.

An example of using tungsten oxide is also described in JP-A-56-11859, and SnO ₂ and S are used.
As an example of using an n compound as an active material of a lithium battery, Li _1.03 Co _0.95 Sn _0.04 O of a secondary battery positive electrode active material is used.
₂ (EP86-106,301), addition of SnO ₂ to V ₂ O ₅ of a secondary battery positive electrode active material (Japanese Patent Application Laid-Open No. 2-158,05).
6), addition of SnO ₂ to α-Fe ₂ O ₃ of the secondary battery negative electrode active material (preferred addition range of SnO ₂ is 0.5 to 10 mol%) (JP-A-62-219,465), positive electrode of primary battery SnO _{2 of} active material (electrochemistry and industrial physical chemistry 46 volumes
No. 7, page 407, 1978) is known. Further, as an example of using SnO ₂ or a Sn compound for an electrochromic electrode, SnO ₂ can reversibly insert Li ions (Journal of Electrochemical Society, Vol. 140, No. 5, L81 1993).
, InO ₂ 8 mol% Sn-doped film (ITO) can reversibly insert Li ions (Solid State Ionics 28-30, 173).
3 pages (issued in 1988) are known. But,
In an electrochromic system, the electrode is made transparent so that it is formed into a thin film by a vapor deposition method or the like, so that it is generally operated at a considerably low current, unlike the practical range of a battery. In "Solid State Ionics" of the above-mentioned document, an experimental example of 1 μA to 30 μA / cm ² is shown.

As a positive electrode active material, Japanese Patent Publication No. 4-3014
Japanese Patent Publication No. 63-59507 discloses a spinel compound.
The publication describes cobalt oxide. On the other hand, Sn
An oxide mainly composed of is used as a negative electrode active material, and by combining these with a positive electrode active material, high discharge potential, high capacity,
Although it is possible to obtain a non-aqueous secondary battery having good charge / discharge cycle characteristics and improved safety, the charge / discharge cycle characteristics are unsatisfactory as described above. Strongly desired.

[0006]

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

[0007]

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 the negative electrode active material is represented by the general formula (4) SnSi _t P _u M ⁶ _v O _s General formula (4) (wherein M ⁶ Is a small amount selected from Ge, B, Al and Pb
At least one. t = 0 to 2.0, u = 0.01 to 4.0,
The numbers v = 0 to 2.0 and s = 1.0 to 26 are represented. )so
Either largely amorphous oxide represented Ranaru could be achieved by a non-aqueous secondary battery comprising.

[0008]

The amorphous oxide referred to in the present invention is preferably mainly amorphous when incorporated in a battery. The term "amorphous" as used herein means a substance having a broad scattering band having an apex at a 20 value of 20 ° to 40 ° by an X-ray diffraction method using CuKα rays, and has a crystalline diffraction line. Good. Preferably, the strongest intensity of the crystalline diffraction lines observed in the 2θ value of 40 ° or more and 70 ° or less is 20 ° in the 2θ value.
It is preferably 500 times or less, more preferably 100 times or less, particularly preferably 5 times or less, and most preferably crystallinity of the diffraction line intensity at the apex of the broad scattering band seen at 40 ° or less. That is, it has no diffraction line.

[0010]

[0011]

[0012]

[0013]

[0014]

[0015]

[0016]

[0017]

[0018]

[0019]

[0020]

[0021]

[0022]

[0023]

The negative electrode active material used in the present invention is represented by the general formula (4). ^{_{SnSi t P u M 6 v O}} s formula (4) wherein, M ⁶ is at least one selected Ge, B, Al, from Pb, preferably, Ge, Al, B,
Al is particularly preferable. t is 0 to 2.0, preferably 0 to 1.5. u is 0.01 to 4.0, preferably 0.01 to 3.5. v is 0 to 2.
It is 0, preferably 0 to 1.5. s is 10-2
6 and particularly preferably 1.02 to 10.

Examples of the oxide represented by the general formula (4) include SnP _0.01 O _1.025 , SnP _0.01 O _2.025 , SnP.
_0.05 O _1.125 , SnP _0.05 O _2.125 , SnP _0.1 O _1.25 ,
SnP _0.1 O _2.25 , SnP _0.2 O _1.5 , SnP _0.2 O _2.5 ,
SnP _0.3 O _1.75 , SnP _0.3 O _2.75 , SnP
_0.7 O _2.75 , SnP _0.8 O ₃ , SnPO ₃ . ₅ , SnP _0.9 G
e _0.1 O _3.45 , SnP _0.8 Ge _0.2 O _3.4 , SnP _0.5 Ge
_0.5 O _3.25 , SnP _0.9 Pb _0.1 O _3.45 , SnP _0.8 Pb
_0.2 O _3.4 , SnP _0.5 Pb _0.5 O _3.25 , SnGe _0.9 P _0.1
O _3.05 , SnGe _0.8 P _0.2 O _3.1 , SnPb _0.9 P _0.1 O
_3.05 , SnPb _0.8 P _0.2 O _3.1 , SnP _0.8 Ge _0.1 Pb
_0.1 O _3.4 , SnP _1.2 O ₄ , SnP _1.5 O ₄ . ₇₅ , SnP ₂
O ₆ , SnP ₂ O ₇ , SnP _0.8 O ₃ , SnSi _0.25 B _0.2 P
_0.2 O ₃ , SnSi _0.5 B _0.2 P _0.2 O ₃ , SnSi _0.9 P _{0.1
O 2.25, SnSi 0.8 P 0.2 O} 3.1, SnSi 0.7 P 0. 3 O
_2.75 , SnSi _0.5 P _0.5 O _3.25 , SnSi _0.3 P _0.7 O
_3.35 , SnSi _0.2 P _0.8 O _3.4 , SnSi _0.5 P _0.1 O
_2.25 , SnSi _0.1 Ge _0.1 P _0.9 O _3.65 , SnSi _0.2 G
e _0.1 P _0.7 O _3.35 , SnSi _0.6 Ge _0.4 P _0.1 O _3.25 ,
SnSi _0.6 Ge _0.2 P _0.2 O _3.1 , SnSi _0.7 Ge _0.1 P
_0.2 O _3.1 , SnSi _0.8 Ge _0.1 P _0.1 O _3.05 , SnSi
_0.8 Ge _0.1 P _0.3 O _3.55 , SnSiGe _0.1 P
_0.1 O _3.45 , SnSiGe _0.2 P _0.2 O _3.9 , SnSiGe
_0.1 P _0.2 O _3.7 , SnSi _0.1 Al _0.1 P _0.9 O _3.6 , Sn
Si _0.3 Al _0.1 P _0.7 O _3.5 , SnSi _0.6 Al _0.3 P _0.1
O _2.9 , SnSi _0.6 Al _0.2 P _0.2 O ₃ , SnSi _0.6 Al
_0.1 P _0.3 O _3.1 ,

SnSi _0.8 Al _0.1 P _0.1 O ₃ , SnSi
_0.8 Al _0.1 P _0.2 O _3.25 , SnSi _0.8 Al _0.2 P _0.2 O
_3.4 , SnSi _0.7 Al _0.2 P _0.3 O _3.45 , SnSi _0.4 A
l _0.2 P _0.6 O _3.6 , SnSiAl _0.2 P _0.4 O _3.5 , SnS
iAl _0.1 P _0.1 O _3.4 , SnSiAl _0.2 P _0.2 O _3.8 , S
nSiAl _0.1 P _0.2 O _3.65 , SnSi _0.1 B _0.1 P _0.9 O
_3.6 , SnSi _0.3 B _0.1 P _0.7 O _3.5 , SnSi _0.6 B _0.3
P _0.1 O _2.9 , SnSi _0.6 B _0.2 P _0.2 O ₃ , SnSi _0.6
B _0.1 P _0.3 O _3.1 , SnSi _0.8 B _0.1 P _0.1 O ₃ , SnS
i _0.8 B _0.1 P _0.3 O _3.5 , SnSiB _0.1 P _0.1 O _3.4 , S
nSiB _0.2 P _0.2 O _3.8 , SnSiB _0.1 P _0.2 O _3.65 ,
SnSi _0.1 Pb _0.1 P _0.9 O _3.6 , SnSi _0.3 Pb _0.1 P
_0.7 O _3.5 , SnSi _0.6 Pb _0.3 P _0.1 O _2.9 , SnSi
_0.6 Pb _0.2 P _0.2 O ₃ , SnSi _0.6 Pb _0.1 P _0.3 O _3.1 ,
SnSi _0.8 Pb _0.1 P _0.1 O ₃ , SnSi _0.8 Pb _0.1 P
_0.3 O _3.5 , SnSiPb _0.1 P _0.1 O _3.4 , SnSiPb
_0.2 P _0.2 O _3.8 , SnSiPb _0.1 P _0.2 O _3.65 , SnP
Al _0.1 O _3.65 , SnPAl _0.3 O _3.95 , SnP _0.8 Al
_0.1 O _3.15 , SnP _0.8 Al _0.3 O _2.45 , SnP _0.5 Al
_0.1 O _2.4 , SnP _0.5 Al _0.3 O _2.7, etc., but not limited to these. Further, the valence of Sn and M ^{6 in} the general formula (4) is not particularly limited and may be a single valence or a mixture of each valence. Further, the amount of M ⁶ of the compound represented by the general formula (4) can be continuously changed in the range of 0 to 2 molar equivalents with respect to Sn, and accordingly the amount of oxygen (the general formula (4) In, the value of s) also changes continuously.

The general formula (4) is preferably represented by the general formula (5). At least one ^{_{SnSi t P u Al v M 7}} w O s formula (5) wherein, M ⁷ is that Ge, B, selected from Pb. t is 0 to 2.0, preferably 0 to 1.5. u is 0.01 to 4.0, preferably 0.01
~ 3.5. v and w are 0 to 2.0, preferably 0 to 1.5. s is 1.0 to 26, and particularly preferably 1.02 to 10.

Examples of the oxide represented by the general formula (5) are SnP _0.01 O _1.025 , SnP _0.01 O _2.025 , SnP.
_0.05 O _1.125 , SnP _0.05 O _2.125 , SnP _0.1 O _1.25 ,
SnP _0.1 O _2.25 , SnP _0.2 O _1.5 , SnP _0.2 O _2.5 ,
SnP _0.3 O _1.75 , SnP _0.3 O _2.75 , SnP
_0.7 O _2.75 , SnP _0.8 O ₃ , SnPO ₃ . ₅ , SnP _1.2 O
₄ , SnP _1.5 O ₄ . ₇₅ , SnP ₂ O ₆ , SnP ₂ O ₇ , Sn
P _0.8 O ₃ , SnSi _0.9 P _0.1 O _2.25 , SnSi _0.8 P _0.2
O _3.1 , SnSi _0.7 P _0.3 O _2.75 , SnSi _0.5 P _0.5 O
_3.25 , SnSi _0.3 P _0.7 O _3.35 , SnSi _0.2 P _0.8 O
_3.4 , SnSi _0.5 P _0.1 O _2.25 , SnSi _0.1 Al _0.1
P _0.9 O _3.6 , SnSi _0.3 Al _0.1 P _0.7 O _3.5 , SnSi
_0.6 Al _0.3 P _0.1 O _2.9 , SnSi _0.6 Al _0.2 P _0.2 O ₃ ,
SnSi _0.6 Al _0.1 P _0.3 O _3.1 , SnSi _0.8 Al _0.1 P
_0.1 O ₃ , SnSi _0.8 Al _0.1 P _0.2 O _3.25 , SnSi _0.8
Al _0.2 P _0.2 O _3.4 , SnSi _0.7 Al _0.2 P _0.3 O _3.45 ,
SnSi _0.4 Al _0.2 P _0.6 O _3.6 , SnSiAl _0.2 P _0.4
O _3.5 , SnSiAl _0.1 P _0.1 O _3.4 , SnSiAl _0.2
P _0.2 O _3.8 , SnSiAl _0.1 P _0.2 O _3.65 , SnPAl
_0.1 O _3.65 , SnPAl _0.3 O _3.95 , SnP _0.8 Al _0.1 O
_3.15 , SnP _0.8 Al _0.3 O _2.45 , SnP _0.5 Al _0.1 O
_2.4 , SnP _0.5 Al _0.3 O _2.7 , SnSi _0.5 P _0.5 Al
_0.1 Ge _0.1 O _3.6 , SnSi _0.5 P _0.5 Al _0.1 B
_0.1 O _3.55 , SnSi _0.5 P _0.5 Al _0.1 Pb _0.1 O
_{It is 3.5} mag, but is not limited to these.

In the present invention, the compounds represented by the general formulas ( 4 ) to (5) as described above are mainly used as the negative electrode active material, so that the charge and discharge cycle characteristics are more excellent and the high discharge voltage, It is possible to obtain a highly safe non-aqueous secondary battery. In the present invention, a particularly excellent effect can be obtained by using a compound containing Sn and having a valence of Sn of 2 as the negative electrode active material. The valence of Sn can be determined by a chemical titration operation. For example Physics and Chemistry
It can be analyzed by the method described on page 165 of Glasses Vol.8 No.4 (1967). It is also possible to determine from the night shift by solid state nuclear magnetic resonance (NMR) measurement of Sn. For example, in wide measurement, metallic Sn (zero-valent Sn) has a peak in an extremely low magnetic field of about 7,000 ppm with respect to Sn (CH ₃ ) ₄ , whereas SnO
At (= 2 valence), around 100 ppm, SnO ₂ (= 4 valence)
Appears at around -600 ppm. In the case of having the same ligand as described above, the night shift greatly depends on the valence of Sn which is the central metal, so that the valence can be determined at the peak position determined by the ¹¹⁹ Sn-NMR measurement.

Various compounds can be included in the negative electrode active material of the present invention. For example, Group Ia elements (Li, Na,
K, Rb, Cs), transition metals (Sc, Ti, V, Cr,
Mn, Fe, Co, Ni, Cu, Zn, Y, Zr, N
b, Mo, Tc, Ru, Rh, Pd, Ag, Cd, lanthanoid metal, Hf, Ta, W, Re, Os, Ir,
Pt, Au, Hg) and Group IIa elements (Be, M) of the periodic table
g, Ca, Sr, Ba) VIIb group element (F, Cl, B)
r, I) can be included. In addition, various compounds that increase electron conductivity (for example, compounds of Sb, In, Nb)
The dopant may be included. The amount of compound added is 0
-20 mol% is preferable.

As the method for synthesizing the composite oxide mainly composed of the oxides represented by the general formulas ( 4 ) to (5) 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 .
Compound, P compound, M ⁶ Compound (G e , B, Al, P b )
May be mixed and fired. Examples of the Sn compound include SnO, SnO ₂ , Sn ₂ O ₃ , Sn ₃ O ₄ , and S.
n ₇ O ₁₃ · H ₂ O, Sn ₈ O ₁₅ , stannous hydroxide, stannic oxyhydroxide, stannic acid, stannous oxalate, stannous phosphate, orthostannic acid, metastannic acid, para Stannic acid, stannous fluoride, stannic fluoride, stannous chloride, stannic chloride, stannous bromide, stannic bromide, stannous iodide, stannous iodide, selenium Examples thereof include tin oxide, tin telluride, stannous pyrophosphate, tin phosphide, stannous sulfide, and stannic sulfide.

Examples of the Si compound include SiO ₂ and S
iO, halogenated organosilicon compounds such as silicon tetrachloride, silicon tetrabromide, trichloromethylsilane, dimethyldichlorosilane, trimethylchlorosilane, tetramethylsilane,
Examples thereof include organosilicon compounds such as tetraethylsilane, alkoxysilane compounds such as tetramethoxysilane and tetraethoxysilane, and hydrosilane compounds such as trichlorohydrosilane. Examples of the Ge compound include GeO ₂ , GeO, germanium tetrachloride, germanium tetrabromide, alkoxy germanium compounds such as germanium tetramethoxide, and germanium tetraethoxide. Examples of the Pb compound include PbO ₂ , PbO, Pb ₂ O ₃ , Pb ₃ O ₄ , PbCl ₂ ,
Examples thereof include lead chlorate, lead perchlorate, lead nitrate, lead carbonate, lead formate, lead acetate, lead tetraacetate, lead tartrate, lead diethoxide, and lead di (isopropoxide).

Examples of the P compound include phosphorus pentaoxide, phosphorus oxychloride, phosphorus pentachloride, phosphorus trichloride, phosphorus tribromide,
Examples thereof include trimethyl phosphoric acid, triethyl phosphoric acid, tripropyl phosphoric acid, stannous pyrophosphate, and boron phosphate. Examples of the B compound include boron trioxide,
Examples thereof include boron trichloride, boron tribromide, boron carbide, boric acid, trimethyl borate, triethyl borate, tripropyl borate, tributyl borate, boron phosphide and boron phosphate. Examples of the Al compound include aluminum oxide (α-alumina, β-alumina), aluminum silicate, aluminum tri-iso-propoxide, aluminum tellurite, aluminum chloride, aluminum boride, aluminum phosphide, aluminum phosphate, lactic acid. Examples thereof include aluminum, aluminum borate, aluminum sulfide, aluminum sulfate, aluminum boride and the like. Examples of the Sb compound include antimony tribromide, antimony trichloride, diantimony trioxide, triphenyl antimony and the like.

The firing conditions are preferably a temperature raising 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 higher and 2000 ° C. or lower, and the firing temperature is preferably 250 ° C. or higher and 1500 ° C. or lower, and further preferably 350 ° C. or higher and 1500 ° C.
Or less, particularly preferably 500 ° C or higher and 1500 ° C
And the firing time is 0.01 hours or more 1
It is preferably 00 hours or less, more preferably 0.5 hours or more and 70 hours or less, particularly preferably 1 hour or more and 20 hours or less, and the temperature decreasing rate is 2 ° C or more and 10 ⁷ ° C or less per minute. It is preferably 4 ° C or more and 10 ⁷ ° C or less, particularly preferably 6 ° C or more and 10 ⁷ ° C or less, and particularly preferably 1
It is 0 ° C. or higher and 10 ⁷ ° C. or lower. The rate of temperature rise in the present invention is the average rate of temperature increase from "50% of the firing temperature (displayed in ° C)" to "80% of the firing temperature (displayed in ° C)", and the rate of temperature drop in the present invention is "Baking temperature (℃
80% of "displayed" to "50% of firing temperature (displayed in ° C)"
Is the average rate of temperature drop until reaching.

The temperature may be lowered in the firing furnace or may be taken out of the firing furnace and put in water for cooling. Also, ceramics processing (Gihodo Publishing 1
987) page 217, the Gun method Hammer-An.
It is also possible to use ultra-quenching methods such as the vil method, the slap method, the gas atomizing method, the plasma spray method, the centrifugal quenching method, and the melt drag method. Alternatively, cooling may be performed by using a single roller method or a twin roller method described in New Glass Handbook (Maruzen 1991), page 172. In the case of a material that melts during firing, the fired product may be continuously taken out while supplying the raw material during firing. In the case of a material that melts during firing, it is preferable to stir the melt. The firing gas atmosphere is preferably an atmosphere having an oxygen content of 5% by volume or less, and more preferably an inert gas atmosphere. Examples of the inert gas include nitrogen, argon, helium, krypton, xenon and the like.

The average particle size of the compounds represented by the general formulas ( 4 ) to (5) used in the present invention is preferably 0.1 to 60 μm. A well-known crusher or classifier is used to obtain a predetermined particle size. 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 which water or an organic solvent such as methanol is allowed to coexist can be performed as necessary. In order to obtain the desired particle size, it is preferable to carry out classification. The classification method is not particularly limited, and a sieve, an air classifier, or the like can be used as necessary. Classification is dry type,
Both wet type can be 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), and / or Al, G
a, In, Ge, Sn, Pb, Sb, Bi, Si, P,
You may mix B etc. Mixing amount is 0 for transition metal
-30 mol% is preferable.

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,
It is preferable to mix and synthesize such that the total molar ratio of at least one selected from Cr, Mn, Fe, Co, Ni, Mo, and W is 0.3 to 2.2. Particularly preferable lithium-containing transition metal oxide positive electrode active material used in the present invention is a lithium compound / transition metal compound (transition metal here means V, Cr, Mn, Fe, Co,
It is preferable to mix and synthesize such that the total molar ratio of at least one selected from Ni) is 0.3 to 2.2. Particularly preferable lithium-containing transition metal oxide positive electrode active material used in the present invention is Lix QOy (wherein Q is mainly at least one of Co, Mn and N).
i, V, transition metal containing Fe, x = 0.2 to 1.2, y
= 1.4 to 3) is preferable. As Q, besides transition metals, Al, Ga, In, Ge, Sn, Pb, S
You may mix b, Bi, 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 active material used in the present invention is Li _x CoO ₂ ,
Li _x NiO ₂ , Li _x MnO ₂ , Li _x Co _a Ni _1-a O ₂ ,
Li _x Co _b V _1-b O ₂ , Li _x Co _b Fe _1-b O ₂ , Li _x M
_{n 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 z, Li x Mn c Fe 2-c O 4,
Mixture of Li _x Mn ₂ O ₄ and MnO ₂ , Li _2x MnO ₃ and M
nO ₂ mixture, Li _x Mn ₂ O ₄ , Li _2x MnO ₃ and Mn
A mixture of O ₂ (where x = 0.2-1.2, a = 0.1
~ 0.9, b = 0.8 to 0.98, c = 1.6 to 1.9.
6, z = 2.01 to 5). More preferable lithium-containing metal oxide positive electrode active materials used in the present invention are Li _x CoO ₂ , Li _x NiO ₂ , and Li _x Mn.
O ₂ , Li _x Co _a Ni _1-a O ₂ , Li _x Co _b V _1-b O _z , L
i _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 = 0.7 to 1.2, a
= 0.1 to 0.9, b = 0.8 to 0.98, c = 1.6
˜1.96, z = 2.01 to 2.3).

The most preferable lithium-containing transition metal oxide positive electrode active material used in the present invention is Li _x Co.
O ₂ , Li _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 =
0.7-1.2, a = 0.1-0.9, b = 0.9-
0.98, z = 2.01 to 2.3). The most preferable lithium-containing transition metal oxide positive electrode active material used in the present invention is Li _x CoO ₂ , Li _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 = 0.7 to 1.
2, a = 0.1 to 0.9, b = 0.9 to 0.98, z =
2.02-2.3). Here, the above-mentioned x value is a value before the start of charge / discharge, and increases / decreases due to charge / 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 for example, 2
50 to 2000 ° C. is preferable, especially 350 to 1500 ° C.
Is preferred. Upon firing, it is preferable to calcine at 250 to 900 ° C. The firing time is preferably 1 to 72 hours, more preferably 2 to 20 hours. The mixing method of the raw materials may be dry or wet. Also, after firing, 20
You may anneal at 0 degreeC-900 degreeC. The firing gas atmosphere is not particularly limited, and either an oxidizing atmosphere or a reducing atmosphere can be used. For example, in air, or a gas adjusted to an oxygen concentration of any ratio, or hydrogen, carbon monoxide,
Examples thereof include nitrogen, argon, helium, krypton, xenon, carbon dioxide and the like.

When synthesizing the positive electrode active material of the present invention, a method of chemically inserting lithium ions into a transition metal oxide is to synthesize lithium metal, lithium alloy or butyl lithium 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.
The specific surface area is not particularly limited, but it is 0.
01-50 m < ² > / g is preferable. The pH of the supernatant when 5 g of the positive electrode active material is dissolved in 100 ml of distilled water is preferably 7 or more and 12 or less. 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 vibrating mill, a satellite ball mill, a planetary ball mill, a swirling airflow type jet mill, a sieve and the like are used. The positive electrode active material obtained by firing may be used after being washed with water, an acidic aqueous solution, an alkaline aqueous solution, or an organic solvent.

The combination of the negative electrode active material and the positive electrode active material used in the present invention is preferably the compound represented by the general formula (4) and Li _x CoO ₂ , Li _x NiO ₂ , and Li _x.
Co _a Ni _1-a O ₂ , Li _x MnO ₂ , Li _x Mn ₂ O
₄ or Li _x Co _b V _1-b O _z (where x = 0.7
~ 1.2, a = 0.1 to 0.9, b = 0.9 to 0.9
8, z = 2.02-2.3). With such a combination, it is possible to obtain a non-aqueous secondary battery having a high discharge voltage, a high capacity, and excellent charge / discharge cycle characteristics.

The equivalent of lithium insertion into the compounds represented by the general formulas ( 4 ) to (5) used in the present invention is 3 to 10 equivalents, and the ratio of the amount used with the positive electrode active material is adjusted according to this equivalent. Decide To the usage rate based on this equivalent,
It is preferable to apply a coefficient of 0.5 to 2 times. 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.
At this time as well, the usage ratio based on this equivalent is 0.5
It is preferable to multiply by a factor of two.

As the negative electrode active material which can be used in combination with the present invention, lithium metal and lithium alloy (Al, A
l-Mn, Al-Mg, Al-Sn, Al-In, Al
Examples include -Cd and calcined carbonaceous compounds capable of inserting and extracting lithium ions or lithium metal. The purpose of the combined use of the lithium metal or lithium alloy is to insert lithium into the composite oxide mainly composed of the oxides represented by the general formulas (1) to (5) used in the present invention, in the battery, The battery reaction does not utilize the dissolution / precipitation reaction of lithium metal or the like.

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 fiber and metal (copper, nickel, aluminum, silver, etc.) powder, metal Conductive material such as fiber or polyphenylene derivative 1
It can be included as a seed or a mixture thereof.
The combined use of graphite and acetylene black is particularly preferred. The addition amount is preferably 1 to 50% by weight, and particularly 2 to 30% by weight.
Weight percent is preferred. 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 binder is preferably added in an amount of 1 to 50% by weight, particularly 2 to 30% by weight.
Is preferred. 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 0
-30% by weight is preferred.

As an electrolyte, an organic solvent such as propylene carbonate, ethylene carbonate, butylene carbonate, dimethyl carbonate, diethyl carbonate, γ-butyrolactone, 1,2-dimethoxyethane, tetrahydrofuran, 2-methyltetrahydrofuran is used. , Dimethyl sulfoxide, 1,3-dioxolane,
Formamide, dimethylformamide, dioxolane,
Acetonitrile, nitromethane, methyl formate, methyl acetate, methyl propionate, ethyl propionate, phosphate triester, trimethoxymethane, dioxolane derivative, sulfolane, 3-methyl-2-oxazolidinone,
A solvent prepared by mixing at least one aprotic organic solvent such as a propylene carbonate derivative, a tetrahydrofuran derivative, diethyl ether, and 1,3-propanesartone and a lithium salt soluble in the solvent, for example, Li.
ClO ₄ , LiBF ₆ , LiPF ₆ , LiCF ₃ SO ₃ , L
_{iCF 3 CO 2, LiAsF 6,} LiSbF 6, LiB 10 C
l ₁₀ , lower aliphatic lithium carboxylate, LiAlC
It is composed of at least one salt such as l ₄ , LiCl, LiBr, LiI, lithium chloroborane, and lithium tetraphenylborate. Above all, Li is added to a mixed solution of propylene carbonate or ethylene carbonate and 1,2-dimethoxyethane and / or diethyl carbonate.
_{CF 3 SO 3, LiClO 4,} LiBF 4 and / or an electrolyte containing LiPF ₆ is preferred. The amount of these electrolytes 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 concentration of the supporting electrolyte 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 NI
_{2, Li 3 N-LiI-} LiOH, LiSiO 4, LiS
_{iO 4 -LiI-LiOH, xLi 3} PO 4 - (1-x)
Li ₄ SiO ₄ , Li ₂ SiS ₃ , phosphorus sulfide compounds and the like are effective. In the organic solid electrolyte, a polyethylene oxide derivative or a polymer containing the derivative (JP-A-63-13).
5, 447), a polypropylene oxide derivative or a polymer containing the derivative, a polymer containing an ionic dissociative group (JP-A-62-254, 302, JP-A-62-254, 303,
63-193,954), a mixture of a polymer containing an ionic dissociative group and the aprotic electrolyte (US Pat.
792, 504, 4,830, 939, JP-A-62-
22, 375, 62-22, 376, JP-A-1-9.
5, 117), a phosphoric acid ester polymer (JP-A-61-161).
256, 573) is effective. Further, there is also a method of adding polyacrylonitrile to the electrolytic solution (Japanese Patent Laid-Open No. 62-
278,774). Also known is a method in which an inorganic and organic solid electrolyte is used in combination (JP-A-60-1,768).

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.

Further, it is 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, carbon dioxide gas can be included in the electrolytic solution in order to have suitability for high temperature storage. (JP-A-59-
134, 567) Further, the mixture of the positive electrode and the negative electrode may contain an electrolytic solution or an electrolyte. For example, the ion-conductive polymer or nitromethane described in JP-A-48-3
6,633), electrolytic solution (JP-A-57-124,870)
It is known how to include. Further, the surface of the positive electrode active material can be modified. For example, the surface of a metal oxide is treated with an esterifying agent (Japanese Patent Application Laid-Open No. 55-163,77).
9) or treatment with a chelating agent (JP-A-55-16)
3,780), conductive polymers (JP-A-58-163,1).
88, No. 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, it is possible to provide an ion conductive polymer or polyacetylene layer (JP-A-58-111,276) or to treat with LiCl (JP-A-58-142,771).

The collector of the electrode active material may be any electron conductor as long as it does not chemically 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 mounted on 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.

[0056]

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 13.5 g of tin monoxide and 6.0 g of silicon dioxide were dry-mixed and placed in an alumina crucible and placed in an argon atmosphere at 15 ° C.
The temperature was raised to 1000 ° C./min. After firing at 1000 ° C. for 12 hours, the temperature was lowered to room temperature at 10 ° C./min, and the sample was taken out from the firing furnace to obtain SnSiO ₃ . The compound was roughly crushed and further crushed with a jet mill to give an average particle size of 4.5 μm.
It was obtained of SnSiO _3. (Compound 1-A) This compound 1
As shown in FIG. 1, -A is a substance having a broad peak having an apex at a 2θ value of around 28 ° in an X-ray diffraction method using CuKα rays, and has a 2θ value of 40 ° or more and 70 ° or more.
No crystalline diffraction line was observed below °. In the same manner, stoichiometric amounts of raw materials were mixed, fired and pulverized to synthesize the compounds shown below. Also, those compounds are C
The X-ray diffraction method using uKα rays had a broad scattering band having an apex at 20 ° to 40 ° in 2θ value. In addition, when the diffraction line intensity at the apex of the broad scattering band which is seen in the 2θ value of 20 ° or more and 40 ° or less is A, and the crystalline diffraction line is seen in the 2θ value of 40 ° or more and 70 ° or less, the most The value of B / A is shown together with the compound number, where the strong intensity is B (B = 0 when there is no crystalline diffraction line).

SnGeO ₃ (Compound 1-B, B / A =
0), SnSi _0.8 P _0.1 B _0.1 O ₃ (Compound 1-C, B /
A = 0), SnSi _0.9 Ge _0.1 O ₃ (Compound 1-D, B
/ A = 0), SnSi _0.9 Pb _0.1 O ₃ (Compound 1-E,
B / A = 0), SnSi _0.5 Ge _0.5 O ₃ (compound 1-
F, B / A = 0), SnSi _0.5 Pb _0.5 O ₃ (Compound 1
-G, B / A = 0.3), SnGe _0.9 Pb _0.1 O ₃ (Compound 1-H, B / A = 0), SnSi _0.8 O _2.4 (Compound 1-I, B / A = 0.1), SnSi _1.2 O _3.4 (Compound 1-J, B / A = 0), SnSi _1.5 O ₄ (Compound 1-
K, B / A = 0), PbSiO ₃ (Compound 1-L, B /
A = 0), PbGeO ₃ (Compound 1-M, B / A =
0), PbSi _0.9 Ge _0.1 O ₃ (Compound 1-N, B / A
= 0), SnPO _3.5 (Compound 1-O, B / A = 0),
SnBO _2.5 (Compound 1-P, B / A = 0), SnSi
_0.9 O _2.8 (Compound 1-Q, B / A = 0) was obtained.

Synthesis Example-2 1.35 g of tin monoxide and 0.6 g of silicon dioxide are dry-mixed and placed in an alumina crucible, and the mixture is placed in an argon atmosphere at 15 ° C.
The temperature was raised to 1000 ° C./min. After firing at 1000 ° C. for 10 hours, it was poured onto a stainless steel wheel in an argon atmosphere and rapidly cooled. The compound was roughly pulverized and further pulverized by a vibration mill to obtain SnSiO ₃ having an average particle size of 3.5 μm. (Compound 2-A) Further, in X-ray diffraction, B / A =
It was 9.5.

Synthetic Example-3 15.1 g of tin dioxide and 0.6 g of silicon dioxide were dry-mixed and placed in an alumina crucible, and the mixture was placed in air at 1200 ° C. for 1 hour.
It was baked for 0 hours. After firing, it was cooled to room temperature and taken out from the firing furnace to obtain SnSi _0.1 O _2.2 . The compound was pulverized with a jet mill to obtain SnSi _0.1 O _2.2 having an average particle size of 4 μm.
Got (Compound 3-A) Also, B / in X-ray diffraction
A = 0. In the same manner, the respective stoichiometric amounts of the raw materials were mixed, fired and crushed to obtain SnSi _0.3 O _2.6
(Compound 3-B, B / A = 2.4), SnGe _0.1 O _2.2
(Compound 3-C, B / A = 7.4), SnGe _0.3 O _2.6
(Compound 3-D, B / A = 4.7), SnPb _0.1 O _2.2
(Compound 3-E, B / A = 7.5), SnPb _0.1 O _2.6
(Compound 3-F, B / A = 16.5), SnSi _0.1 G
e _0.1 O _2.4 (Compound 3-G, B / A = 9.5), SnS
i _0.1 Pb _0.1 O _2.4 (Compound 3-H, B / A = 29.
1), SnSi _0.01 O _2.02 (Compound 3-I, B / A =
7.1), SnSi _1.5 O ₅ (Compound 3-J, B / A =
0), SnSi ₂ O ₆ (Compound 3-K, B / A = 0), P
bSi _0.1 O _2.2 (Compound 3-L, B / A = 5.3), P
bGe _0.3 O _2.6 (Compound 3-M, B / A = 2.3), G
eSi _0.1 O _2.2 (Compound 3-N, B / A = 0), GeS
i _0.3 O _2.6 (Compound 3-O, B / A = 0), SnP _0.3
O _2.75 (Compound 3-P, B / A = 1.4), SnB _0.3
O _2.45 (Compound 3-Q, B / A = 6.4) was obtained.

Synthesis Example-4 13.5 g of tin monoxide, 4.8 g of silicon dioxide and 1.42 g of phosphorus pentoxide were weighed in dry air having a dew point of -50 ° C.
Next, dry mixing was performed in a ball mill in this dry air.
Then, put it in an alumina crucible and put it in an argon atmosphere at 10 ° C.
The temperature was increased to 1100 ° C./min. After firing at 1100 ° C. for 10 hours, it was cooled to room temperature at 8.3 ° C./min to obtain a glassy compound. Milling the compound in a jet mill,
Further, wind force classification was performed to obtain compound 4-A having an average particle size of 4 μm.
Got Also, B / A = 0 in X-ray diffraction.
In the same manner, stoichiometric amounts of the raw materials were mixed, fired and pulverized. However, Al ₂ O ₃ and Sb
Sb ₂ O ₃ was used as a raw material. SnSi _0.9 respectively
P _0.1 O _3.05 (Compound 4-B, B / A = 0), SnSi
_0.7 P _0.3 O _3.15 (Compound 4-C, B / A = 0), SnS
i _0.5 P _0.5 O _3.25 (Compound 4-D, B / A = 0), Sn
Si _0.2 P _0.8 O _3.4 (Compound 4-E, B / A = 0), S
nSi _0.8 P _0.1 Sb _0.1 O ₃ (Compound 4-F, B / A =
0.5) was obtained.

Synthesis Example-5 10.78 g of tin monoxide, 3.6 g of silicon dioxide, 4.11 g of stannous pyrophosphate and 2.1 g of germanium dioxide were dry mixed in a ball mill. Next, it was placed in an alumina crucible and heated to 1100 ° C. at 10 ° C./min in an argon atmosphere. After firing at 1100 ° C. for 10 hours, the fired product was put into water in an argon atmosphere and rapidly cooled to obtain a glassy compound. The compound was wet-milled using a ball mill with water as a medium. Next, with the powder dispersed in water,
Coarse particles were removed through a m sieve. After removing water by decantation, it was dried at 150 ° C. for 1 hour. Compound 5-A having an average particle size of 3.1 μm was obtained. Also, X
B / A = 0 in the line diffraction.

In the same manner, stoichiometric amounts of the raw materials were mixed, fired and pulverized. However, as the Al raw material, Al ₂
O ₃ was used. SnSi _0.7 Ge _0.1 P _0.2 O respectively
_3.1 (Compound 5-B, B / A = 0), SnSi _0.6 Ge
_0.4 P _0.1 O _3.25 (Compound 5-C, B / A = 0), SnS
i _0.2 Ge _0.1 P _0.7 O _3.35 (Compound 5-D, B / A =
0), SnSi _0.8 P _0.1 Al _0.1 O ₃ (Compounds 5-E, B
/ A = 0), SnSi _0.8 P _0.2 Al _0.1 O _3.25 (Compound 5-F, B / A = 0), SnSi _0.6 P _0.1 Al _0.3 O _2.9
(Compound 5-G, B / A = 0), SnSi _0.6 P _0.3 Al
_0.1 O _3.1 (Compound 5-H, B / A = 0), SnSi _0.3
P _0.7 Al _0.1 O _3.5 (Compound 5-I, B / A = 1.
5), SnSi _0.8 P _0.2 O _3.1 (Compound 5-J, B / A
= 0), SnSi _0.6 P _0.4 Al _0.2 O _3.5 (compound 5-
K, B / A = 0), SnSi _0.1 P _0.9 Al _0.1 O _3.6 (Compound 5-L, B / A = 0), SnSi _0.8 Al _0.2 P _0.2
O _3.4 (compound 5-M, B / A = 0), SnSi 0.7 Al
_0.2 P _0.3 O _3.45 (Compound 5-N, B / A = 0), SnS
i _0.4 Al _0.2 P _0.6 O _3.6 (Compound 5-O, B / A =
0), SnPAl _0.1 O _3.65 (Compound 5-P, B / A =
0) was obtained.

Example 1 As a method for preparing a mixture, in the negative electrode material, 82% by weight of the compound 1-A 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
Of 82% by weight, flake graphite as a conductive agent 8% by weight, acetylene black 4% by weight, and tetrafluoroethylene as a binder in a mixing ratio of 6% by weight. (13 mmΦ, compound A-1
Adapted to the lithium insertion capacity of. 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.

As the current collector, a SUS316 net having a thickness of 80 μm was welded to a coin can for both the positive and negative electrode cans.
200 μl of 1 mol / l LiPF ₆ (a 2: 2: 6 volume mixture of ethylene carbonate, butylene carbonate and dimethyl carbonate) was used as the electrolyte, and a microporous polypropylene sheet and polypropylene nonwoven fabric were used as the separator. Was used by impregnating a non-woven fabric. Then, a coin type non-aqueous secondary battery as shown in FIG. 2 was produced in the same dry box as above. In the coin-type battery of FIG. 2, 1 is a negative electrode sealing plate, 2 is a negative electrode mixture pellet, 3 is a separator, 4 is a positive electrode mixture pellet, 5 is a current collector, 6 is a positive electrode case, and 7 is a gasket.

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 were started from 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 performance (60% of the first discharge capacity)
The number of cycles that becomes the capacity of each) is shown. Synthesis example-1
For the compounds 1-B to 1-Q synthesized in 1., 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 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.

[0067]

[Table 1]

Example-2 Example-2 except that the compound 2-A synthesized in Synthesis Example-2 was used in place of the negative electrode active material 1-A 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. Table 2
The symbols shown in (a), (b), (c) and (d) are the same as in Example-1. From this result, it is understood that the negative electrode active material obtained by quenching used in the present invention is excellent in charge / discharge cycle property, and gives a non-aqueous secondary battery having high discharge voltage and high capacity.

[0069]

[Table 2]

Example-3 Example-3 except that the compound 3-A synthesized in Synthesis Example-3 was used in place of the negative electrode active material 1-A 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 3. Table 3
The symbols shown in (a), (b), (c) and (d) are the same as in Example-1. Compound 3 synthesized in Synthesis Example-3
With respect to -B to 3-Q, coin-type non-aqueous secondary batteries were produced by the same method, and a charge / discharge test was conducted. The results are shown in Table 3. From these results, it is understood 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 higher capacity.

[0071]

[Table 3]

Comparative Example-1 In Example-1, Sn was used instead of the negative electrode active material 1-A.
A coin type non-aqueous secondary battery was prepared in the same manner as in Example 1 except that O ₂ (a broad scattering band showing amorphousness was not observed in the X-ray diffraction method using CuKα ray) was used. It was produced and a charge / discharge test was performed. The results are shown in Table 4. SnO (CuKα line X as negative electrode active material)
In the line diffraction method, a broad scattering band showing an amorphous property was not observed), 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 4. The abbreviations shown in Table 4 are (a),
(B), (c), and (d) are the same as in Example-1. From these results, it can be seen that when the tin composite oxide used in the present invention is used as the negative electrode active material, it is particularly excellent in charge / discharge cycle characteristics and capacity as compared with SnO ₂ and SnO.

[0073]

[Table 4]

Comparative Example-2 In Example-1, Fe ₂ was used in place of the negative electrode active material 1-A.
A coin-type non-aqueous secondary battery was prepared in the same manner as in Example 1 except that O ₃ was used, and a charge / discharge test was conducted. The results are shown in Table 5. The abbreviations shown in Table 5 are (a),
(B), (c), and (d) are the same as in Example-1. Using amorphous V ₂ O ₅ and LiCoVO ₄ as the negative electrode active material, a coin type non-aqueous secondary battery was prepared in the same manner.
A charge / discharge test was performed. The results are shown in Table 5. From these results, when the tin composite oxide used in the present invention is used as the negative electrode active material, Fe ₂ O ₃ , amorphous V ₂ O ₅ , L
It can be seen that it is superior to iCoVO ₄ in terms of charge / discharge cycle characteristics, discharge voltage, and discharge capacity.

[0075]

[Table 5]

[0076] In Example -4 Example -1 but using LiNiO ₂ in place of LiCoO 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 and discharge test Was done. The results are shown in Table 6. The abbreviations shown in Table 6 are the same as in Example-1 (a), (b), (c), and (d). LiCo _0.95 V as positive electrode active material
_A coin type non-aqueous secondary battery was prepared by the same method for _0.05 O _2.07 , LiMn ₂ O ₄ , and LiMnO ₂ , and a charge / discharge test was conducted. The results are shown in Table 6. from this result,
Using any positive electrode active material, charge and discharge cycle characteristics,
It can be seen that the discharge voltage and discharge capacity are all excellent.

[0077]

[Table 6]

Example-5 Compound 1-A 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 the 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 flake graphite, 3% by weight of acetylene black, 3% by weight of polytetrafluoroethylene aqueous dispersion 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. As shown in FIG. 3, nickel and aluminum lead plates were spot-welded to the respective ends of the negative electrode sheet and the positive electrode sheet, and then dehydrated and dried at 150 ° C. for 2 hours in dry air having a dew point of −40 ° C. or less. Figure 3
[Fig. 3] is a cross-sectional view of a cylindrical battery.

Furthermore, the dehydrated and dried positive electrode sheet (8),
A microporous polypropylene film separator (Celguard 2400), a dehydrated and dried negative electrode sheet (9) and a separator (10) were laminated in this order, and this was spirally wound with a winding machine. The wound body was housed in a bottomed cylindrical battery can (11) made of iron and plated with nickel and also serving as a negative electrode terminal. Furthermore, as an electrolyte, 1 mol /
Li-LiPF ₆ (a 2: 2: 6 volume mixture of ethylene carbonate, butylene carbonate and dimethyl carbonate) was injected into the battery can. A battery lid (12) having a positive electrode terminal was caulked via a gasket (13) to produce a cylindrical battery. The positive electrode terminal (12) was connected to the positive electrode sheet (8), and the battery can (11) was connected to the negative electrode sheet (9) by a lead terminal in advance. FIG. 2 shows a cross section of the cylindrical battery. Incidentally, (14) is a safety valve. Charge / discharge conditions were 4.3 to 2.7 V and 1 mA / cm ² . The results are shown in Table 7. The abbreviations shown in Table 7 are the same as in Example-1 (b), (c), and (d).
(E) shows the discharge capacity per 1 ml of AA battery.

[0080]

[Table 7]

Example-6 Compounds 1-A to 1-Q, Compounds 4-A to 4-F, Compound 5-A synthesized in Synthesis Example-1, Synthesis Example-4 and Synthesis Example-5
A ~ 5-P coin type non-aqueous secondary battery was produced according to Example-1, and the following safety test was performed. After repeating 50 cycles of charging / discharging 50 coin-type non-aqueous secondary batteries at 5 mA / cm ² , the batteries were disassembled and the negative electrode pellets were taken out into the air at 60% RH to test whether they spontaneously ignite. Was carried out. As a result, 0 coin cells were ignited.
It was an individual.

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-6.
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.

Comparative Example-4 SnSiO ₃ (Compound 1-A) synthesized in Synthesis Example 1 as a negative electrode active material was heated at 700 ° C. for 2 hours and then cooled to room temperature to obtain crystalline SnSiO ₃ . No amorphous peak was found by X-ray diffraction. A coin type non-aqueous secondary battery was prepared in the same manner as in Example 1 except that this crystalline SnSiO ₃ was used, and a charge / discharge test was conducted. The results are shown in Table 8. The abbreviations shown in Table 8 are (a), (b),
Both (c) and (d) are the same as in Example-1. From these results, it can be seen that when the amorphous tin composite oxide used in the present invention is used as the negative electrode active material, it is particularly excellent in charge / discharge cycle characteristics and capacity as compared with the crystalline tin composite oxide.

[0084]

[Table 8]

Example-7 In Example-1, except that the compound 4-A synthesized in Synthesis Example-4 was used instead of the negative electrode active material 1-A 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 9. Table 9
The symbols shown in (a), (b), (c) and (d) are the same as in Example-1. A coin-type non-aqueous secondary battery was produced by the same method for the compounds 4-B to 4-F and 5-A to 5-P synthesized in Synthesis Example-4 and Synthesis Example-5, and a charge / discharge test was conducted. It was The results are shown in Table 9. From these results, it is understood 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 higher capacity. Further, it is understood that the charge / discharge cycle property of the compound containing P is further excellent.

[0086]

[Table 9]

Example-8 In Example-4, the compound 1-A was used as the negative electrode active material.
A cylindrical battery was prepared in the same manner as in Example-4, except that the compound 4-A synthesized in Synthesis Example-4 was used instead of, and a charge / discharge test was conducted. The abbreviations shown in Table 10 are (a),
(B), (c), (d), and (e) are the same as in Example-1. A coin-type non-aqueous secondary battery was produced by the same method for the compounds 4-B to 4-F and 5-A to 5-P synthesized in Synthesis Example-4 and Synthesis Example-5, and a charge / discharge test was conducted. It was The results are shown in Table 10.

[0088]

[Table 10]

[0089]

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 compound 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 an X-ray diffraction pattern of compound 1-A.

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

FIG. 3 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 case 7 gasket 8 Positive electrode sheet 9 Negative electrode sheet 10 separator 11 battery cans 12 Battery lid 13 gasket 14 Safety valve

─────────────────────────────────────────────────── ─── Continuation of front page (56) References JP-A-7-230800 (JP, A) JP-A-7-220721 (JP, A) (58) Fields investigated (Int.Cl. ⁷ , DB name) H01M 4/00-4/04 H01M 4/36-4/62 H01M 10/40

Claims (8)

(57) [Claims] 1. A positive electrode active material, negative electrode active material, relates to non-aqueous secondary battery comprising a nonaqueous electrolyte containing a lithium salt, the negative electrode active material is formula (4) SnSi _t P _u M ⁶ _v O _s General formula (4) (wherein M ⁶ Is a small amount selected from Ge, B, Al and Pb
At least one. t = 0 to 2.0, u = 0.01 to 4.0,
The numbers v = 0 to 2.0 and s = 1.0 to 26 are represented. )so
Nonaqueous secondary battery, wherein the predominantly amorphous oxide or Ranaru shown. 2. A nonaqueous secondary battery according to claim 1, wherein the negative electrode active material is characterized in that it is a largely amorphous oxide when the battery is embedded. At least one wherein the negative electrode active material is selected general formula _{(5) SnSi t P u Al} v M 7 w O s formula (5) (wherein, M ⁷ is Ge, B, and Pb At least one: t = 0 to 2.0, u = 0.01 to 4.0, v = 0
.About.2.0, w = 0 to 2.0, and s = 1.0 to 26. Claim 1 or claim characterized in that it is a composite oxide mainly composed mainly of amorphous oxide represented by)
2. The non-aqueous secondary battery according to 2. 4. The temperature rise rate of the negative electrode active material is 4 ° C. or more per minute 2
The temperature is raised to 000 ° C. or lower, the temperature is raised to 250 ° C. to 1500 ° C. for 0.01 hour to 100 hours, and the temperature is decreased at 2 ° C. to 10 ⁷ ° C. per minute. Item 4. The non-aqueous secondary battery according to any one of item 3 . 5. The negative electrode active material is heated at a temperature rising rate of 10 ° C. or more and 2000 ° C. or less per minute, and 250 ° C. or more and 1500 ° C.
The non-aqueous secondary according to any one of claims 1 to 4 , which is fired at a temperature falling rate of 2 ° C or more and 10 ⁷ ° C or less per minute for 0.01 hour or more and 100 hours or less. battery. 6. The non-aqueous secondary battery according to any one of claims 1 to 5 , wherein the positive electrode active material is a lithium-containing transition metal oxide. 7. At least one of the positive electrode active materials comprises Li
_x QO _y (In the formula, at least one of Q is Co, M
transition metals including n, Ni, V and Fe, x = 0.2 to 1.
2, y = 1.4 to 3), The non-aqueous secondary battery according to any one of claims 1 to 6 . 8. At least one of the positive electrode active materials comprises Li
_x CoO ₂ , Li _x NiO ₂ , Li _x MnO ₂ , Li _x
Co _a Ni _1-a O ₂ , Li _x Co _b V _1-b O _z , Li _x
Co _b Fe _1-b O ₂ , Li _x Mn ₂ O ₄ , Li _x Mn _{c
Co 2-c O 4, Li} x Mn c Ni 2-c O 4, Li x Mn
_c V _2-c O ₄ , Li _x Mn _c Fe _2-c O ₄ (where x =
0.2-1.2, a = 0.1-0.9, b = 0.8-
0.98, c = 1.6~1.96, claim, characterized in that is from z = 2.01 2.3) 1 to claim 7
The non-aqueous secondary battery according to any one of 1.