JPH07122299A - Non-aqueous secondary battery - Google Patents

Abstract

PURPOSE:To provide a lithium ion type non-aqueous electrolyte secondary battery excellent in electric discharging capacity and electric charging/discharging cycle performance. CONSTITUTION:In a secondary battery constituted of a positive electrode active material, a negative electrode active material, and a non-aqueous electrolyte including lithium salt, the negative electrode active material is composed of a transition metal oxide composition. The positive electrode active material is composed of lithium containing manganese composite oxide having the spinnel type structure expressed by the formula Li1+x[Mn2-yAz]O4 (wherein -1.0<x<1.7, 0<y<1.2, 0.02<z<1.0, and M represents one or more kinds of metals).

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a lithium ion non-aqueous electrolyte secondary battery having improved charge / discharge characteristics, charge / discharge cycle performance and safety.

[0002]

2. Description of the Related Art Light metal alloys or lithium containing lithium
A material that absorbs and releases um ions is used as the electrode active material.
A water electrolyte type secondary battery has high voltage and high energy density.
It is being actively researched because of its merits. These two
Safer than lithium alloy as a negative electrode active material for secondary batteries
There is a tendency for high-performance lithium-ion storage materials to be used.
It The positive electrode active material contains Li intercalation.
As a layered compound utilizing₂O_Four, Li₂M
nO₃, LiCoO₂, LiCo_0.5Ni_0.5O ₂, L
iNiO₂, MoS₂Etc. are generally used. these
Among them, it is particularly disclosed in JP-A-55-136131.
LiCoO₂Is a high discharge potential of 3.5 V or more with respect to Li
And is advantageous in that it has a high capacity. But the real
During use, the crystal structure gradually breaks down due to repeated charging and discharging.
Cycle performance problem that battery characteristics deteriorate
And high cost due to small supply of cobalt raw material
Including the problems of. Therefore, large amount of supply and low cost
Lix Mn made from manganese which is₂O_Four
A secondary battery using a positive electrode as a positive electrode material is disclosed in JP-A-3-14727.
6 and 4-123769, etc. But,
In this case, a carbonaceous material was used as the negative electrode active material.
In terms of battery capacity and cycle performance,
Therefore, for practical use, a negative electrode active material with a higher capacity and a
It is important to use manganese-based positive electrode active materials with excellent
Come on.

[0003]

SUMMARY OF THE INVENTION A first object of the present invention is to solve the above problems and provide a lithium ion non-aqueous electrolyte secondary battery excellent in charge / discharge characteristics and cycle performance, The second problem is to provide a secondary battery excellent in safety, and the third problem is to provide a secondary battery advantageous in terms of raw material cost.

[0004]

An object of the present invention is to provide a 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 comprises a transition metal oxide, The substance has the general formula Li ₁ + x [Mn ₂ -y Az].
O4 (-1.0 <x <1.7, 0 <y <1.2,0.0
2 <z <1.0, A is one or more kinds of metals) and is composed of a lithium-containing manganese composite oxide having a spinel structure, which can be solved by a method using a non-aqueous electrolyte secondary battery. It was

As the positive electrode active material of the secondary battery of the present invention, a manganese-containing oxide having a spinel type or spinel-like structure is used. The spinel type oxide has the general formula A
It has a structure represented by (B ₂ ) O 4, and in the formula, oxygen anions are arranged in a cubic close-packed form and occupy a part of the faces and vertices of tetrahedra and octahedra. The unit cell is composed of 8 molecules, and oxygen occupies position 32e in the Fd3m space. The unit cell occupies 64 octahedral lattice gaps in three non-crystallographically equivalent positions 8a, 8b, 48f. In this spinel, the B cations are located in the lattice gaps of the 16d octahedron (the empty octahedron is 16
c) The A cation is located at the site of the tetrahedral lattice gap of 8a. Each 8a octahedron has four adjacent empty 1s
A channel that shares a surface with a 6c octahedron, whereby the A cation diffuses (for example, 8a → 16c → 8a → 16c).
Will be provided. On the other hand, the 8b tetrahedron shares a face with the 16d octahedron formed by the B cation, which makes the cation occupation energetically disadvantageous. The 48f tetrahedron shares a face with both the 16d and 16c octahedra. Depending on the distribution state of cation A, A (B ₂ O ₄ is called normal spinel, B (A, B) O ₄ is called reverse spinel. Ax By (A ₁ -x B ₁ -y) which is an intermediate state between these is called. The structure of O ₄ also exists as a spinel.

A typical manganese oxide having a normal spinel structure is LiMn ₂ O ₄ , which is a positive electrode active material. In this structure, half the Mn cations are trivalent and half are tetravalent. Λ-also known as active material
MnO ₂ is a defective spinel structure in which lithium is removed from the structure of LiMn ₂ O ₄ , as shown in US Pat. No. 4,246,253.
All cations are tetravalent. The manganese oxide positive electrode active material used in the present invention includes normal spinel type, reverse spinel type, and defect-free spinel structure or defective non-stoichiometric spinel structure.

The manganese composite oxide of the present invention is obtained by adding a metal cation to the above-mentioned spinel-type manganese oxide having a crystal structure, and the cation replaces the manganese cation in the crystal structure. Doped with a geometrical or irregular geometry. Alternatively, a part of the cation may be present in the crystal structure at a position deviating from the site occupied by the manganese cation while forming a structural strain. The metal cation is preferably a transition metal cation, more preferably a divalent to tetravalent transition metal cation. These metal cations form a partially amorphous structure by being doped into the structure,
By changing the interstitial distance, an energy-favorable field for lithium insertion and desorption is provided, or a tough structure with little structural deterioration due to lithium insertion and desorption is provided. It contributes to the improvement of capacity and cycleability as a substance. The transition metals referred to in the present invention include Sc to Zn having an element number of 21 to 30; Yd to Cd having an element number of 39 to Cd; and La having an element number of 57 to Hg having an element number of 80.

Cations contained in the positive electrode active material of the present invention
Lithium-containing manganese with a doped spinel structure
The preferred composition of the oxide is the general formula Li₁+ x [Mn₂-y A
z] O_Four(-1.0 <x <1.7, 0 <y <1.2,
0.02 <z <1.0, A is one or more metals)
It Among them, the more preferable composition is the general formula Li₁-x [Mn
₂-y Az] O_Four(0 <x <1.0, 0 <y <1.0,
0.02 <z <1.0, M is one or more metals)
It A more preferable composition is one in which the amount of metal cation added is
It is the case of less than 20% with respect to
i₁-x [Mn₂-y Az] O_Four(0.2 <x <1.0,0
<Y <0.4, 0.02 <z <0.4, A is one or more
(Metallic) manganese composite oxide with spinel structure
Is. Also, it is preferable that y = z is not satisfied in the above general formula.
Good

The preferred specific examples of the lithium-containing manganese composite oxide which is the positive electrode active material of the present invention are shown below (structures represented by a decimal or integer multiple of the general formula are also included in the scope of the present invention). In the structural formula, M is a divalent to tetravalent metal cation, preferably a transition metal cation,
For example, A = Ni, Co, Cu, Fe, Ti, Cr,
V, Zr, Nb, Ru, S, Ge, Ga, Sb, Te and the like. _{Li 4 Mn 3. 9 A 0} . 1 O 9 LiMn 0. 9 A 0. 1 O 2 Li 2 Mn 0. 9 A 0. 1 O 3 Li 5 Mn 3. 95 A 0. 05 O 9 Li 4 Mn 4 _{. 9 A 0. 1 O 12} Li 2 Mn 4. 9 A 0. 1 O 11 Li 2 Mn 3. 9 A 0. 1 O 9 Li 2 Mn 7. 4 A 0. 1 O 16 Li 0. 7 Mn 1 _{in. 9 a 0. 1 O 4} Li 0. 95 Mn 1. 2 a 0. 8 O 4 in addition, the general formula for the positive electrode active material of the present invention,
Oxidation of a holland ore skeleton structure as described in JP-A-4-270125, in which Li is partially or mostly (for example, 95% or more) substituted with cations such as H, K, Na, and ammonium ions. Manganese compounds are also included. The Holland ore type compound in which hydrogen is substituted as a cation can be easily obtained, for example, by an operation of subjecting the lithium-manganese composite oxide of the above general formula to an acid delithiation treatment at high temperature.

The manganese composite oxide of the positive electrode active material of the present invention is obtained by reacting a lithium salt and a manganese salt or a manganese oxide in the solid phase at a high temperature in the presence of a metal oxide as a dopant or a salt thereof. can get. When using lithium carbonate and manganese dioxide as raw materials, the firing temperature is 350 ° C to 900 ° C, preferably 350 ° C to 50 ° C.
It is 0 ° C. and the firing time is 8 to 48 hours. In addition, lithium nitrate having a low melting point (melting point 261
(° C) is used, the firing temperature is from 300 ° C to 900 ° C.
And preferably 300 to 500 ° C. Examples of manganese oxides include λ-MnO ₂ , electrolytically prepared MnO ₂ (EMD), and chemically prepared MnO.
₂ (CMD) and mixtures thereof can be used. Besides, as the lithium raw material, a lithium-manganese composite oxide (for example, Li ₂ Mn ₄ O ₉ or the like) can be used. In this case, the lithium-manganese composite oxide is mixed with a manganese raw material such as manganese dioxide and
Baking is performed in the range of 0 ° C to 500 ° C.

As the negative electrode active material of the present invention, an oxide or a composite oxide composed of one or more transition metals is used.
The oxide is A [B ₂ ] O ₄ or A [B · C] O ₄
(B and C are transition metal cations, and A is a monovalent cation such as lithium) An oxide active material having a spinel structure, or electrochemical insertion of lithium ion into the active material structure (anodic charging) An oxide (anode active material precursor) generated by the above is preferable. Of these, preferred in the present invention are active material precursors of the type that produce a negative electrode active material by inserting lithium ions into a transition metal oxide. For example, the active material precursor is synthesized by mixing two or more kinds of transition metal compounds, or a lithium compound and one or more kinds of transition metal compounds are mixed in a lithium compound / total transition metal compound molar ratio. It can be mixed and synthesized so as to be 3.1 or less. However, two or more transition metals are
At least one of i, V, Mn, Co, Ni, Fe, Cr, Nb, and Mo is included. At least one of the negative electrode active material precursors is Lip MOr (where M is at least one transition metal of at least one of Ti, V, Mn, Co, Fe, Nb, and Mo, p = 0 to 3. 1, r = 1.6-4.
1, however, the sum of M is set to 1, so it may be multiplied by an integer when there are multiple transition metals or when a crystallographic composition formula is displayed.)
The lithium-containing transition metal oxide represented by Further, a more preferable lithium-containing transition metal oxide has a structural formula of Lip M ₁ q1 M ₂ q2 ... Mnqn Or.
(Here, M is at least one of Ti, V, Mn, Co,
The transition metal containing Ni and Fe p = 0 to 3.1, q1 +
q2 + ... + qn = 1, n = 1 to 10, r = 1.6 to
It is shown in 4.1). The most preferable lithium-containing transition metal oxide in the above formula is Lip Coq V ₁ -q O
r, Lip Niq V ₁ -q Or (where p = 0.3 to 2.
2, q = 0.02 to 0.7, r = 1.5 to 2.5). Further, particularly preferable lithium-containing transition metal oxides include Lip CoVO ₄ and Lip NiVO ₄ (where p = 0.3 to 2.2). The above operation of converting the active material precursor composed of a transition metal oxide into an active material is performed by inserting lithium by electrochemical charging. In the above formula, the p value is a value before the start of charging / discharging, and is increased (decreased) by charging (charging). Therefore, the negative electrode active material is one in which the content of lithium is increased in the composition formula of the transition metal oxide precursor, and as a result, the X-ray diffraction pattern is substantially different from the precursor. .

The negative electrode active material precursor of the present invention can be synthesized by a method in which the above raw materials are mixed and fired in a solid phase or by a solution reaction, but the firing method is particularly preferable. The firing temperature is
It may be a temperature at which a part of the raw material compound is decomposed and melted, and is usually 250 to 2000 ° C., preferably 350.
~ 1500 ° C, more preferably 500 ° C to 1000 ° C
Is. The firing time is preferably 4 to 48 hours, and 6 to 20 hours.
Time is more preferred.

With respect to the active material of the present invention, the gas atmosphere for firing is not particularly limited, but in the positive electrode active material, it is in air or in a gas containing a large proportion of oxygen (for example, about 30% or more),
The negative electrode active material is preferably in the air or a gas having a low oxygen content (for example, about 10% or less) or an inert gas (nitrogen gas, argon gas).

The average particle size of the positive electrode active material and the negative electrode active material used in the present invention is preferably 0.03 to 50 μm, and particularly preferably 0.1 μm to 10 μm. The average particle size as used herein is a mode diameter indicating the most frequent point, and is an average value of values visually observed from an electron micrograph or a value measured by a particle size distribution measuring device. The specific surface area of these active materials is preferably 0.1 to 50 m ² / g. The preferable specific surface area of the positive electrode active material is 5 to 100 m ² /
It is g.

The positive electrode active material and the negative electrode active material of the present invention are preferably synthesized by firing a mixture of a lithium compound and a transition metal compound described below. Examples of the lithium compound include oxygen compounds, oxyacid salts and halides. As the transition metal compound,
A monovalent to hexavalent transition metal oxide, the same transition metal salt, or the same transition metal complex salt is used.

Preferred lithium compounds used in the synthesis of the active material include lithium hydroxide, lithium oxide, lithium carbonate, lithium nitrate, lithium sulfate, lithium sulfite, lithium phosphate, lithium tetraborate, lithium chlorate and lithium perchlorate. , Lithium thiocyanate, lithium formate, lithium acetate, lithium oxalate, lithium citrate, lithium lactate, lithium tartrate, lithium pyruvate, lithium trifluoromethanesulfonate, lithium tetraborate, lithium hexafluorophosphate, lithium fluoride, Examples thereof include lithium chloride, lithium bromide and lithium iodide.

A preferred transition metal compound is T
iO ₂ (rutile or anatase type), lithium titanate, acetylacetonato titanyl, titanium tetrachloride, titanium tetraiodide, titanyl ammonium oxalate, VOd (d = 2)
~ 2.5 d = 2.5 compound is vanadium pentoxide),
VOd lithium compound, vanadium hydroxide, ammonium metavanadate, ammonium orthovanadate,
Ammonium pyrovanadate, vanadium oxosulfate,
Vanadium oxytrichloride, vanadium tetrachloride, Mn
O ₂ , Mn ₂ O ₃ , manganese hydroxide, manganese carbonate, manganese nitrate, manganese sulfate, ammonium manganese sulfate, manganese sulfite, manganese phosphate, manganese borate,
Manganese chlorate, manganese perchlorate, manganese thiocyanate, manganese formate, manganese acetate, manganese oxalate, manganese citrate, manganese lactate, manganese tartrate, manganese stearate, manganese fluoride, manganese chloride manganese bromide, manganese iodide, Manganese acetylacetonate, iron oxide (2,3 valent), iron trioxide, iron hydroxide (2,3)
Trivalent), iron chloride (2,3 valent), iron bromide (2,3 valent), iron iodide (2,3 valent), iron sulfate (2,3 valent), ammonium iron sulfate (2,3 valent) ), Iron nitrate (2,3 valent) iron phosphate (2,
Trivalent), iron perchlorate, iron chlorate, iron acetate (2,3 valent),
Iron citrate (2,3 valent), ammonium iron citrate (2,3 valent, iron oxalate (2,3 valent), ammonium iron oxalate (2,3 valent), CoO, Co ₂ O ₃ Co ₃ O ₄ , LiC
oO ₂ , cobalt carbonate, basic cobalt carbonate, cobalt hydroxide, cobalt sulfate, cobalt nitrate, cobalt sulfite, cobalt perchlorate, cobalt thiocyanate, cobalt oxalate, cobalt acetate, cobalt fluoride, cobalt chloride,
Cobalt bromide, cobalt iodide, hexaamminecobalt complex salt (as salts, sulfuric acid, nitric acid, perchloric acid, thiocyanic acid, oxalic acid, acetic acid, fluorine, chlorine, bromine, iodine) nickel oxide, nickel hydroxide, nickel carbonate, Basic nickel carbonate, nickel sulfate nickel nitrate, nickel fluoride, nickel chloride, nickel bromide, nickel iodide, nickel formate, nickel acetate, nickel acetylacetonate, niobium oxychloride, niobium pentachloride, niobium pentaiodide, Niobium oxide, niobium dioxide, niobium trioxide, niobium pentoxide,
Niobium oxalate, niobium methoxide, niobium ethoxide, niobium propoxide, niobium butoxide, lithium niobate, MoO ₃ , MoO ₂ , LiMo ₂ O ₄ , molybdenum pentachloride, ammonium molybdate, lithium molybdate, molybdo ammonium phosphate, oxidation Examples include molybdenum acetylacetonate.

Among these, particularly preferred combinations of lithium compounds and transition metal compounds are lithium hydroxide, lithium carbonate, lithium acetate, MnO ₂ , Mn ₂ O ₃ ,
Manganese hydroxide, manganese carbonate, manganese nitrate, Co
O, Co ₂ O ₃ , Co ₃ O ₄ , LiCoO ₂ , cobalt carbonate, basic cobalt carbonate, cobalt hydroxide, cobalt sulfate, cobalt nitrate, nickel oxide, nickel hydroxide,
Examples thereof include nickel carbonate, basic nickel carbonate, nickel sulfate, nickel nitrate, nickel acetate, vanadium pentoxide, and ammonium vanadate.

Preferred manganese compounds used for synthesizing the positive electrode active material in the present invention include MnO ₂ and Mn.
Examples include ₂ O ₃ , manganese hydroxide, manganese carbonate, manganese nitrate, manganese ammonium sulfate, manganese acetate, manganese oxalate, and manganese citrate.

The negative electrode active material used in the present invention can be obtained by chemically inserting lithium ions into a negative electrode active material precursor of a transition metal oxide and / or a lithium-containing transition metal oxide. For example, a method of reacting with lithium metal, a lithium alloy, butyl lithium, or the like, or electrochemically inserting lithium ions is preferable. In the present invention, it is particularly preferable to electrochemically insert lithium ions into the transition metal oxide that is the negative electrode active material precursor. Above all, it is most preferable to electrochemically insert lithium ions into the lithium-containing transition metal oxide that is the precursor of the negative electrode active material. As a method for electrochemically inserting lithium ions, a lithium-containing transition metal oxide (referred to as a negative electrode active material precursor in the present invention) as a positive electrode active material,
The negative electrode active material can be obtained by discharging a redox system (for example, an open system (electrolysis) or a closed system (battery)) made of a non-aqueous electrolyte containing lithium metal and a lithium salt. Further, the most preferred embodiment is an oxidation comprising a lithium-containing transition metal oxide as the positive electrode active material, a negative electrode active material precursor having a composition formula different from that of the positive electrode active material as the negative electrode active material, and a non-aqueous electrolyte containing a lithium salt. This is a method of inserting lithium ions by charging a reduction system (for example, an open system (electrolysis) or a closed system (battery)).

The amount of lithium ions inserted is not particularly limited, but is 27 to 1340 mA per 1 g of the negative electrode active material precursor.
h (corresponding to 1 to 50 mmol) is preferable, and 40 to 1070
mAh (corresponding to 1.5 to 40 mmol) is more preferable. Further, 54 to 938 mAh (corresponding to 2 to 35 mmol) is most preferable. The cut-off voltage of the charge / discharge cycle cannot be uniquely determined because it changes depending on the type and combination of the positive electrode active material and the negative electrode active material used, but the discharge voltage can be increased and the voltage that can substantially maintain the cycleability, In the case of the positive electrode, a charge termination voltage of 4.5 to 4.0 V with respect to Li is preferable.

The negative electrode active material used in the present invention is one in which the basic structure of the crystal of the precursor is changed by the insertion of lithium ions, and this change is preferably X by CuKα radiation.
In the diffraction pattern of the line, the diffraction angle (2θ) is 5 to 70.
It can be confirmed by reducing the intensity of the diffraction maximum peak value to ⅕ or less within the range of degrees. This decrease is preferably 1/10 or less, and particularly preferably 1/20 or less. Here, the intensity of 0 means that substantially all the negative electrode active material precursor was changed to a chargeable / dischargeable negative electrode active material, and specifically, it was reduced to the baseline noise level of the X-ray diffraction spectrum. Means that. Furthermore, it is desirable that at least one of the peaks other than the above-mentioned maximum peak (main peak) disappears, or a new peak appears.

The structure of the compound obtained by calcining by the method of the present invention was analyzed based on the X-ray crystal diffraction spectrum, and its chemical composition formula was determined by inductively coupled plasma (ICP) emission spectroscopy and simple method. Was calculated based on the weight difference of the powder before and after firing.

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) or the like, or a calcined carbonaceous compound capable of inserting and extracting lithium ions or lithium metal (for example,
JP-A-58-209,864, 61-214,41
7, the same 62-88, 269, the same 62-216, 170,
63-13, 282, 63-24, 555, 63
-121,247, 63-121,257, 63-
155, 568, 63-276, 873, 63-3
14,821, JP-A-1-204,361, and 1-22.
1, 859, 1-259, 360, etc.). The purpose of the combined use of the lithium metal and lithium alloy is to insert lithium ions 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 fibers and metals (copper, nickel, aluminum, silver (JP-A-63-1).
48, 554), powders, metal fibers, or polyphenylene derivatives (Japanese Patent Laid-Open No. 59-20971) can be included as one kind or a mixture thereof. The combined use of graphite and acetylene black is particularly preferred. The amount added is not particularly limited, but is preferably 1 to 50% by weight, and particularly preferably 2 to 30% by weight. For carbon and graphite, 2 to 15% by weight is particularly preferable.

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

As the electrolyte, organic solvents such as propylene carbonate, ethylene carbonate, butylene carbonate, dimethyl carbonate, diethyl carbonate, γ-butyrolactone, 1,2-dimethoxyethane, tetrahydrofuran, 2-methyltetrahydrofuran, dimethylsulfoxide, 1 , 3-dioxolane,
Formamide, dimethylformamide, dioxolane,
Acetonitrile, nitromethane, methyl formate, methyl acetate, phosphoric acid triester (JP-A-60-23, 97)
3), trimethoxymethane (JP-A-61-4,17)
0), a dioxolane derivative (JP-A-62-15,77).
1, 62-222, 372, 62-108, 474).
, Sulfolane (JP-A-62-31959), 3-methyl-2-oxazolidinone (JP-A-62-44,96)
1), propylene carbonate derivative (JP-A-62-2)
90,069, 62-290,071), tetrahydrofuran derivative (JP-A-63-32,872), diethyl ether (JP-A-63-62,166), 1,3-propane sultone (JP-A-63). -102, 173) and a mixture of at least one aprotic organic solvent and a lithium salt soluble in the solvent, for example, LiCl
O ₄ , LiBF ₆ , LiPF ₆ , LiCF ₃ SO ₃ , L
_{iCF 3 CO 2, LiAsF 6,} LiSbF 6, LiB
₁₀ Cl ₁₀ (JP-A-57-74,974), lower aliphatic lithium carboxylate (JP-A-60-41,773), Li
AlCl ₄ , LiCl, LiBr, LiI (JP-A-60
247,265), lithium chloroborane (Japanese Patent Application Laid-Open No. 6-242242).
1-165,957), lithium tetraphenylborate (Japanese Patent Laid-Open No. 61-214,376), and the like. Above all, a mixture of propylene carbonate or ethylene capato and 1,2-dimethoxyethane and / or diethyl carbonate is mixed with LiCF.
Electrolytes containing ₃ SO ₃ , LiClO ₄ , LiBF ₄ and / or LiPF ₆ are 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 volume ratio of the solvent is not particularly limited, but in the case of a mixed solution of propylene carbonate or ethylene capote and 1,2-dimethoxyethane and / or diethyl carbonate, 0.4 / 0.6 to 0.6.
/0.4 (mixing ratio when both 1,2-dimethoxyethane and diethyl carbonate are used is 0.4 / 0.6-
0.6 / 0.4) is preferable. The concentration of the supporting electrolyte is not particularly limited, but is 0.2 to 3 per liter of the electrolytic solution.
Molar is preferred.

In addition to the electrolytic solution, the following solid electrolyte is also used.
Can be used. As the solid electrolyte, an inorganic solid electrolyte is used.
It is divided into degrading and organic solid electrolyte. For inorganic solid electrolyte
Is often Li nitride, halide, oxyacid salt, etc.
Are known. Above all, Li₃N, LiI, Li_FiveN
I₂, Li₃N-LiI-LiOH, LiSiO_Four, L
iSiO_Four-LiI-LiOH (JP-A-49-81,8
99), xLi₃PO _Four-(₁-X) Li_FourSiO
_Four(JP-A-59-60,866), Li₂SiS₃(Special
KAISHO 60-501,731), phosphorus sulfide compounds
62-82, 665) and the like are effective. Organic solid electrolysis
In terms of quality, polyethylene oxide derivatives or those containing
Polymer (JP-A-63-135,447), polypro
A pyrene oxide derivative or a polymer containing the derivative,
A polymer containing an on-dissociative group (JP-A-62-254, 30)
2, ibid. 62-254, 303, ibid. 63-193, 95
4), a polymer containing an ionic dissociative group and the above aprotic
Mixtures of electrolytes (US Pat. No. 4,792,504;
4,830,939, JP-A-62-22,375 and 6
2-22, 376, 63-2, 375, 63-2
2,776, JP-A-1-95,117), phosphate ester
Rupolymer (Japanese Patent Laid-Open No. 61-256,573) is effective.
It In addition, add polyacrylonitrile to the electrolyte
There is also a method (JP-A-62-278,774). Also, nothing
Of using a machine with an organic solid electrolyte (JP-A-60-1,
768) is also known.

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

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-49-108,525), triethylphosphite (JP-A-47-4,376),
Triethanolamine (JP-A-52-72,425),
Cyclic ether (JP-A-57-152,684), ethylenediamine (JP-A-58-87,777), n-glyme (JP-A-58-87,778), hexaphosphoric acid triamide (JP-A-58-87,777). 87,779), nitrobenzene derivatives (JP-A-58-214,281), and sulfur (JP-A-5-79).
9-8, 280), quinone imine dyes (JP-A-59-6)
8,184), N-substituted oxazolidinones and N, N'-
Substituted imidazolidinone (JP-A-59-154,77)
8), 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 (Japanese Patent Laid-Open No. 60-7
9,677), 2-methoxyethanol (JP-A-60-
89,075), aluminum trichloride (JP-A-61-8)
8, 466), a monomer of a conductive polymer electrode active material (JP-A-61-161,673), triethylenephosphonamide (JP-A-61-208,758), trialkylphosphine (JP-A-62-80, 976), morpholine (JP-A-62-80,977), an aryl compound having a carbonyl group (JP-A-62-86,673), hexamethylphosphoric triamide and 4-alkylmorpholine (JP-A-62-86,673). -217,575), bicyclic tertiary amine (JP-A-62-217,578), oil (JP-A-62-287,580), quaternary phosphonium salt (JP-A-63-121,268). , Tertiary sulfonium salts (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 (Japanese Patent Laid-Open No. 48-36,6).
32). Further, the electrolytic solution may contain carbon dioxide gas in order to have suitability for high temperature storage (JP-A-59-13).
4,567).

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 (JP-A-48-36,633),
A method is known in which an electrolytic solution (JP-A-57-124,870) is included. 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 (JP-A-55-163,779) or a chelating agent (JP-A-55-163,780), a conductive polymer (JP-A-55-163). 58-163, 188, 59-1
4,274), polyethylene oxide, etc.
0-97, 561).
Also, the surface of the negative electrode active material can be modified. For example, an ion conductive polymer or a polyacetylene layer is provided (JP-A-58-111,276), 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 or stainless steel whose surface is treated with carbon, nickel, titanium or silver, or an Al—Cd alloy is used. It is also used to oxidize the surface of these materials. As the shape, 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 1 to 50
Those having a thickness of 0 μm are used.

The shape of the battery can be any of coins, buttons, sheets, cylinders, corners and the like. In coins and buttons, the mixture of the positive electrode active material and the negative electrode active material is used after being pressed into a pellet shape. The thickness and diameter of the pellet are determined by the size of the battery. In the sheet, cylinder, and corner, the mixture of the positive electrode active material and the negative electrode active material is
It is used after being coated, dried, dehydrated and pressed on the current collector. The coat thickness, length and width are determined by the size of the battery, but the coat thickness in the compressed state after drying is particularly preferably 1 to 2000 μm. As a method for drying or dehydrating the pellets or sheets, a commonly used method may be used, but in particular vacuum, infrared rays, far infrared rays,
Electron beams, low-humidity air, etc. can be used alone or in combination. The temperature is preferably 80 to 350 ° C.
Particularly, 100 to 250 ° C. is preferable. The pellet or sheet pressing method may be a generally used method, but in particular,
A die pressing method and a calendar pressing method are preferable. The pressing pressure is not particularly limited, but can be any. With coins and buttons,
The mixture of the positive electrode active material and the negative electrode active material is used after being pressed into a pellet shape. The thickness and diameter of the pellet are determined by the size of the battery. Further, in the sheet, the cylinder and the corner, the mixture of the positive electrode active material and the negative electrode active material is used after being coated, dried, dehydrated and pressed on the current collector.
The coat thickness, length and width are determined by the size of the battery, but the coat thickness in the compressed state after drying is particularly preferably 1 to 2000 μm. As a method for drying or dehydrating the pellets or sheets, a generally used method may be used, but in particular, vacuum, infrared rays, far infrared rays, electron beams, low humidity air, etc. may be used alone or in combination. The temperature is preferably 80 to 350 ° C. Particularly, 100 to 250 ° C. is preferable. The pellet or sheet may be pressed by a generally used method, 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 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. For the can and the lead plate, a metal or alloy having electrical conductivity can be used. For example, metals such as iron, nickel, titanium, chromium, molybdenum, copper and aluminum or alloys thereof are used. As the sealing agent for sealing, a conventionally known compound or mixture such as asphalt can be used.

[0035]

EXAMPLES The present invention will be described in more detail with reference to the following examples of battery production, but the present invention is not limited to the examples as long as the gist of the invention is not exceeded. [Synthesis Example of Negative Electrode Active Material Precursor] CoO as Co Raw Material
29.0 g, V ₂ O ₅ 36.4 g as a V raw material, and Li ₂ CO ₃ 14.8 g as a Li raw material were mixed, and the mixed powder was dried at 130 ° C., and then 1 at 750 ° C. in an electric furnace in air.
It was baked for 8 hours. After gradually cooling to room temperature, it was pulverized with a vibration mill for 2 minutes to obtain negative electrode active material precursor particles having an average particle size of 6.5 μm. From the pattern of the X-ray diffraction spectrum by Cu-Kα ray, the composition of particles is
LiCoVO described in S File No 38-1396
Confirmed to be ₄ .

As raw materials for transition metals other than Co or typical elements, NiO, MoO ₃ , TiO ₂ , Cr ₂ O ₃ ,
MnO ₂ , Fe ₂ O ₃ , Nb ₂ O ₅ , WO ₃ , SnO ₂
By using one or more of these as raw materials CoO, V ₂
O ₅ and LiCO ₃ were mixed and fired to synthesize the negative electrode active material of the present invention (average particle size 5 to 7 μm) having the composition shown below. The composition formula was determined based on X-ray diffraction and inductively coupled plasma (ICP) emission analysis. Compound 1 LiNiVO ₄ Compound _{2 Li 1. 01 Co 0.} 6 Ni 0. 4 V 0. 99 O 3. 9 Compound _{3 Li 0. 01 Co 0.} 5 V 0. 89 Mo 0. 1 O 4. 3 Compound 4 _{Li 1. 03 Co 1. 0} V 0. 98 Ti 0. 1 O 4. 2 compound _{5 Li 1. 03 Co 1.} 0 V 0. 98 Cr 0.1 O 4. 6 compound _{6 Li 1. 03 Co 1.} 0 _{V 0. 98 Mn 0. 1} O 4. 2 compound _{7 Li 1. 03 Co 1.} 0 V 0. 98 Fe 0. 1 O 4. 2 compound _{8 Li 1. 03 Co 1.} 0 V 0. 98 Nb 0 . ₁ O _{4. 3} compound _{9 Li 1. 03 Co 1.} 0 V 0. 98 W 0. 1 O 4. 3 compound _{10 Li 1. 03 Co 1.} 0 V 0. 99 Sn 0. 1 O 4. 2 compound _{11 Li 1. 03 Co 1.} 0 V 0. 98 Sb 0. 1 O 4. 3 compound _{12 Li 1. 0 Ti 1.} 0 O 2. 3 compound _{13 Co 1. 0 V 1.} 0 O 3. 0

[Synthesis Example of Positive Electrode Active Material] Li₂Mn₃._FiveCo₀._FiveO₉(Or Li₀.₈₉Mn₁.
₅₅Co₀._{twenty two}O_Four) Synthesis of Li₂CO₃And MnO₂And CoCO₃The molar ratio is approximately
Mix so as to be 1: 3.5: 0.5, and mix the mixture with air.
After heating at 400 ℃ for 12 hours, further at 750 ℃ for 2 hours
While heating, Li₂Mn₃._FourCo₀.₆O₉Has the composition of
Spinel type lithium manganese cobalt composite oxidation of the present invention
The thing was synthesized. Li₀.₉Mn₂.₉₅Ge₀.₀₅O_FourSynthesis of Li₂CO₃And MnO₂And GeO₂The molar ratio is approximately
0.45: 2: 0.03 so that the mixture becomes
Heat in air at 800 ° C for 48 hours to obtain Li₀.₉Mn₁.
₉₅Ge₀.₀₃O_FourOf the present invention having the composition of
Mumanganese germanium composite oxide was synthesized. Li₂Mn_Four._FiveCo₀._FiveO₁₁(Or Li₀.₇₃Mn₁.
₆₄Co₀.₁₈O_Four) Synthesis of the above compound Li₂Mn₃._FiveCo₀._FiveO₉Λ-MnO
₂In the air so that the molar ratio is about 1: 1.
By heating at 250 ° C. for 24 hours at room temperature.
Tium manganese cobalt oxide Li₂Mn_Four._FiveCo₀._Five
O₁₁Was synthesized. Li₂Mn_Four._FiveNi₀._FiveO₁₁(Or Li₀.₇₃Mn₁.
₆₄Ni₀.₁₈Synthesis of O4) Li₂CO₃And MnO₂And NiCO₃The molar ratio is approximately
Mix so as to be 1: 3.5: 0.5, and mix the mixture with air.
In a heating chamber at 370 ° C. for 12 hours to obtain Li₂Mn ₃._FiveNi
₀._FiveO₉A compound having the following composition was obtained. This Li₂Mn₃._FiveN
i₀._FiveO₉Λ-MnO prepared electrolytically₂(EMD)
And equimolar to 300 ℃ in air
And the spinel type lithium man of the present invention.
Gun Nickel Oxide Li₂Mn_Four._FiveNi₀._FiveO₁₁Synthesize
did. Li_FourMn_Four._FiveCo₀._FiveO₁₂(Or Li₁.₃₃Mn₁.
_FiveCo₀.₁₇O_Four) Synthesis of Li₂CO₃And λ-MnO₂And CoCo₃And Li: M
The molar ratio of n: Co becomes about 4: 4.5: 0.5.
And heat the mixture in air at 500 ° C for 48 hours.
Then Li4 Mn_Four._FiveCo₀._FiveO₁₂The composition of Lithium
Ngan cobalt composite oxide was synthesized. Li_FourMn_Four._FiveCo₀._FourTi₀.₁O₁₂(Or Li₁.
₃₃Mn₁._FiveCo₀.₁₃Ti ₀.₀₃O_Four) Synthesis of Li_FourMn_Four._FiveCo₀._FiveO₁₂And TiO₂(Ana
Tase) is mixed at a molar ratio of about 1: 0.1.
And heated in air at 750 ° C. for 8 hours to obtain Li _FourMn_Four.
_FiveCo₀._FourTi₀.₁O₁₂The composite oxide of the present invention having the composition
Synthesized. Li₁.₀₅Mn₁.₈Cr₀.₂O_FourSynthesis of Li₂CO₃Chemically prepared with MnO₂With (CMD)
Cr₂O₃And are mixed at a molar ratio of 1: 6.9: 0.2.
And heated at 830 ° C. for 12 hours to obtain Li₁.₀₅Mn₁.₈C
r₀.₂O_FourThe composite oxide of the present invention having the composition of was synthesized.

Besides this, a composite oxide having the following composition was synthesized by following the above method. _{Li 0. 95 Mn 1. 7} Fe 0. 2 O 4 Li 1. 05 Mn 1. 8 V 0. 1 O 4 Li 0. 98 Mn 1. 7 Sc 0. 3 O 4 Li 1. 03 Mn 1. 8 _{Mo 0. 1 O 4 Li 0} . 97 Mn 1. 8 W 0. 3 O 4

[Preparation of electrode mixture and coin battery and charge / discharge test] For the negative electrode, 82% by weight of the negative electrode active material or its precursor, and 10% by weight and 2% by weight of scaly graphite and acetylene black as conductive agents, respectively. %, Polyvinylidene fluoride as a binder was mixed at a mixing ratio of 6% by weight, and the mixture was compression molded into pellets (13 mmΦ, 20 mg, active material weight 16.4 mg). The one that was sufficiently dried with a tap was used as a negative electrode. In addition, the negative electrode for the comparative experiment was 1. 1. Coke (LPC-U, manufactured by Nippon Steel Chemical Co., Ltd.) as a carbonaceous material, crushed to an average particle size of 10 μm. Pulverized pitch coke (manufactured by Mitsubishi Kasei) is crushed to an average particle size of 2.5 μm for 1300
2. Heat-treated in an electric furnace for 2 hours at ℃ Pellets (16 mg) prepared from three kinds of multi-layer graphite carbon material having a graphite structural component with an average particle diameter of 23 μm, obtained by firing polyacrylonitrile-based synthetic fiber at 2800 ° C. were used.

Regarding the positive electrode, a positive electrode mixture prepared by mixing 85% by weight of the positive electrode active material, 10% by weight of scaly graphite as a conductive agent, and 5% by weight of tetrafluoroethylene as a binder. Compression molded pellets (13m
mΦ, 60 mg, and 51 mg as the active material weight) were prepared and dehydrated and dried on a far infrared heater in a dry box (dry air having a dew point of −40 to −70 ° C.) to be used as a positive electrode.

An 80 μm thick SUS316 net was used as a current collector, and this net was welded to positive and negative electrode cans for coin batteries, respectively. 1 mol / l LiPF6 as electrolyte
250 μL of an equal volume mixture of ethylene carbonate and diethylene carbonate containing ₆ was used to impregnate a separator made of a microporous polypropylene sheet and a polypropylene nonwoven fabric. Set the positive electrode pellet and the negative electrode active material precursor pellet on the current collector, insert the separator between the positive electrode and the negative electrode, and use the crimping machine in the dry box to combine the positive electrode and the negative electrode can. An ion battery was produced. Using this lithium ion battery, a charge / discharge test was conducted at a constant current density of 1.0 mA / cm ² . All tests started with charging. The charge cutoff voltage is 3.9 V, and the discharge cutoff voltage is 1.
The charging / discharging performance was evaluated at 8 V by cycling between 4.5 V and 3.0 V.

A material selected from the positive electrode active material and the negative electrode active material precursor shown in the above synthesis examples and the active material having a similar spinel structure synthesized by the same method is combined as follows to obtain a lithium ion. A secondary battery was produced. Negative electrode active material precursor cathode active material cell 1 (the present _{invention) LiCoVO 4 Li 0. 9 Mn} 1. 95 Ge 0. 03 O 4 cell 2 (the present _{invention) LiCoVO 4 Li 0. 9 Mn} 1. 50 Ge 0. 45 O ₄ cells 3 (present _{invention) LiCoVO 4 Li 0. 9 Mn} 1. 95 Ti 0. 03 O 4 cell 4 (present _{invention) LiCoVO 4 Li 0. 9 Mn} 1. 50 Ti 0. 45 O 4 cell 5 (the _{invention) LiCoVO 4 Li 2 Mn 4.} 5 Co 0. 5 O 11 cell 6 (present _{invention) LiCoVO 4 Li 2 Mn 4.} 0 Co 1. 0 O 11 cell 7 (present _{invention) LiCoVO 4 Li 4 Mn 4.} 5 Co _{0. 5} O ₁₂ cell 8 (present _{invention) LiCoVO 4 Li 0. 9 Mn} 1. 7 Cr 0. 2 O 4 cell 9 (present invention) compound _{1 Li 2 Mn 4. 5 Co} 0. 5 O 11 cell 10 (invention) compound _{2 Li 4 Mn 4. 5 Co} 0. 4 Ti 0. 1 O 12 cell 11 (present invention) compound _{3 Li 1. 05 Mn 1.} 8 Cr _{0. 2} O ₄ cell 12 (present invention) Compound _{4 Li 2 Mn 4. 5 Ni} 0. 5 O 11 cell 13 (present invention) Compound _{5 Li 2 Mn 4. 5 Cr} 0. 5 O 11 cell 14 (the present invention ) compound _{8 Li 2 Mn 4. 5 Ge} 0. 5 O 11 cell 15 (present invention) compound _{10 Li 1. 05 Mn 1.} 8 Fe 0. 2 O 4 cell 16 (present invention) compound 11 Li ₂ Mn _{4. 5} Co _{0. 5} O ₁₁ cell 17 (present invention) compound _{12 Li 4 Mn 4. 5 Co} 0. 4 Ti 0. 1 O 12 negative electrode active material the positive electrode active material cell 18 (Comparative example) coke Li ₂ Mn _{4. 5} Co _{0. 5} O ₁₁ cell 19 (Comparative example) pitch coke _{Li 2 Mn 4. 5 Co 0} . 5 O 11 cell 20 (Comparative example) multilayer graphitic carbon _{Li 2 Mn 4. 5 Cr 0} . 5 O 11

A battery in which each of the above negative electrode active material precursors was incorporated into the negative electrode was charged (insertion of lithium ion) at a constant current of 1 mA until the open circuit voltage of the negative electrode to the positive electrode reached -3.9V. did. 1mA for fully charged battery
Alternatively, the battery was discharged at a constant current of 5 mA, terminated at -1.8 V, and the battery was set in the charging start state. This one
The negative electrode active material precursor was converted into the negative electrode active material by performing the charging operation once.

Table 1 summarizes the results of evaluation of the charge / discharge performance of the lithium ion secondary battery with each combination of positive electrode / negative electrode in terms of electric capacity, number of charge / discharge cycles and safety. The discharge capacity is 1.8 V and indicates the capacity per weight of the active material until the end of the discharge. The cycle property means the number of charge / discharge cycles required until the initial capacity drops to 60%.

[0045]

[Table 1]

From the results shown in Table 1, the lithium ion non-aqueous secondary battery made by the combination of the negative electrode active material of the transition metal oxide and the positive electrode active material of the spinel type lithium manganese composite oxide disclosed in the present invention was used as the carbonaceous material. It can be seen that the battery has excellent performance in all aspects of capacity, charge / discharge efficiency, and cycleability with respect to a comparative battery having a negative electrode.

[0047]

The transition metal composite oxide is used as the negative electrode active material,
By using a lithium-ion secondary battery that uses a metal-doped spinel type lithium manganese composite oxide as a positive electrode active material and a non-aqueous solution as an electrolyte, high discharge capacity, high charge / discharge efficiency, and excellent cycleability can be obtained. In addition, the cost advantage of using inexpensive manganese can be obtained.

Claims (9)

[Claims] 1. A 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 comprises a transition metal oxide, and the positive electrode active material comprises the general formula Li
₁ + x [Mn ₂ -y Az] O 4 (-1.0 <x <1.7,0
<Y <1.2, 0.02 <z <1.0, A is one or more metals), and the non-aqueous electrolyte secondary battery comprises a lithium-containing manganese composite oxide having a spinel structure. . 2. The non-aqueous electrolyte secondary battery according to claim 1, wherein y = z is not satisfied in the general formula of the positive electrode active material. 3. The positive electrode active material has a general formula of Li ₁ -x [Mn _2-
y Az] O ₄ (0 <x <1.0, 0 <y <1.0, 0.
02 <z <1.0, A is a lithium-containing manganese composite oxide having a spinel structure represented by one or more metals), and the non-aqueous electrolyte secondary battery according to claim 1. 4. The non-aqueous electrolyte secondary battery according to claim 3, wherein y = z is not satisfied in the general formula of the positive electrode active material. 5. The positive electrode active material has a general formula of Li ₁ -x [Mn _2-
y Az] O ₄ (0.2 <x <1.0, 0 <y <0.4,
0.02 <z <0.4, A is one or more metals and y =
The non-aqueous electrolyte secondary battery according to claim 1, further comprising a lithium-containing manganese composite oxide having a spinel structure represented by z). 6. The non-aqueous electrolyte secondary battery according to claim 1, wherein A is one or two kinds of transition metals. 7. The negative electrode active material comprises Lix MOj (where M is Ti, V, Mn, Co, Fe, Ni, Nb,
Represents at least one transition metal selected from Mo, x
Is in the range of 0.17 to 11.25 and j is in the range of 1.6 to 4.1). Water electrolyte secondary battery. 8. The negative electrode active material is a negative electrode active material precursor, the basic structure of the crystal is changed by the insertion of lithium ions to produce the negative electrode active material, and the changed basic structure of the crystal is repeatedly charged and discharged. The non-aqueous electrolyte secondary battery according to claim 1, which is a lithium-containing transition metal oxide having a property not changed by 9. The non-aqueous electrolyte is propylene carbonate,
The non-aqueous electrolyte secondary battery according to claim 1, comprising a supporting salt and a mixture of solvents selected from ethylene carbonate, diethyl carbonate and methyl propionate.