JPH06349491A - Nonaqueous secondary battery - Google Patents

Abstract

PURPOSE:To provide a nonaqueous secondary battery having high discharge operating voltage, a large discharge capacity, and good charge/discharge cycle characteristics by using a specific vanadium composite oxide for a negative electrode active material, and containing molybdenum. CONSTITUTION:A vanadium composite oxide having the composition of at least one kind of MaVbMocOd is used for a negative electrode active material. At least one kind is selected among Ca, Mg, Cd, Co, Ni, Cu, Mn, Zn, or other transition metals for the constituent M. The composition ratios of the constituents are selected in the range of 1<=a<=11, 1<=b<=6, 0<=c/b<=2, 3<=d<=40, for example. When a lithium metal and a lithium alloy for inserting lithium ions are concurrently used, a negative electrode active material having no deposition of the lithium metal caused by a charge and a discharge can be formed, thereby a safe, large-capacity secondary battery is obtained.

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 As a negative electrode active material for non-aqueous secondary batteries,
Typical examples are titanium metal and lithium alloy,
When used, lithium metal grows in a dendritic form during charging and discharging,
Short circuit, the activity of the dendritic metal itself is high,
There is a risk of ignition. On the other hand, recently
A fired carbonaceous material that can store and release titanium is actually
It has come to be used. The drawback of this carbonaceous material is
Since it is electrically conductive, it can be used when overcharging or quick charging.
Lithium metal may be deposited on the carbonaceous material,
Eventually, the dendritic metal will be deposited. this
To avoid this, devise a charger or reduce the amount of positive electrode active material.
We have adopted a method to prevent overcharging.
However, the latter method limits the amount of active material.
Therefore, the discharge capacity is also limited. Also charcoal
Since the material has a relatively low density, it has a capacity per volume
The discharge capacity is limited by the double meaning of being low.
Becomes Meanwhile, lithium metal or lithium alloy or charcoal
As a negative electrode active material other than the base material, lithium ion is used.
TiS that can be occluded and released₂, LiTiS₂(Rice
Patent No. 3,983,476), WO with rutile structure
₂(U.S. Pat. No. 4,198,476), Liq Fe (F
e₂) O_FourSuch as spinel compounds (JP-A-58-220,
362), electrochemically synthesized Fe₂O₃Richiu
Compound (US Pat. No. 4,464,447), Fe₂O
₃Lithium compound (JP-A-3-112,070), N
b₂O_Five(JP-B-62-59,412, JP-A-2-82
4, 47), iron oxide, FeO, Fe₂O₃, Fe
₃O_Four, Cobalt oxide, CoO, Co₂O₃, Co₃O
_Four(JP-A-3-291,862) is known. this
All of these compounds have high redox potentials, so
Realizes a non-aqueous secondary battery with high discharge voltage and high capacity
It has not been. As the positive electrode active material, LiMn₂O_Four,
Li₂MnO₃, Γ-βMnO₂And LiMn₂O_FourMultiple
Compound oxide, γ-βMnO₂And Li₂MnO₃Complex oxidation of
Thing, LiCoO₂, LiCo0.5 Ni0.5 O₂, LiN
iO₂, V₂O_Five, Amorphous V₂O_Five, V₆O₁₃, LiV
₃O₈, VO₂, Ti compound TiS₂, Mo compounds
MoS₂, MoO₃, LiMo₂O_FourAre known
It Both are negative electrode active materials that are metal chalcogenides.
As a combination with a polar active material, TiS₂And LiTiS
₂(US Pat. No. 983,476), chemically synthesized
Li0.1 V₂O_FiveAnd LiMn₁-r Mer O₂(0.1 <
r <1 Me = transition metal JP-A-63-210,02
8), the same Li_0.1V₂O_FiveAnd LiCo₁-s Fes O
₂(S = 0.05-0.3 63-21 1,56
4), the same Li_0.1V₂O_FiveAnd LiCo₁-t Nit O
₂(T = 0.5 to 0.9 JP-A-1-294,36
4), V₂O_FiveAnd Nb₂O_Five+ Lithium metal (JP-A-2
-82447), V₂O_FiveAnd TiS₂Electrochemically
Liu Fe formed₂O₃(U.S. Pat. No. 4,464,4
47 Journal of Power Sources Volume 8 2
89, 1982), Li as a positive electrode active material and a negative electrode active material
Niv Co₁-v O₂(0 ≦ v <1 JP-A-1-120,
765 In the specification, from the examples, the positive electrode active material and the negative electrode active material are described.
The substances are described as the same compound. ), LiCoO₂
Or LiMn₂O_FourAnd iron oxide, FeO, Fe
₂O₃, Fe₃O_Four, Cobalt oxide, CoO, Co₂O
₃Or Co₃O_Four(JP-A-3-291,862)
Which is known. Also, any combination of these is 3
Non-water with discharge voltage lower than V class and low discharge capacity
It is a secondary battery. On the other hand, vanadium composite oxide is non-aqueous.
Cu as a positive electrode active material of a secondary battery₂V₂O₂(JP-A-5
8-192268), CuV₂O₆(JP-A-58-17
8957), Cu_FiveV₂O_Ten(JP-A-58-17895
Although 8) has been proposed, it was used as a negative electrode active material.
I can't find any examples. As a negative electrode active material, lithium
By changing the basic structure of the crystal by inserting ON,
The basic structure of the crystal after the change does not change due to charge and discharge
Transition metal oxides have been proposed, among them lithium
Contained vanadium complex oxides are said to be preferable (special features
Japanese Patent Application No. 4-106642). This allows high discharge voltage and high
Capacity can be obtained, but lithium metal or
Discharge voltage compared to non-aqueous secondary batteries using gold as the negative electrode,
The capacity is inferior, and further improvement is strongly desired.
ing.

[0003]

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

[0004]

Means for Solving the Problems The object of the present invention has been surprisingly achieved by diligent studies, and was accomplished by using a specific vanadium composite oxide as the negative electrode active material. That is, in a non-aqueous secondary battery composed of a positive electrode active material, a negative electrode active material, and a non-aqueous electrolyte containing a lithium salt,
At least one of the negative electrode active materials is MaVbMocO.
d (where M is at least one selected from transition metals other than V and Mo, Ca and Mg, 1 ≦ a ≦ 11, 1 ≦ b ≦
By using the vanadium composite oxide represented by 6, 0 ≦ c / b ≦ 2, 3 ≦ d ≦ 40), the object of the present invention can be achieved.

In the present invention, M in the above formula is at least one selected from transition metals other than V and Mo, and Ca and Mg. The term “transition metal other than V and Mo” as used in the present invention means Sc of atomic number 21. To Ge of atomic number 32, from Y of atomic number 39 to Te of atomic number 52, and from La of atomic number 57 to Bi of atomic number 83, metal elements other than V and Mo, among which transition metals are preferable. Are Cd, Co, Ni, Cu, Mn, and Zn. In the present invention, by using the vanadium composite oxide represented by Ma Vb Od (where M, a, b and d are the same as above) as the negative electrode active material, the discharge voltage, discharge capacity and cycle Although a non-aqueous secondary battery having excellent characteristics can be obtained, it may further contain Mo if necessary, and the inclusion of Mo further improves its discharge capacity and cycle characteristics. The amount of Mo contained is 2 equivalents or less with respect to vanadium, and more preferably 0.1 equivalent or more and 1.5 equivalents or less. Further, in the present invention, the vanadium composite oxide may have a single-phase structure or a multi-phase structure, and in particular, by including Mo, depending on the synthesis conditions and the amount of Mo, a solid solution structure and a multi-phase structure may be obtained. Any phase structure can be adopted (for example, Journal of Solid State Chemistry, 56, 84 (1985). In the present invention, any of them is effective.

Examples of the vanadium composite oxide used in the present invention include CaV ₃ O ₈ , CaVO ₃ , and Ca ₂ V _2.
O ₇ , CaV ₂ O ₆ , Ca ₃ V ₂ O ₈ , CdV ₃ O ₈ ,
CdVO ₃ , Cd ₂ V ₂ O ₇ , CdV ₂ O ₆ , Cd ₃ V
₂ O ₈ , CoV ₃ O ₈ , CoVO ₃ , Co ₂ V ₂ O ₇ ,
CoV ₂ O ₆ , Co ₃ V ₂ O ₈ , NiV ₃ O ₈ , NiV
O ₃ , Ni ₂ V ₂ O ₇ , NiV ₂ O ₆ , Ni ₃ V
₂ O ₈ , MgV ₃ O ₈ , MgVO ₃ , Mg ₂ V ₂ O ₇ ,
MgV ₂ O ₆ , Mg ₃ V ₂ O ₈ , MnV ₃ O ₈ , MnV
O ₃ , Mn ₂ V ₂ O ₇ , MnV ₂ O ₆ , Mn ₃ V
₂ O ₈ , ZnV ₃ O ₈ , ZnVO ₃ , Zn ₂ V ₂ O ₇ ,
ZnV ₂ O ₆ , Zn ₃ V ₂ O ₈ , CuV ₃ O ₈ , CuV
O ₃ , Cu ₂ V ₂ O ₇ , CuV ₂ O ₆ , Cu ₃ V
₂ O ₈ , Cu ₅ V ₂ O ₁₀ , Cu ₁₁ V ₆ O ₂₆ , Cu ₃ V ₅
Examples thereof include, but are not limited to, O ₄ and Mo-containing substances thereof. In addition, C of the above compound
d, Co, Ni, Cu, Mn, Zn, Ca, and Mg may be partially replaced with another transition metal, Ca or Mg.

Vanadium complex oxide used in the present invention
Of these, N is particularly preferable.₂V ₂Moi Oj (here
And N is Ca, Mg, Cd, Co, Ni, Cu, Mn, Z
at least one selected from n, 0 ≦ i ≦ 4, 7 ≦ j ≦
19) Vanadium complex oxide represented by NV, NV₂Mok
Om (where N is the same as above, 0≤k≤4, 6≤m≤1
Vanadium complex oxide represented by 8), or N₃V₂
Mon Op (where N is the same as above, 0 ≦ n ≦ 4, 8 ≦
a vanadium complex oxide represented by p ≦ 20),
Use of these vanadium composite oxides as polar active materials
Therefore, the discharge voltage, discharge capacity, and cycle characteristics are
A more excellent non-aqueous secondary battery can be obtained. these
As the vanadium composite oxide, for example, Ca₂V
₂O₇, CaV ₂O₆, Ca₃V₂O₈, Cd₂V₂O
₇, CdV₂O₆, Cd₃V₂O₈, Co₂V₂O₇,
CoV₂O₆, Co₃V₂O₈, Ni₂V₂O₇, Ni
V₂O₆, Ni₃V₂O₈, Mg₂V₂O₇, MgV₂
O₆, Mg₃V₂O₈, Mn₂V ₂O₇, MnV
₂O₆, Mn₃V₂O₈, Zn₂V₂O₇, ZnV₂O
₆, Zn ₃V₂O₈, Cu₂V₂O₇, CuV₂O₆,
Cu₃V₂O₈, And those containing Mo
Cd, Co, Ni, Cu, M of the above compound
n, Zn, Ca, Mg, some other transition metals, Ca or
It may be replaced with Mg.

The negative electrode active material used in the present invention is an M compound (where M is V, a transition metal other than Mo, Ca or Mg).
Metal selected from the above) and V compound, and Mo if necessary
The compound can be mixed and fired or synthesized by a solution reaction, but the firing method is particularly preferable.

The calcination temperature for synthesis of the vanadium composite oxide used in the present invention is as follows: the M compound used in the present invention (where M is the same as above), the V compound, and optionally Mo.
It may be a temperature at which a part of the compound decomposes and melts, and for example, it is preferably 250 to 1500 ° C, and particularly 350 to 120
0 ° C is preferred.

The synthesis firing gas atmosphere of the vanadium composite oxide used in the present invention is not particularly limited, but the firing is performed in air, a gas whose oxygen concentration is arbitrarily adjusted, or an inert gas (nitrogen gas, argon gas, etc.). can do.

The preferred M compound used in the present invention (
Where M is the same as above), calcium oxide, carbonic acid
Calcium, calcium hydroxide, calcium chloride, bromide
Calcium, calcium iodide, calcium acetate, formic acid
Lucium, calcium sulphate, calcium nitrate, oxidized cad
Cadmium, cadmium chloride, cadmium bromide, cadmium iodide
Um, cadmium sulfate, cadmium nitrate, cadmium sulfide
Mu, CoO, Co₂O ₃, Co₃O_Four, Cobalt carbonate,
Basic cobalt carbonate, cobalt hydroxide, cobalt sulfate,
Cobalt nitrate, cobalt sulfite, cobalt perchlorate, chi
Cobalt cyanate, cobalt oxalate, cobalt acetate, fluorine
Cobalt iodide, cobalt chloride, cobalt bromide, cobalt iodide
G, hexaamminecobalt complex salt (as salts, sulfuric acid, glass
Acid, perchloric acid, thiocyanic acid, oxalic acid, acetic acid, fluorine, salt
Element, bromine, iodine), nickel oxide, nickel hydroxide, charcoal
Nickel acid, basic nickel carbonate, nickel sulfate, nitric acid
Nickel, nickel fluoride, nickel chloride, nickel bromide
, Nickel iodide, nickel formate, nickel acetate, nickel
Queracetylacetonate, copper oxide (mono and divalent), hydroxy
Copper oxide, copper sulfate, copper nitrate, copper phosphate, copper fluoride, copper chloride, chloride
Ammonium copper, copper bromide, copper iodide, copper formate, copper acetate, oxalate
Copper acid, copper citrate, magnesium oxide, magnesia hydroxide
Um, Magnesium chloride, Magnesium bromide, Magnesium iodide
Nesium, magnesium carbonate, magnesium sulfate, nitric acid
Magnesium, magnesium methoxide, magnesium
Muetoxide, magnesium acetate, magnesium formate
MnO₂, Mn₂O₃, Manganese hydroxide, carbonate man
Cancer, manganese nitrate, manganese sulfate, manganese sulfate
Monium, manganese sulfite, manganese phosphate, man borate
Cancer, manganese chlorate, manganese perchlorate, thiocyanate
Manganese acid, manganese formate, manganese acetate, manganese oxalate
Manganese citrate, manganese lactate, manganese tartrate
Manganese stearate, manganese fluoride, manganese chloride
, Manganese bromide, manganese iodide, manganese acetylate
Setonate, zinc oxide, zinc chloride, zinc bromide, iodine
Lead, zinc carbonate, zinc sulfate, zinc nitrate, zinc formate, subacetic acid
Examples include lead, zinc sulfide, zinc stearate, etc.
It

Preferred V compounds used in the present invention are VOE (Vanadium pentoxide for compounds with E = 2 to 2.5E = 2.5), lithium compounds of VOE, vanadium hydroxide, ammonium metavanadate, orthovanazine. Examples thereof include ammonium acid salt, ammonium pyrovanadate, vanadium oxosulfate, vanadium oxytrichloride, and vanadium tetrachloride.

The preferred Mo compounds used in the present invention include MoO ₃ , MoO ₂ , MoC ₁₃ , MoC ₁₄ ,
MoC ₁₅ , molybdenyl acetylacetonate and the like can be mentioned.

These M compounds, V compounds and Mo compounds
In addition, compounds that generally increase ionic conductivity, or
Is an amorphous forming agent containing P, B, Si (for example,
P₂O _Five, Li₃PO_Four, H₃BO₃, SiO₂Such)
It may be mixed with and fired. Also, such as Na, K
It may be mixed with potassium metal ions and fired. Combination of the above
Dry or wet mix and fire under arbitrary conditions
And the vanadium composite oxide used in the present invention
Obtainable. (For example, Anariji Timika,
47, 805 (1957))

The vanadium composite oxide used in the present invention has a lithium ion content of 0 to Li.
A non-aqueous secondary battery of 3V class can be obtained by having a potential of -1V and combining with a certain kind of positive electrode active material.

The vanadium composite oxide used in the present invention may or may not change the basic structure of the crystal by inserting lithium ions, and if it changes, the basic structure of the crystal after the change is filled. It does not change due to discharge, and acts as a negative electrode active material by absorbing and desorbing lithium ions due to the changed basic structure. (Patent application 4
-106642)

All of the vanadium composite oxides used in the present invention are considered to be compounds that occlude and release lithium ions and change the valence of the transition metal upon charge and discharge. Therefore, the negative electrode active material of the present invention is a negative electrode active material having a concept that is fundamentally different from the method of depositing and dissolving lithium by charging and discharging like a metal negative electrode active material such as lithium metal or lithium alloy. Similarly, when compared to carbonaceous compounds,
Carbon is not a compound whose valence changes clearly, but also a compound which has high conductivity and easily deposits lithium metal during charging. Therefore, the negative electrode active material of the present invention is a negative electrode active material whose concept is fundamentally different from that of lithium metal or carbonaceous material.

Each of the vanadium composite oxides used in the present invention is stable by charge and discharge, does not deposit lithium metal, is safe and has a large discharge capacity, and is excellent in cycle characteristics.

As the negative electrode active material which can be used in combination with the present invention, lithium metal and lithium alloy (Al, A
1-Mn (US Pat. No. 4,820,599), Al-M
g (JP-A-57-98977), Al-Sn (JP-A-Sho 6)
3-6, 742), Al-In, Al-Cd (Japanese Unexamined Patent Publication No.
-144,573), etc., and a calcined carbonaceous compound capable of inserting and extracting lithium ions or lithium metal (for example, JP-A-58-209,864, 61-214,417,
62-88, 269, 62-216, 170, 6
3-13, 282, same 63-24, 555, same 63-1
21,247, 63-121,257, 63-15
5,568, 63-276, 873, 63-31.
4,821, JP-A-1-204,361, and 1-22.
1,859, 1-254,360, etc.). The purpose of the combined use of the lithium metal and lithium alloy is to insert lithium ions in the battery,
As a battery reaction, a dissolution and precipitation reaction of lithium metal or the like is not used.

Examples of the positive electrode active material used in the present invention include transition metal oxides capable of reversibly occluding and releasing lithium ions, and lithium-containing transition metal oxides are particularly preferable.

Preferred Lithium Content Used in the Present Invention
As the metal oxide positive electrode active material, Lix CoO₂, Li
x NiO₂, Lix CoA Ni₁-A O₂, Liz CoB
V₁-B Oz, Lix CoB Fe₁-B O₂, Lix CoF
AG O₂, Lix Mn₂O_Four, Lix MnD Co₂-D O
_Four, Lix MnD Ni₂-D O_Four, Lix MnD V₂-DOz
 , Lix MnD Fe₂-D O_Four, Lix Mn₂O_FourAnd M
nO₂Mixture of Li ₂xMnO₃And MnO₂A mixture of
Lix Mn₂O_Four, Li₂xMnO₃And MnO₂A mixture of
(Here, A = Al, In or Sn, x = 0.6 to 1.
2, A = 0.1 to 0.9, B = 0.8 to 0.98, D =
1.6-1.96, F = 0.85-1, G = 0-0.
1, z = 2.01 to 5).

Further preferred Lithiu used in the present invention
As a positive electrode active material containing a metal oxide, Lix Co
O₂, Lix NiO₂, Lix CoA Ni₁-A O₂, L
ix CoB V1-B Oz, Lix CoB Fe₁-B O₂, L
ix CoF AG O₂, Lix Mn ₂O_Four, Lix MnD
Co₂-D O_Four, Lix MnD Ni₂-D O_Four, Lix Mn
DV₂-D O_Four, Lix MnD Fe₂-D O_Four(Where A =
Al, In or Sn, x = 0.7 to 1.04, A =
0.1 to 0.9, B = 0.8 to 0.98, D = 1.6 to
1.96, F = 0.85-1, G = 0-0.1, z =
2.01 to 5).

The average particle size of the positive electrode active material and the negative electrode active material used in the present invention is not particularly limited, but is 0.2 to 50 μm.
m is preferred. 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 swirling airflow type jet mill, a sieve and the like are used.

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 black 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, polyvinyl pyrrolidone,
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 the organic solvent.
Len carbonate, ethylene carbonate, butylene car
Carbonate, dimethyl carbonate, diethyl carbonate
Methyl ethyl carbonate, γ-butyrolactone,
1,2-dimethoxyethane, tetrahydrofuran, 2-
Methyltetrahydrofuran, dimethylsulfoxide,
1,3-dioxolane, formamide, dimethylform
Amide, dioxolane, acetonitrile, nitrometa
, Methyl formate, methyl acetate, methyl propionate,
Ethyl ropionate, phosphoric acid triester (JP-A-60-
23,973), trimethoxymethane (JP-A-61-
4,170), dioxolane derivative (JP-A-62-1)
5,771, 62-22,372, 62-108,
474), sulfolane (JP-A-62-31959),
3-methyl-2-oxazolidinone (JP-A-62-4)
4,961), propylene carbonate derivative
62-290,069, 62-290,071), TE
Trahydrofuran derivative (JP-A-63-32,87)
2), diethyl ether (JP-A-63-62, 16)
6), 1,3-propane sultone (Japanese Patent Laid-Open No. 63-10
At least an aprotic organic solvent such as
Solvent mixed with at least one kind and lithium soluble in the solvent
Salt, eg LiClO_Four, LiBF_Four, LiPF₆,
LiCF₃SO₃, LiCF₃CO ₂, LiAsF₆,
LiSbF₆, LiB_TenCl_Ten(JP-A-57-74,9
74), lower aliphatic lithium carboxylate (JP-A-60-
41,773), LiAlCl_Four, LiCl, LiB
r, LiI (JP-A-60-247,265), chlorobot
Lanthanum (JP-A-61-165,957), four-phase
Lithium Nylborate (JP-A 61-214,376)
Which is composed of one or more salts. Above all, professional
Pyrene carbonate or ethylene carbonate and 1,2
-Dimethoxyethane and / or diethylcarbonate
LiCF in the mixed solution₃SO₃, LiClO_Four, Li
BF_FourAnd / or LiPF₆Electrolytes containing
Good The amount of these electrolytes added to the battery is particularly limited.
However, the amount of positive and negative electrode active materials and battery
The required amount can be used depending on the size. Volume ratio of solvent
Is not particularly limited, but propylene carbonate or
Is ethylene capote versus 1,2-dimethoxyethane and
In the case of a mixed solution of // or diethyl carbonate, 0.
4 / 0.6 to 0.6 / 0.4 (1,2-dimethoxyethane
The mixing ratio when using both diethyl carbonate and diethyl carbonate
0.4 / 0.6 to 0.6 / 0.4) is preferable. Supporting electricity
The concentration of the denaturation is not particularly limited, but 1 liter of electrolytic solution
It is preferably 0.2 to 3 mol.

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-A-59-60,866), Li ₂ SiS ₃ (JP-A-60-501,731), phosphorus sulfide compound (JP-A-62-82,665) and the like are 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 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. Sheets and nonwoven fabrics made of olefinic polymers such as polypropylene, glass fibers, or polyethylene are used because of their resistance to organic solvents and hydrophobicity. The pore size of the separator is in the range generally used for batteries. For example, 0.01 to 10
μm 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)

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 (Japanese Patent Laid-Open No. 48-36,6).
33), a method of adding an electrolytic solution (JP-A-57-124,870) is known.

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 that does not undergo 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. When the shape of the battery is a sheet, a cylinder, or a corner, 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. As a coating method, a general method can be used. For example, reverse roll method, direct roll method, blade method, knife method,
Extrusion method, curtain method, gravure method, bar method, dip method, and squeeze method can be mentioned. Among them, the blade method, the knife method, and the extrusion method are preferable. The coating is preferably performed at a speed of 0.1 to 100 m / min. At this time, a good surface condition of the coating layer can be obtained by selecting the above-mentioned coating method according to the solution physical properties and drying properties of the mixture. The thickness, length and width of the coating layer are determined by the size of the battery, but the thickness of the coating layer is 1 to 1 in the compressed state after drying.
2000 μm is particularly preferred.

As a method for drying or dehydrating the pellets or sheets, a generally adopted method can be used. In particular, it is preferable to use hot air, vacuum, infrared rays, far infrared rays, electron beams, and low humidity air alone or in combination.
The temperature is preferably in the range of 80 to 350 ° C, particularly 100 to
A range of 250 ° C is preferred. Water content of the entire battery is 200
0 ppm or less is preferable, and 500 ppm or less for each of the positive electrode mixture, the negative electrode mixture and the electrolyte is preferable from the viewpoint of cycleability. As the pellet or sheet pressing method, a generally adopted method can be used, but a die pressing method or a calendar pressing method is particularly preferable. The pressing pressure is not particularly limited, but 0.2 to 3 t / cm ² is preferable. The press speed of the calendar press method is 0.1 to 50 m
/ Min is preferred. The pressing temperature is preferably room temperature to 200 ° C.

The mixture sheet is rolled or folded and inserted into a can, the can and the sheet are electrically connected, an electrolytic solution is injected, and a sealing plate is used to form a battery can. At this time, the safety valve can be used as a sealing plate. Other than safety valve,
Various safety elements known in the art may be provided. For example, a fuse, a bimetal, a PTC element or the like is used as the overcurrent prevention element. In addition to the safety valve, as a measure for increasing the internal pressure of the battery can, a method of making a cut in the battery can, a method of cracking a gasket or a method of cracking a sealing plate can be used. Further, the charger may be provided with a circuit incorporating measures against overcharging and overdischarging. For the can and the lead plate, a metal or alloy having electrical conductivity can be used. For example, metals such as iron, nickel, titanium, chromium, molybdenum, copper and aluminum, or alloys thereof are used. Welding methods for caps, cans, sheets, and lead plates are known methods (eg, DC or AC electric welding,
Laser welding and ultrasonic welding) can be used. As the sealing agent for sealing, a conventionally known compound or mixture such as asphalt can be used.

[0037]

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 7.48 g of CoO and 18.2 g of V ₂ O ₅ were dry-mixed and calcined in air at 800 ° C. for 12 hours. After firing, it was cooled to room temperature and taken out from the firing furnace to obtain CoV ₂ O ₆ . The compound was pulverized by a vibration mill to give an average particle size of 5 μm.
CoV ₂ O ₆ was obtained. CdV ₂ O ₆ , NiV ₂ O ₆ ,
CuV ₂ O ₆ , MnV ₂ O ₆ , ZnV ₂ O ₆ , MgV ₂
For O ₆ and CaV ₂ O ₆ , instead of CoO, CdO, NiO, CuO, MnO and Z were used in the same manner.
It was synthesized by using a stoichiometric amount of nO, MgO, and CaO and pulverized.

Synthesis Example-2 CoO 7.48 g, V ₂ O ₅ 18.2 g, MoO ₃
1.44 g was dry mixed and calcined in air at 800 ° C. for 12 hours. After firing, it was cooled to room temperature and taken out from the firing furnace to obtain CoV ₂ Mo0.1 O6.3. The compound was pulverized by a vibration mill to obtain CoV ₂ Mo having an average particle size of 4.5 μm.
0.1 O6.3 was obtained. CoV ₂ Mo0.2 O6.6, CoV ₂
Mo0.5 O7.5, CoV ₂ Mo0.8 O8.4, CoV ₂ M
o1.0 O ₉ , CoV ₂ Mo1.5 O10.5, CoV ₂ Mo3.
For 0 O10 and CoV ₂ Mo4.0 O18, the amounts of MoO ₃ were 2.88 g, 7.20 g and 1 respectively in the same manner.
1.52g, 14.4g, 21.6g, 43.2g, 5
It was synthesized by using 7.6 g and pulverized.

Synthesis Example-3 CdV ₂ Mo0.8 O8.4, NiV ₂ Mo0.8 O8.4, C
uV ₂ Mo0.8 O8.4, MnV ₂ Mo0.8 O8.4, Zn
V ₂ Mo0.8 O8.4, MgV ₂ Mo0.8 O8.4, CaV
₂ For Mo0.8O8.4, CdO, NiO and Cu were used instead of CoO in the same manner as in Synthesis Example-2.
O, MnO, ZnO, MgO, and CaO were synthesized by using stoichiometric amounts and pulverized.

Synthesis Example 4 CoO 15.0 g, V₂O_Five Dry mix 18.2g
Then, it was baked in air at 800 ° C. for 12 hours. After firing, room
Cool to a high temperature and remove from the firing furnace to remove Co₂V ₂O₇To
Obtained. 3. The compound was pulverized by a vibration mill to give an average particle size of 4.
8 μm Co₂V₂O₇Got Cd₂V₂O₇, Ni
₂V₂O₇, Cu₂V₂O₇, Mn₂V₂O₇, Zn₂
V₂O₇, Mg₂V₂O₇, Ca₂V₂O₇about
In the same way, instead of CoO, CdO and Ni respectively
O, CuO, MnO, ZnO, MgO, CaO are stoichiometric
It was synthesized by using a stoichiometric amount and crushed.

Synthesis Example-5 CoO 15.0 g, V ₂ O ₅ 18.2 g, MoO ₃
2.88 g was dry mixed and calcined in air at 800 ° C. for 12 hours. After firing, it was cooled to room temperature and taken out from the firing furnace to obtain Co ₂ V ₂ Mo0.2 O7.6. The compound was pulverized by a vibration mill to obtain Co ₂ V ₂ having an average particle diameter of 5.3 μm.
Mo0.2 O7.6 was obtained. Cd ₂ V ₂ Mo0.2 O7.6, N
i ₂ V ₂ Mo0.2 O7.6, Cu ₂ V ₂ Mo0.2 O7.6,
Mn ₂ V ₂ Mo0.2 O7.6, Zn ₂ V ₂ Mo0.2 O7.6
, Mg ₂ V ₂ Mo0.2 O7.6, Ca ₂ V ₂ Mo0.2 O
For 7.6, instead of CoO, CdO, NiO, CuO, MnO, ZnO, MgO, and
It was synthesized by using a stoichiometric amount of CaO and ground.

Synthesis Example 6 CoO 22.4 g, V₂O_Five Dry mix 18.2g
Then, it was baked in air at 800 ° C. for 12 hours. After firing, room
Cool to a high temperature and remove from the firing furnace to remove Co₃V ₂O₈To
Obtained. The compound was pulverized by a vibration mill to give an average particle size of 5.
1 μm Co₃V₂O₈Got Cd₃V₂O₈, Ni
₃V₂O₈, Cu₃V₂O₈, Mn₃V₂O₈, Zn₃
V₂O₈, Mg₃V₂O₈, Ca₃V₂O₈about
In the same way, instead of CoO, CdO and Ni respectively
O, CuO, MnO, ZnO, MgO, CaO are stoichiometric
It was synthesized by using a stoichiometric amount and crushed.

Synthesis Example 7 CoO 22.4 g, V ₂ O ₅ 18.2 g, MoO ₃
2.88 g was dry mixed and calcined in air at 800 ° C. for 12 hours. After firing, it was cooled to room temperature and taken out from the firing furnace to obtain Co ₃ V ₂ Mo0.2 O8.6. The compound was pulverized with a vibration mill to obtain Co ₃ V ₂ having an average particle size of 4.5 μm.
Mo0.2 O8.6 was obtained. Cd ₃ V ₂ Mo0.2 O8.6, N
i ₃ V ₂ Mo0.2 O8.6, Cu ₃ V ₂ Mo0.2 O8.6,
Mn ₃ V ₂ Mo0.2 O8.6, Zn ₃ V ₂ Mo0.2 O8.6
, Mg ₃ V ₂ Mo0.2 O8.6, Ca ₃ V ₂ Mo0.2 O
For 8.6, instead of CoO by the same method, CdO, NiO, CuO, MnO, ZnO, MgO,
It was synthesized by using a stoichiometric amount of CaO and ground.

Example 1 As a method for preparing a mixture, in the positive electrode material, a positive electrode active material was used.
% By weight, 12% by weight of flake graphite as a conductive agent, binder
As tetrafluoroethylene at a mixing ratio of 6% by weight
Positive electrode pellets (13 mm
Φ, 0.14g) in a dry box (dew point -40 to -7
After thoroughly dehydrating with a far infrared heater in 0 ° C, dry air)
Using. In the negative electrode material, 82% by weight of the negative electrode active material
12% by weight of flake graphite as an agent, and polyacetic acid as a binder
Press the mixture containing 6% by weight of vinylidene fluoride mixed.
Compression molded negative electrode pellets (13 mmΦ, 0.030
g) Far infrared heater in the same dry box as above
It was used after being thoroughly dehydrated. 8 for both positive and negative electrode cans
Weld a 0 μm thick SUS316 net to a coin can
Using. 1 mol / l LiPF6 as electrolyte₆
(Ethylene carbonate and diethylene carbonate etc.
250 μl of the volume mixture), and a separator
-As microporous polypropylene sheet and polypropylene
Use a non-woven fabric to impregnate the electrolyte with the electrolyte
I was there. Then, the coin type non-aqueous secondary battery as shown in FIG.
It was made in the same dry box as. This non-aqueous battery
0.75mA / cm²At a constant current density of 4.3 to 1.
A charge / discharge test was conducted in the range of 8V. (All tests are
I started with the electric power. ) As the negative electrode active material, CoV synthesized in Synthesis Example-1
₂O₆, CdV₂O₆, NiV₂O₆, CuV₂O₆,
MnV₂O₆, ZnV₂O₆, MgV₂O₆, CaV ₂
O₆Was used. The results of the charge / discharge test are shown in Table 1. still,
In Table 1, (a) second cycle discharge capacity (negative electrode
(MAH per 1 g of active material), (a) Second cycle
-Ron efficiency (%), (c) Average discharge voltage in the second cycle
Pressure (V), (d) until the capacity reaches 60% of the maximum capacity
Indicates the number of cycles (times).

[0046]

[Table 1]

Comparative Example 1 82% by weight of carbonaceous coal-based coke (manufactured by Nippon Steel Chemical Co., Ltd., trade name LPC-u) was used as a negative electrode active material, and acetylene black (manufactured by Denki Kagaku Co., Ltd., trade name Denka) as a negative electrode conductive agent. 12% by weight of black) as a negative electrode binder,
A coin type non-aqueous secondary battery was produced in the same manner as in Example 1 except that 6% by weight of an ethylene-propylene-diene copolymer (Sumitomo Chemical Co., Ltd., trade name ESPREN) was used, and 0.75 mA / 3.95 at a constant current density of cm ^2.
A charge / discharge test was performed in the range of -3.2V. (The tests were all started from charging.) The results are shown in Table 1. From now on, the non-aqueous secondary battery using the vanadium composite oxide of the present invention as the negative electrode active material is the one using the carbonaceous material. In comparison, it can be seen that both discharge capacity and cycle characteristics are excellent.

Comparative Example 2 A non-aqueous secondary battery was prepared in the same manner as in Example 1 except that WO ₂ was used as the negative electrode active material, and a charge / discharge test was conducted in the same manner as in Example 1. . The results are shown in Table 1. From this, the non-aqueous secondary battery using the vanadium composite oxide of the present invention as the negative electrode active material has a larger discharge capacity and a higher discharge voltage than those using WO _2. Moreover, it can be seen that the cycle characteristics are also excellent.

Comparative Example 3 Example 1 except that Fe ₃ O ₄ was used as the negative electrode active material.
A non-aqueous secondary battery was prepared in the same manner as in 1. and a charge / discharge test was conducted in the same manner as in Example-1. The results are shown in Table 1. From this, the non-aqueous secondary battery using the vanadium composite oxide of the present invention as the negative electrode active material has a larger discharge capacity than the one using Fe ₃ O ₄ and has a higher discharge voltage. It is found that the value is high and the cycle characteristics are also excellent.

Example 2 As the negative electrode active material, CoV ₂ MoO.
1 O6.3, CoV ₂ Mo0.2 O6.6, CoV ₂ Mo0.5
O7.5, CoV ₂ Mo0.8 O8.4, CoV ₂ Mo1.0 O
9, CoV ₂ Mo1.5 O10.5, CoV ₂ Mo3.0 O15,
A non-aqueous secondary battery was prepared in the same manner as in Example 1 except that CoV ₂ Mo4.0 O18 was used, and a charge / discharge test was conducted in the same manner as in Example 1. The results are shown in Table 2. From this result, it is understood that the discharge capacity and the cycle characteristics are further improved by including Mo.

[0051]

[Table 2]

Example 3 As a negative electrode active material, CdV ₂ MoO.
8 O8.4, NiV ₂ Mo0.8 O8.4, CuV ₂ Mo0.8
O8.4, MnV ₂ Mo0.8 O8.4, ZnV ₂ Mo0.8 O
8.4, MgV ₂ Mo0.8 O8.4, CaV ₂ Mo0.8 O8.
A non-aqueous secondary battery was prepared in the same manner as in Example-1 except that 4 was used, and a charge / discharge test was conducted in the same manner as in Example-1. The results are shown in Table 3. From this result, it is understood that the discharge capacity and the cycle characteristics are further improved by including Mo.

[0053]

[Table 3]

Example 4 Co ₂ V synthesized in Synthesis Example 4 as a negative electrode active material
₂ O ₇ , Cd ₂ V ₂ O ₇ , Ni ₂ V ₂ O ₇ , Cu ₂ V ₂
O ₇ , Mn ₂ V ₂ O ₇ , Zn ₂ V ₂ O ₇ , Mg ₂ V ₂ O
₇ , using Ca ₂ V ₂ O ₇ , 0.11g positive electrode pellet
A non-aqueous secondary battery was prepared in the same manner as in Example-1 except that the above was used, and a charge / discharge test was conducted in the same manner as in Example-1. The results are shown in Table 4. From this result, the discharge capacity of the non-aqueous secondary battery using the negative electrode active material in this example,
It can be seen that both discharge voltage and cycle characteristics are excellent.

[0055]

[Table 4]

Example 5 Co ₂ V ₂ Mo synthesized in Synthesis Example 5 as a negative electrode active material
0.2 O7.6, Cd ₂ V2 Mo0.2 O7.6, Ni ₂ V ₂ M
o0.2 O7.6, Cu ₂ V ₂ Mo0.2 O7.6, Mn ₂ V _{2
Mo0.2 O7.6, Zn 2 V 2 Mo0.2} O7.6, Mg 2 V
_A non-aqueous secondary battery was prepared in the same manner as in Example 4 except that ₂ Mo0.2 O7.6 and Ca ₂ V ₂ Mo0.2 O7.6 were used, and was charged in the same manner as in Example 1. A discharge test was conducted. The results are shown in Table 5. From this result, it is understood that the discharge capacity and the cycle characteristics are further improved by including Mo.

[0057]

[Table 5]

Example 6 Co ₃ V synthesized in Synthesis Example 6 as a negative electrode active material
₂ O ₈ , Cd ₃ V ₂ O ₈ , Ni ₃ V ₂ O ₈ , Cu ₃ V _{2
O 8, Mn 3 V 2 O} 8, Zn 3 V 2 O 8, Mg 3 V 2 O
_A non-aqueous secondary battery was prepared in the same manner as in Example 4 except that ₈ and Ca ₃ V ₂ O ₈ were used, and a charge / discharge test was conducted in the same manner as in Example 1. The results are shown in Table 6. From these results, it can be seen that the non-aqueous secondary battery using the negative electrode active material in this example is excellent in discharge capacity, discharge voltage and cycle characteristics.

[0059]

[Table 6]

Example 7 Co synthesized in Synthesis Example 7 as a negative electrode active material₃V₂Mo
0.2 O8.6, Cd₃V ₂Mo0.2 O8.6, Ni₃V₂M
o0.2 O8.6, Cu₃V₂Mo0.2 O8.6, Mn₃V₂
Mo0.2 O8.6, Zn₃V₂Mo0.2 O8.6, Mg₃V
₂Mo0.2 O8.6, Ca₃V₂Use Mo0.2 O8.6
A non-aqueous secondary battery was prepared in the same manner as in Example 4 except for the above.
Then, a charge / discharge test was conducted in the same manner as in Example-1. So
The results are shown in Table 7. From this result, include Mo
This will further improve the discharge capacity and cycle characteristics.
I understand.

[0061]

[Table 7]

Example-8 CoV of Example-1₂O₆Implementation of non-aqueous secondary battery using
Example-2 CoV₂Mo _0.8O_8.4Non-aqueous secondary battery using
Pond, Co of Example-4₂V₂O₇Non-aqueous secondary battery using
Pond, Co of Example-6₃V₂O₈Non-aqueous secondary battery using
The same safety test as the
Was carried out. 50 non-aqueous secondary batteries each 5mA /
cm²20 cycles charge / discharge at 4.3-1.8V under the condition
After repeating the procedure, disassemble the battery and remove 60% of the negative electrode pellet.
RH Take it out into the air and check if it spontaneously ignites
It was As a result, no ignition was observed in all non-aqueous secondary batteries.
won.

Comparative Example 4 As a negative electrode pellet, a Li-Al alloy (80% -20%) was used.
Fifty non-aqueous secondary batteries were prepared in the same manner as in Example-1 except that the weight ratio, 15 mmΦ, and 0.6 mm thickness) was used. These batteries were charged and discharged for 20 cycles under the same conditions as in Example-8, and the same safety test as in Example-8 was conducted.
As a result, 32 negative electrode pellets ignited. This shows that the negative electrode active material of the present invention is safer than the Li-Al alloy.

[0064]

As in the present invention, by using a specific vanadium composite oxide as the negative electrode active material, and further by including molybdenum in it, a high discharge operating voltage, a large discharge capacity and a good charge and discharge can be obtained. A safe non-aqueous secondary battery having cycle characteristics can be obtained.

[Brief description of drawings]

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

[Explanation of symbols]

 1 Negative Electrode Sealing Plate 2 Negative Electrode Mixture Pellet 3 Separator 4 Positive Electrode Mixture Pellet 5 Current Collector 6 Positive Electrode Case 7 Gasket

─────────────────────────────────────────────────── ───

[Procedure amendment]

[Submission date] September 30, 1993

[Procedure Amendment 1]

[Document name to be amended] Statement

[Correction target item name] 0013

[Correction method] Change

[Correction content]

Preferred Mo compounds used in the present invention include MoO ₃ , MoO ₂ , MoCl ₃ , MoCl ₄ ,
MoCl ₅ , molybdenyl acetylacetonate and the like can be mentioned.

Claims (5)

[Claims] 1. 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 is Ma Vb Moc Od (where M
Is at least one selected from transition metals other than Mo and V, Ca and Mg, 1 ≦ a ≦ 11, 1 ≦ b ≦ 6, 0 ≦ c / b
≦ 2,3 ≦ d ≦ 40) a vanadium composite oxide represented by the formula: non-aqueous secondary battery 2. The vanadium composite oxide is Ne Vf Mog.
Oh (where N is Ca, Mg, Cd, Co, Ni, C
at least one selected from u, Mn, and Zn, 1 ≦ e ≦
11, 1 ≦ f ≦ 6, 0 ≦ g / f ≦ 2, 3 ≦ h ≦ 40). 3. The vanadium composite oxide is N ₂ V ₂ Moi.
Oj (where N is Ca, Mg, Cd, Co, Ni, C
at least one selected from u, Mn, and Zn, 0 ≦ i ≦
4. The non-aqueous secondary battery according to claim 1, wherein 4 ≦ 7 ≦ j ≦ 19). 4. The vanadium composite oxide is NV2 Mok O.
m (where N is Ca, Mg, Cd, Co, Ni, Cu,
At least one selected from Mn and Zn, 0 ≦ k ≦ 4,
6. The non-aqueous secondary battery according to claim 1, wherein 6 ≦ m ≦ 18). 5. The vanadium composite oxide is N3 V2 Mon.
Op (where N is Ca, Mg, Cd, Co, Ni, C
at least one selected from u, Mn, and Zn, 0 ≦ n ≦
4. 8 ≦ p ≦ 20), The non-aqueous secondary battery according to claim 1.