JPH0729600A - Nonaqueous secondary battery - Google Patents

Abstract

PURPOSE:To lengthen cycle life by setting a molar ratio of a positive active material to a negative active material in a specified range, and by containing a transition metal oxide in the negative active material in a nonaqueous secon dary battery containing the positive active material, the negative active material, and a lithium salt. CONSTITUTION:CoVO3.7 and others as a negative active material, graphite or acetylene black as a conductor, ethyleneacrylate or copolymer of ethylene and maleic anhydride as a binder are kneaded with toluene, and the kneaded material is applied to both sides of a copper foil current collector, dried, then cut to prepare a negative sheet. A positive sheet is prepared by using LiCoO2 as a positive active material. Thickness of each sheet is controlled so that the ratio of the positive active material to the negative active material becomes 1.6-5.0. Microporous polypropylene is used as a separator 4, and it is wound with the negative and positive sheets in a specified shape, then they are put into a negative can 2. The negative sheet is connected to a negative electrode 3 and the positive electrode 5 is connected to a positive cap 8 which also acts as a safety vent 7. Lithium hexafluorophosphate is poured in the negative can 2.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a non-aqueous secondary battery having an improved cycle life during charge / discharge.

[0002]

2. Description of the Related Art Lithium-ion secondary batteries are non-aqueous secondary batteries with high energy density, and their importance is increasing with the miniaturization of electronic devices. But,
As described in JP-A-2-56871,
Conventional lithium batteries, especially non-aqueous electrolyte secondary batteries using a negative electrode active material of lithium metal or lithium alloy as a negative electrode active material have the qualities that can be a secondary battery having a high energy density. There is a problem that the cycle life is shortened due to deterioration of performance due to dendrite of lithium and the like due to repetition.

[0003]

An object of the present invention is to provide a non-aqueous secondary battery having an excellent cycle life.

[0004]

[Means for Solving the Problems] The above-mentioned problems can be solved in 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. (1) Positive electrode active material, negative electrode active material and lithium In a non-aqueous secondary battery comprising a non-aqueous electrolyte containing a salt, the molar ratio of the positive electrode active material to the negative electrode active material is 1.6 or more and 5 or less, and the negative electrode active material contains a transition metal oxide. Characteristic non-aqueous secondary battery. (2) The negative electrode active material is a transition metal oxide in which the basic crystal structure is changed by inserting lithium ions, and the basic crystal structure after the change is in a state of not being changed by charge and discharge, and , The negative electrode active material is Li _p MO
_j (however, M is Ti, V, Mn, Co, Fe, Ni,
Represents at least one transition metal selected from Cr, Nb and Mo, p is 0 or more and 3.1 or less, and j
Is 1.6 or more and 4.1 or less), wherein the non-aqueous secondary battery according to (1) comprises a transition metal oxide. (3) The negative electrode active material is Li _x M _q V _1-q O _j (where M represents a transition metal, x is 0.17 or more and 11.2 or more).
5 or less, q is 0 or more and 0.7 or less, and j
Is 1.3 or more and 4.1 or less), and the non-aqueous secondary battery according to (2), comprising a lithium-containing transition metal oxide. (4) A value obtained by dividing the total volume of the positive electrode and the negative electrode by the volume of the battery is 0.4 or more and 0.7 or less, and the facing area of the positive electrode and the negative electrode of the battery is the volume of the battery. The non-aqueous secondary battery according to (3), wherein the divided value is 15 cm ² / ml or more and 50 cm ² / ml or less. (5) The difference between the electrode body diameter and the battery can inner diameter is 30 μm or more 3
It was achieved by the non-aqueous secondary battery described in (3), which has a thickness of 100 μm or less.

The non-aqueous secondary battery of the present invention has a basic structure composed of a positive electrode active material, a negative electrode active material and a non-aqueous electrolyte containing a lithium salt.

The transition metal referred to in the present invention has an element number of 2.
From 1 of Sc to Zn of element number 30 and Y of element number 39 to Cd of element number 48 and La of element number 57 to Hg of element number 80.

The number of moles referred to in the present invention is a value obtained by dividing the total number of moles of each component of the positive electrode active material by the total number of moles of the negative electrode active material. Here, the number of moles of the negative electrode active material is the number of moles before insertion of lithium ions. The method for determining the molar quantity of the active material component containing two or more atomic species is the sum of atomic mole numbers of the transition metal component when the component contains a transition metal. If the active material component does not contain a transition metal, it is the sum of the atomic moles of the cation component in it, and if the cation component and the anion component cannot be determined, the total of the atomic moles of the active material component is Total.

The range of the molar ratio of the positive electrode active material to the negative electrode active material in the present invention is preferably 1.6 or more and 5 or less, more preferably 2.5 or more and 4.5 or less, and further preferably 3.25 or more 4. It is less than or equal to 0.0.

Total volume of positive electrode and negative electrode in the present invention
{(Volume including active material, conductive agent, binder, current collector, etc.,
More specifically, the width x length x thickness of the positive electrode sheet and the negative electrode sheet
Total width x length x thickness of the board (thickness is caliper or
Or measured with a micrometer)} by the volume of the battery
The value is preferably 0.4 or more and 0.7 or less, and
It is preferably 0.45 or more and 0.65 or less, and most preferably
It is preferably 0.5 or more and 0.6 or less, and the battery is positive.
The value obtained by dividing the facing area of the pole and the negative electrode by the volume of the battery is preferable.
15 cm²/ Ml or more 50 cm²/ Ml or less, and more
Preferably 20 cm²/ Ml or more 40 cm²/ Ml or less,
Most preferably 25 cm²/ Ml or more 30 cm ²/ Ml or less
It The volume of the battery in the present invention means the internal volume of the battery.
Not the total volume of the battery, including the battery can and voids inside the battery.
It More specifically, the battery has, for example, a unit cell outer diameter of 1
3.8 mm, AA type with unit cell height (shoulder height) of 48.0 mm
When the battery volume is 7.2 ml, the electrode length is
Preferably 180 mm or more and 330 mm or less, more preferably
220 mm or more and 290 mm or less, most preferably 240 mm or less
Upper 270 mm or less. The negative electrode is preferably 200 mm or more
Upper 380 mm or less, more preferably 220 mm or more and 300 mm
Or less, most preferably 250 mm or more and 280 mm or less
It The electrode width of the positive electrode is preferably 32 mm or more and 45 mm or less
Lower, more preferably 35 mm or more and 41 mm or less, most preferably
Is 37 mm or more and 39 mm or less, and the negative electrode is preferably
35 mm or more and 46 mm or less, more preferably 38 mm or more 44
mm or less, most preferably 40 mm or more and 42 mm or less.
The positive electrode preferably has a thickness of 150 μm or more and 400 μm or more.
m or less, more preferably 200 μm or more and 300 μm or less
Lower, most preferably 230 μm or more and 270 μm or less
Therefore, the negative electrode is preferably 60 μm or more and 200 μm or less,
More preferably 90 μm or more and 180 μm or less, most preferably
In other words, it is 110 μm or more and 130 μm or less. Positive and negative electrodes
The facing area of is preferably 100 cm²More than 400cm²Since
Lower, more preferably 120 cm²More than 300cm²Since
Below, most preferably 150 cm²More than 250cm²so
is there.

The electrode diameter in the present invention is the diameter of the circumscribed circle of the cross section of a substantially cylindrical body formed by winding a positive electrode, a negative electrode and a separator. The electrode body is the outermost winding tape,
Although the diameter of the cross-sectional circle slightly varies depending on the location due to the lead tabs and the like near the outer circumference, the electrode body diameter is the distance from the most stressed portion to the outer core when the electrodes are inserted and after battery calibration. In addition, the outer portion does not include a protruding portion that is substantially free of stress such that a part of the end of the separator is turned over to increase the apparent circumscribed circle diameter. In addition, when the electrode body is relatively flexibly deformed to have a substantially circular cross section or a substantially elliptical cross section, it means the substantially maximum value of the diameter of the circumscribing circle when it becomes a substantially circle. . More specifically, the difference between the electrode body diameter of the battery and the inner diameter of the battery can is preferably 30 μm or more and 300 μm or less, more preferably 100 μm or more and 250 μm or less, and most preferably 150 μm or more and 200 μm or less.

A transition metal oxide used in the present invention before insertion of lithium ions (hereinafter referred to as a negative electrode active material precursor).
Is prepared by mixing two or more kinds of transition metal compounds at a desired ratio, 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 of 3.1 or less. It is preferable to mix them so as to be synthesized. However, transition metals include Ti, V, Mn, and C.
The transition metal contains at least one of o, Ni, Fe, Cr, Nb, and Mo. Further, the negative electrode active material precursor is preferably synthesized by mixing a lithium compound and a transition metal compound so that the molar ratio of lithium compound / total transition metal compound is 0.2 to 3.1. Here, the transition metal is the transition metal containing at least one of Ti, V, Mn, Co, Ni and Fe.

At least one of the transition metal oxides as the precursor of the negative electrode active material of the present invention is Li _p MO _j (provided that M
Represents at least one transition metal and at least one of the transition metals is Ti, V, Mn, Co, Ni, F
e, Cr, Nb, and Mo, p is in the range of 0 to 3.1, and j is in the range of 1.6 to 4.1).

The above negative electrode active material precursor further comprises Li _p
M _1q1 M _2q2 ... Mn _qn O _j (however, M ₁ , M ₂ , ...
Each of Mn represents the transition metal, at least one of which represents Ti, V, Mn, Co, Ni or Fe, and p is in the range of 0 to 3.1, q1 + q2.
+ ... + qn = 1, n is in the range 1-10, and j is in the range 1.6-4.1). Further, in the above equation, p is 0.2 to
More preferably, it is in the range 3.1, n is in the range 1 to 4, and j is in the range 1.8 to 4.1. In particular, in the above formula, p is in the range of 0.2 to 3.1, n is in the range of 1 to 3, and j is 1.8 to
It is preferably in the range of 4.1.

The negative electrode active material precursor of the present invention has a valence of 5
Valent to hexavalent stable transition metals (eg, V, Nb,
Cr, Nb, Mo)
Is advantageous in obtaining a high discharge capacity. From this perspective
As the negative electrode active material precursor of the present invention, at least V
It is particularly preferable to include. Negative electrode active material containing the above V
As for quality, Li_pM_1q1M_2q2... Mn_qnV_qO_j
(However, M is a transition metal, and p is in the range of 0 to 3.1.
Alq, q1 + q2 + ... + qn + qv = 1
n ranges from 1 to 9 and j ranges from 1.3 to 4.1
It is preferably in the range). Also includes the above V
The negative electrode active material is Li_pM_q1M_q2V_{1- (q1 + q2 )}O_j(However
However, M is a transition metal, and p is in the range of 0.2 to 3.1.
, Q1 + q2 are in the range 0 to 0.7, and j
Is preferably in the range of 1.3 to 4.1).
Good The negative electrode active material precursor containing V is Li
_pCo _qV_1-qO_j, Li_pNi_qV_1-qO_j(However,
p is in the range of 0.3 to 2.2, and q is 0.02 to 0.
7 and j is in the range 1.5 to 2.5.
Most preferably).

Examples of particularly preferable negative electrode active materials in the present invention include Li _p CoVO ₄ and Li _p NiVO ₄ (where p is in the range of 0.3 to 2.2).
Here, the above-mentioned p value is a value before the start of charging / discharging and increases / decreases due to charging / discharging. The general formula shown in the present invention (eg, Li _p M
In O _j ), the total number of transition metals M is 1.

The negative electrode active material of the present invention can be obtained by inserting lithium ions into a negative electrode active material precursor of a transition metal oxide and / or a lithium-containing transition metal oxide as follows. For example, a method of reacting with lithium metal, a lithium alloy, butyl lithium, or the like, or a method of 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. Above all, it is most preferable to use a lithium-containing transition metal oxide as a negative electrode active material precursor and electrochemically insert lithium ions into the transition metal oxide. As a method of electrochemically inserting lithium ions, a target lithium-containing transition metal oxide (a negative electrode active material precursor in the present invention) is included as a positive electrode active material, and lithium metal and a lithium salt are included as a negative electrode active material. It can be obtained by discharging a redox system composed of a non-aqueous electrolyte (for example, an open system (electrolysis) or a closed system (battery)). Furthermore, a redox system (for example, an open system) composed of a lithium-containing transition metal oxide as a positive electrode active material, a negative electrode active material precursor having a composition formula different from that of the positive electrode active material as a negative electrode active material, and a non-aqueous electrolyte containing a lithium salt. A method obtained by charging (electrolysis) or closed system (battery)) is preferable.

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. Especially 40 to 1
070 mAh (corresponding to 1.5 to 40 mmol) is preferable.
And 54-938 mAh (2-35 mmol equivalent) is the most preferable. The charge-discharge cycle cut-off voltage is
Although it cannot be uniquely determined because it varies depending on the type and combination of the positive electrode active material and the negative electrode active material used, a voltage that can increase the discharge voltage and substantially maintain the cycle property is preferable.

The negative electrode active material thus obtained is one in which the basic structure of the crystal of this precursor is changed, and this change is preferably from the diffraction angle (2θ) 5 of the X-ray diffraction pattern by CuKα rays. This is a change confirmed by changing the intensity of the X-ray diffraction maximum peak in the range of 70 degrees to ⅕ or less. Particularly, 1/10 or less is preferable, and 1/20 or less is most preferable. The intensity 0 here means that substantially all of the precursor of the negative electrode active material has changed to a negative electrode active material capable of charging and discharging, and specifically, noise of the X-ray diffraction pattern (baseline ) Level. Furthermore, it is preferable that at least one of the peaks other than the main peak disappears or a new peak is expressed.

The negative electrode active material thus obtained is generally a lithium-containing transition metal oxide, and the crystal thereof has a diffraction angle (2θ) of 5 to 70 degrees in an X-ray diffraction pattern by CuKα ray. It has a basic structure characterized by the intensity of all X-ray diffraction peaks within the range of 20 to 1000 cps. The peak intensity is preferably 20 to 800 cps, and further 20 to 5
00 cps is preferred, and 20-400 cps is most preferred. As the measurement conditions for the above X-ray diffraction, 40 k
V, 120 mA, scan speed = 32 ° / min. As the standard compound, the signal intensity of the main peak of LiCoO ₂ , 2θ = 18.9 ° (4.691 angstrom), was 7990 cps. (Li
CoO ₂ synthesis method: Li ₂ CO ₃ and CoCO ₃
The mixture is mixed in a mortar so that Co = 1 (molar ratio), transferred to a magnetic crucible, left at 130 ° C. for 1 hour, and then baked in air at 900 ° C. for 6 hours. After cooling at 2 ° C./min, the mixture is ground in a mortar until the average particle size is about 7.5 μm in median diameter. The crystal form of the negative electrode active material is not a layered structure, a spinel structure or a rutile structure, but one having another crystal structure or one having no crystal structure.

Furthermore, in the present invention, "the X-ray diffraction pattern of the negative electrode active material does not substantially change during charge and discharge" means that the crystalline or amorphous material expands and contracts due to the absorption and desorption of lithium ions, which results in It means that the bond distance and the morphology of the particles change, but the basic crystalline or amorphous structure does not change. Specifically, during charging / discharging, the variation range of the lattice (plane) spacing obtained from the peak value of the X-ray diffraction method is preferably −0.5 to 0.5 angstrom,
Furthermore, -0.1 to 0.1 angstrom is preferable. Further, the peak intensity ratio and the half width may vary.

As described above, the X-ray diffraction pattern of the negative electrode active material in which the lithium ions of the present invention are inserted does not substantially change even if charging and discharging are repeated. For example, the negative electrode active material precursor LiCoVO ₄ is V ⁵⁺ (Li ⁺ Co ²⁺ ) O
_The structure represented by ₄ is that when a lithium ion is electrochemically inserted into this oxide, the crystal structure changes to an unknown crystal structure that gives a broad peak around 2 Å or an amorphous structure. This once-changed crystal structure or amorphous structure does not substantially change even if charging and discharging are repeated. This is because the above-mentioned Japanese Patent Laid-Open No. 58-58
-220362, "If lithium ions are inserted too much into the spinel structure, the spinel structure is destroyed and an unknown compound is changed, which is not preferable as an active material of a secondary battery." is there. And
It was discovered that the compound with this new structure has a low redox potential and thus can be used as a negative electrode active material.

The positive electrode active material used in the present invention may be a transition metal oxide capable of reversibly occluding and releasing lithium ions, but a lithium-containing transition metal oxide is preferable. Preferred lithium-containing transition metal oxide positive electrode active materials include lithium-containing Ti, V, Cr, Mn, Fe and Co.
The oxide containing Ni, Cu, Mo and / or W can be mentioned. It is preferable that the positive electrode active material and the negative electrode active material have different composition formulas.

The lithium-containing transition metal oxide which is the positive electrode active material of the present invention comprises a lithium compound and one or more transition metal compounds, and the lithium compound / total transition metal compound molar ratio is 0.3 to 2. It is preferable that they are mixed and synthesized so as to be 0.2 (however, the transition metal is Ti,
At least one selected from V, Cr, Mn, Fe, Co, Ni, Mo and W). Furthermore, as the transition metal,
It is preferably at least one selected from V, Cr, Mn, Fe, Co and Ni.

The lithium-containing transition metal oxide, which is the positive electrode active material of the present invention, is Li _y MO _z (where M is Co,
A transition metal containing at least one selected from Mn, Ni, V and Fe, y is in the range of 0.3 to 1.2, and z is in the range of 1.4 to 3).

Preferred Lithium-Containing Metal Oxides of the Present Invention
As the positive electrode active material of_yCoO₂, Li_yNiO
₂, Li_yCo_aNi_1-aO₂, Li_yCo_bV_1-bO
_z, Li_yCo_bFe_1-bO₂, Li_yMn₂O_Four, L
i_yMn_cCo_2-cO_Four, Li_yMn_cNi_2-cO_Four,
Li_yMn_cV_2-cO_FourAnd Li_yMn_cFe
_2-cO _Four, And Li_yMn₂O_FourAnd MnO₂Mixed with
Thing, Li_2yMn₂O₃And MnO ₂A mixture with, and Li
_yMn₂O_Four, Li_2yMn₂O₃And MnO₂Mixture with
(However, y is in the range of 0.5 to 1.2, and a is 0.1.
Is in the range of 0.9 and b is in the range of 0.8 to 0.98.
, C is in the range 1.6 to 1.96, and z is
2.01 to 5).

Further preferred lithium-containing metal acid of the present invention
The positive electrode active material of the compound is Li_yCoO₂, Li_yN
iO₂, Li_yCo_aNi_1-aO₂, Li_yCo_bV
_1-bO _z, Li_yCo_bFe_1-bO₂, Li_yMn₂O
_Four, Li_yMn_cCo_2-cO_Four, Li_yMn_cNi_2-c
O_Four, Li_yMn_cV_2-cO_Four, Li_yMn_cFe_2-c
O_Four(However, y is in the range of 0.7 to 1.04, and a is
It is in the range of 0.1 to 0.9, and b is 0.8 to 0.98.
Range, c is in the range of 1.6 to 1.96, and
Z is in the range of 2.01 to 2.3).
it can.

The most preferable lithium-containing transition metal oxides of the present invention are Li _y CoO ₂ and Li _y NiO.
₂ , Li _y Co _a Ni _1-a O ₂ , Li _y Mn ₂ O ₄ , L
i _y Co _b V _1-b O _z (where y is in the range of 0.7 to 1.1, a is in the range of 0.1 to 0.9, and b is 0.
9 to 0.98 and z is 2.01-2.
3). Furthermore, y is in the range 0.7 to 1.04, a is in the range 0.1 to 0.9, b is in the range 0.9 to 0.98, and z is 2.02. It is preferably in the range of to 2.3. Here, the above y value is a value before the start of charging / discharging,
It will increase or decrease due to charge and discharge. The oxide of the positive electrode active material used in the present invention may be crystalline or amorphous, but a crystalline compound is preferable.

In the present invention, "the positive electrode active material and the negative electrode active material have different composition formulas" means the following: Different combinations of metal elements, and 2. Positive electrode active material Li _y Co _b V _1-b O _z and negative electrode active material L
In the example of i _x Co _q V _1-q O _j , it means that the values of y and x, b and q, and z and j are not equal at the same time. In particular, this means that b and q and z and j are not equal at the same time. The positive electrode active material and the negative electrode active material used in the present invention are preferably combined with compounds having different standard redox potentials.

The positive electrode active material of the present invention comprises a method of chemically inserting lithium ions into a transition metal oxide, a method of electrochemically inserting lithium ions into a transition metal oxide, or a mixture of a lithium compound and a transition metal compound, It can be synthesized by firing.

In synthesizing the positive electrode active material of the present invention, as a method of inserting lithium ions into a transition metal oxide, a method of reacting lithium metal, a lithium alloy or butyllithium with a transition metal oxide is preferable. . The positive electrode active material used in the present invention is particularly preferably synthesized by mixing a lithium compound and a transition metal compound and firing.

The negative electrode active material precursor of the present invention can also be synthesized by a method of mixing and firing a lithium compound and a transition metal compound or by a solution reaction, but a firing method is particularly preferable. The firing temperature used in the present invention may be a temperature at which a part or all of the mixed compounds used in the present invention cause a solid phase reaction, and for example, 250 to 200.
0 degreeC is preferable and 350-1500 degreeC is especially preferable.
The firing gas atmosphere used in the present invention is not particularly limited, but in the positive electrode active material, air or a gas having a large proportion of oxygen (for example, about 30% or more), and in the negative electrode active material, the proportion of air or oxygen is set. Less gas (eg about 10%
Below) or inert gas (nitrogen gas, argon gas)
Medium is preferred. In addition, for example, when a lithium compound, a vanadium compound or a cobalt compound is mixed and fired, L
iVO ₃ and Li ₃ VO ₄ may be generated.
As described above, a compound having a low activity as a negative electrode active material precursor may be included in the synthesis process. Such a compound may be contained as it is, but may be removed if desired.

The negative electrode active material precursor and the positive 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,
The same transition metal complex salt is used.

Preferred lithium compounds which can be used in the present invention include lithium oxide, lithium hydroxide, lithium carbonate, lithium nitrate, lithium sulfate, lithium sulfite, lithium phosphate, lithium tetraborate, lithium chlorate and perchloric acid. Lithium, lithium thiocyanate,
Lithium formate, lithium acetate, lithium oxalate, lithium citrate, lithium lactate, lithium tartrate, lithium pyruvate, lithium trifluoromethanesulfonate, lithium tetraborate, lithium hexafluorophosphate, lithium fluoride, lithium chloride, bromide Examples thereof include lithium and lithium iodide.

Preferred transition metal compounds that can be used in the present invention include TiO ₂ , lithium titanate,
Acetylacetonato titanyl, titanium tetrachloride, titanium tetraiodide, ammonium titanyl oxalate, VOd, (d = 2 to
2.5, compound of d = 2.5 is vanadium pentoxide), V
Od, lithium compounds, vanadium hydroxide, ammonium metavanadate, ammonium orthovanadate, ammonium pyrovanadate, vanadium oxosulfate, vanadium oxytrichloride, vanadium tetrachloride, lithium chromate, ammonium chromate, cobalt chromate, chromium acetyl Acetonate, MnO 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 acetyl Acetonate, iron oxide (2, 3
Valence), iron trioxide, iron hydroxide (2,3 valence), iron chloride (2,3 valence), iron bromide (2,3 valence), iron iodide (2,3 valence)
Value), iron sulfate (2,3 value), ammonium iron sulfate (2,3)
Trivalent), iron nitrate (2,3 valent) iron phosphate (2,3 valent), iron perchlorate, iron chlorate, iron acetate (2,3 valent), iron citrate (2,3 valent), citric acid Ammonium ferric acid (2,3 valent),
Iron oxalate (2,3 valent), ammonium iron oxalate (2,3)
Price),

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, hexaammine cobalt 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, copper oxide (divalent), copper hydroxide, Copper sulfate, copper nitrate, copper phosphate, copper fluoride, copper chloride, ammonium chloride copper, copper bromide, copper iodide, copper formate, copper acetate, copper oxalate, copper citrate, niobium oxychloride, niobium pentachloride, penta Niobium iodide, niobium monoxide, niobium dioxide, niobium trioxide, niobium pentoxide, niobium oxalate, niobium methoxide, niobium ethoxide, niobium propoxide, niobium oxide Kishido, lithium niobate,
MoO ₃ , MoO ₂ , LiMo ₂ O ₄ , molybdenum pentachloride, ammonium molybdate, lithium molybdate, ammonium molybdophosphate, molybdenum acetylacetonate, WO ₂ , WO ₃ , tungstic acid, ammonium tungstate, ammonium tungstophosphate. Can be mentioned.

Particularly preferred which can be used in the present invention
As a transition metal compound, TiO 2 ₂, Titanyl oxalate
MONOMIUM, VO_d(D = 2-2.5), VO_dRichi
Um compounds, ammonium metavanadate, MnO₂,
Mn₂O₃, Manganese hydroxide, manganese carbonate, man nitrate
Cancer, ammonium manganese sulfate, manganese acetate, oxalic acid
Manganese, manganese citrate, iron oxide (2,3 valent), four
Iron trioxide, iron hydroxide (2,3 valent), iron acetate (2,3)
Value), iron citrate (2,3 value), iron citrate ammoniu
(2,3 values), iron oxalate (2,3 values), iron oxalate ammonium
Um (2,3 valence), CoO, Co₂O₃, Co₃O_Four,
LiCoO₂, Cobalt carbonate, basic cobalt carbonate, water
Cobalt oxide, cobalt oxalate, cobalt acetate, nickel oxide
Gel, nickel hydroxide, nickel carbonate, basic nitric carbonate
Kell, nickel sulfate, nickel nitrate, nickel acetate, acid
Copper (1 and 2), copper hydroxide, copper acetate, copper citrate, M
oO₃, MoO₂, LiMo₂O_Four, WO₂, WO₃To
Can be mentioned.

Particularly preferred which can be used in the present invention
As a combination of a lithium compound and a transition metal compound, an acid
Lithium fluoride, lithium hydroxide, lithium carbonate, lithium acetate
Um and VO_d(D = 2-2.5), VO_dLithiation
Compound, ammonium metavanadate, MnO₂, Mn₂
O₃, Manganese hydroxide, manganese carbonate, manganese nitrate,
Iron oxide (2,3 valence), triiron tetraoxide, iron hydroxide (2,3)
Valence) iron acetate (2,3 valence), iron citrate (2,3 valence),
Ammonium iron enoate (2,3 valent), iron oxalate (2,3)
Valence), ammonium iron oxalate (2,3 valence), CoO, Co
₂O₃, Co₃O_Four, LiCoO₂, Cobalt carbonate, salt
Basic cobalt carbonate, cobalt hydroxide, cobalt sulfate, glass
Cobalt acid, nickel oxide, nickel hydroxide, nickel carbonate
Kell, basic nickel carbonate, nickel sulfate, nickel nitrate
, Nickel acetate, MoO₃, MoO ₂, LiMo₂O
_Four, WO₃Can be mentioned.

As an example of the negative electrode active material precursor of the present invention,
Compounds, but are not limited to these compounds
Absent. For example, LiVO_3.1, LiTiO_2.3, Co
VO _3.7, LiCoVO_4.O, LiCo_0.5V_0.5O
_2.1, LiNiVO_4.0, Li _0.75Ni_0.5V_0.5O
_2.1, Li_1.75Ni_0.5V_0.5O_2.4, LiTi_0.5V
_{0. Five}O_2.9, LiMn_0.5V_0.5O_2.5, LiFe_0.5
Mn_0.5O_2.1, LiCo _O.25V_0.75O_2.8, LiNi
_0.25V_0.75O_2.7, LiNi_0.05V_0.95O_3.1, LiF
e_0.05V_0.95O_3.1, LiMn_0.05V_0.95O_3.0, Li
Ca_0.05V_0.95O_{3. 2}, LiCo_0.75V_0.25O_1.9, L
iMn_0.25Ti_0.5V_0.25O_2.6, LiCr _0.05V_0.95
O_3.2, LiNb_0.05V_0.95O_3.1, LiMo_0.05V
_0.95O_3.0Is. The oxygen number is the weight of the compound before firing.
It is a value obtained from the amount and the weight after firing. Therefore, oxygen
The number is -10% to 10% of the above value due to the accuracy of the measuring method.
It is necessary to add the difference.

In addition to lithium compounds and transition metal compounds,
In general, compounds that enhance ionic conductivity, such as Ca ²⁺ ,
(For example, calcium carbonate, calcium chloride, calcium oxide, calcium hydroxide, calcium sulfate, calcium nitrate, calcium acetate, calcium oxalate, calcium citrate, calcium phosphate) or amorphous formation containing P, B, Si Agents (eg P ₂ O ₅ , Li ₃ P
O ₄ , H ₃ BO ₃ , SiO _{2 and the} like) may be mixed and fired. In addition, alkali metal ions such as Na, K and Mg and / or Sn, Al, Ga, Ge, Ce and I
You may mix with a compound containing n, Bi, etc. (for example, each oxide, hydroxide, carbonate, nitrate, etc.), and bake. Among them, calcium carbonate or P ₂ O ₅
It is preferable to mix with and fire. The addition amount is not particularly limited, but 0.2 to 10 mol% is preferable.

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 0.03 to
50 μm is preferable. A known crusher or classifier can be used to obtain a predetermined particle size. For example,
Mortar, ball mill, vibrating ball mill, satellite ball mill,
A swirling airflow type jet mill, a sieve, etc. can be mentioned.

The chemical formula of the compound obtained by firing was calculated by an inductively coupled plasma (ICP) emission spectral analysis method as a measuring method, and as a simple method from the weight difference between the powders before and after firing.

Materials that can be used with the negative electrode active material of the present invention include lithium metal and lithium alloys (Al, Al-
Mn (US Pat. No. 4,820,599), Al-Mg
(JP-A-57-98977), Al-Sn (JP-A-63-6742), Al-In, Al-Cd.
(JP-A-1-144573) or the like, or a calcined carbonaceous compound capable of inserting and extracting lithium ions or lithium metal (for example, JP-A-58-209864, JP-A-61-214417, and JP-A-62-62). -88269
JP-A-62-216170, JP-A-63
-13282, JP-A-63-24555,
JP-A-63-112247, JP-A-63-121
257, JP-A-63-155568, JP-A-63-276873, and JP-A-63-31482.
1, JP-A-1-204361, JP-A-1-204361
221859, JP-A-1-274360, etc.). The purpose of using the lithium metal or lithium alloy together is to insert lithium ions into the battery, and does not utilize the dissolution / precipitation reaction of lithium metal or the like as the battery reaction.

A conductive agent, a binder, a filler or 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
No. 48554), 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 1
-50% by weight is preferable, and 2-30% by weight is particularly preferable. For carbon and graphite, 2 to 15% by weight is particularly preferable.

As the binder, one kind or a mixture of polysaccharides, thermoplastic resins and polymers having rubber elasticity can be used. Preferred examples are starch, polyvinyl alcohol, carboxymethyl cellulose, hydroxypropyl cellulose, regenerated cellulose,
Diacetyl cellulose, polyvinyl chloride, polyvinylpyrrolidone, polytetrafluoroethylene, polyvinylidene fluoride, polyethylene, polypropylene, ethylene-propylene-diene terpolymer (EPDM), sulfonated EPDM, styrene butadiene rubber, polybutadiene, fluororubber and polyethylene oxide. Can be mentioned. 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 2
-30% by weight is preferred. As the filler, any fibrous material that does not cause a chemical change in the constructed battery can be used. Generally, olefin polymers such as polypropylene and polyethylene, fibers such as glass and carbon are used. The amount of the filler added is not particularly limited, but is preferably 0 to 30% by weight.

The method for preparing the negative electrode mixture or the positive electrode mixture is preferably a dry method or a wet method of adding powders of an active material, a conductive agent, a binder and the like in a dry manner or by adding water or an organic solvent. Further, the binder may be a solution prepared in advance, a dispersion (latex), or a binder. Preferred examples of the mixing device include a mortar, a mixer, a homogenizer, a dissolver, a sand mill, a paint shaker, a kneader, and a dyno mill.

The electrolyte is generally composed of a solvent and a lithium salt (anion and lithium cation) which is soluble in the solvent. As the solvent, propylene carbonate, ethylene carbonate, butylene carbonate,
Dimethyl carbonate, diethyl carbonate, γ-butyrolactone, methyl formate, methyl acetate, 1,2-dimethoxyethane, tetrahydrofuran, 2-methyltetrahydrofuran, dimethylsulfoxide, 1,3-dioxolane, formamide, dimethylformamide, dioxolane, acetonitrile, nitromethane, Ethyl monoglyme, phosphoric acid triester (JP-A-60-23973)
JP-A-61-4170.
JP-A-62-1577.
1, JP-A-62-22372, JP-A-62-62
-108474), sulfolane (JP-A-62-3)
1959), 3-methyl-2-oxazolidinone (JP-A-62-44961), propylene carbonate derivative (JP-A-62-290069, JP-A-6-290069).
2-290071), tetrahydrofuran derivative (JP-A-63-32872), ethyl ether (JP-A-63-62166), 1,3-propanesultone (JP-A-63-102173). Aprotic organic solvents such as, and these are used alone or in combination of two or more. Examples of the cation of a lithium salt that dissolves in these solvents include ClO
_{^{4 -, BF 4 -, PF}} 6 -, CF 3 SO 3 -, CF 3 C
O ₂ ⁻ , AsF ₆ ⁻ , SbF ₆ ⁻ , (CF ₃ SO ₂ ) _{2
^{N -, B 10 Cl 10 2-}} ( JP 57-74974 JP), (1,2-dimethoxyethane) ₂ ClO ₄ ^- (JP 57-74977 JP), lower aliphatic carboxylic acid ion ( JP-A-60-41773), AlCl ₄
^{-, Cl -, Br -,} I - ( JP 60-247265
No.), an anion of a chloroborane compound (JP-A-61)
165957) and tetraphenyl borate ion (JP-A-61-214376).
These 1 type (s) or 2 or more types can be used.
Among them, propylene mosquitoes - BONNET - DOO or ethylene carbonate and 1,2-dimethoxyethane and / or LiCF ₃ SO ₃ in a mixture of diethyl carbonate, Li
An electrolyte containing ClO ₄ , LiBF ₄ and / or LiPF ₆ is preferred.

The amount of these electrolytes added to the battery is not particularly limited, but can be used in a required amount 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. (The mixing ratio when both 1,2-dimethoxyethane and diethyl carbonate are used is 0.4 / 0.6 to 0.6 / 0.4). The concentration of the supporting electrolyte is not particularly limited, but is preferably 0.2 to 3 mol per liter of the electrolytic solution.

In addition to the electrolytic solution, the following solid electrolytes can be used. Solid electrolytes are classified into inorganic solid electrolytes and organic solid electrolytes. Li-nitrides, halides, oxyacid salts, and the like are well known as inorganic solid electrolytes. Among them, Li ₃ N, LiI, Li ₅ N
_{I 2, Li 3 N-LiI} -LiOH, LiSiO 4, L
iSiO ₄ -LiI-LiOH (JP-A-49-8189)
9 _{JP), xLi 3 PO 4 - (} 1-x) Li 4 SiO
₄ (Japanese Patent Laid-Open No. 59-60866), Li ₂ SiS ₃
(JP-A-60-501731), phosphorus sulfide compounds (JP-A-62-82665) and the like are effective.

In the organic solid electrolyte, a polyethylene oxide derivative or a polymer containing the derivative (JP-A-63-1).
35447), polypropylene oxide derivatives or polymers containing these derivatives, polymers containing ion dissociative groups (JP-A-62-254302, JP-A-6-254302).
2-254303, JP-A-63-193954), a mixture of a polymer containing an ion dissociative group and the aprotic electrolyte (US Pat. No. 4,792,504,
U.S. Pat. No. 4,830,939, JP-A-62-223
75, JP 62-22376, and JP 6
3-22375, JP-A-63-22776, JP-A-1-95117), a phosphoric acid ester polymer (JP-A-61-256573), and a polymer containing an aprotic polar solvent. Matrix material (US Pat. No. 4,822,70, US Pat. No. 4,83
0,939, JP-A-63-239779, Japanese Patent Application No. 2-30318, and Japanese Patent Application No. 2-78531) are effective. Furthermore, there is also a method of adding polyacrylonitrile to the electrolytic solution (JP-A-62-278774).
Issue). Further, a method of using an inorganic and organic solid electrolyte in combination (Japanese Patent Laid-Open No. 60-1768) is also known.

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

Other compounds may be added to the electrolyte for the purpose of improving discharge and charge / discharge characteristics. For example, pyridine (JP-A-49-108525), triethylphosphite (JP-A-47-4376), triethanolamine (JP-A-52-72425), cyclic ether (JP-A-57-57425). 152684), ethylenediamine (JP-A-58-87777), n-glyme (JP-A-58-87778), hexaphosphoric acid triamide (JP-A-58-8777).
9), nitrobenzene derivatives (JP-A-58-21)
No. 4281), sulfur (JP-A-59-8280), quinone imine dye (JP-A-59-68184), N-substituted oxazolidinone and N, N'-substituted imidazolidinone (JP-A-59-154778). Gazette), ethylene glycol dialkyl ether (JP-A-59-20)
No. 5167), quaternary ammonium salts (Japanese Patent Laid-Open No. Sho 60).
-30065), polyethylene glycol (JP-A-60-41773), pyrrole (JP-A-60-).
79677), 2-methoxyethanol (JP-A-60-
89075), AlCl ₃ (JP-A-61-884).
No. 66), a monomer of a conductive polymer electrode active material (JP-A 61-161673), triethylene phosphoramide (JP-A 61-208758), trialkylphosphine (JP-A 62-80976). No.), morpholine (JP-A-62-80977),
Aryl compounds having a carbonyl group (JP-A-62-86)
673), crown ethers such as 12-crown 4 (Physical Review (Physical, Review))
B, 42, 6424 (1990)), hexamethylphosphoric triamide and 4-alkylmorpholine (JP-A-62-217575), and bicyclic tertiary amine (JP-A-62-217578). Gazette), oil (JP-A-62-287580), quaternary phosphonium salt (JP-A-63-1212268), tertiary sulfonium salt (JP-A-63-1212269), 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-48-36,6).
32). Further, the electrolytic solution may contain carbon dioxide gas in order to have suitability for high temperature storage (JP-A-59-13).
4567).

Further, the mixture of the positive electrode and the negative electrode can contain an electrolytic solution or an electrolyte. For example, the ion conductive polymer and nitromethane (Japanese Patent Laid-Open No. 48-3663).
3) and an electrolytic solution (JP-A-57-124870).

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-55-163779) or a chelating agent (JP-A-55-163780), a conductive polymer (special Examples of the treatment include treatments with JP-A-58-163188, JP-A-59-14274), polyethylene oxide and the like (JP-A-60-97561). 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-58-142771).
Processing).

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. Further, 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 applied (coated) on the current collector, dried and compressed, and is mainly used. As a coating method, a general method can be used. Examples thereof include a reverse roll method, a direct roll method, a blade method, a knife method, an extrusion method, a curtain method, a gravure method, a bar method, a dip method and a squeeze method. The blade method, knife method and extrusion method are preferred. The coating is preferably carried out 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 particularly preferably 1 to 2000 μm in a compressed state after drying.

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 10
The range of 0 to 250 ° C. is preferable. The water content of the whole battery is preferably 2000 ppm or less, and the content of each of the positive electrode mixture, the negative electrode mixture and the electrolyte is preferably 500 ppm or less from the viewpoint of cycleability. As a 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 is 0.2 to 3 t /
cm ² is preferred. The press speed of the calendar press method is
0.1 to 50 m / min is preferable. Press temperature is room temperature ~
200 ° C. is preferred.

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 conventionally known safety elements may be provided. For example, a fuse, a bimetal, a PTC element or the like is used as the overcurrent prevention element. In addition to the safety valve, a method of making a notch in the battery can, a method of cracking a gasket, or a method of cracking a sealing plate can be used as a measure for increasing the internal pressure of the battery can. Further, the charger may be provided with a circuit incorporating measures against overcharge and overdischarge. For the can and the lead plate, a metal or alloy having electrical conductivity can be used. For example, metals such as iron, nickel, titanium, chromium, molybdenum, copper and aluminum or alloys thereof are used. As a method for welding the cap, the can, the sheet, and the lead plate, a known method (eg, DC or AC electric welding, laser welding, ultrasonic welding) can be used. As the sealing agent for sealing, a conventionally known compound or mixture such as asphalt can be used.

The application of the non-aqueous secondary battery of the present invention is not particularly limited, and specific examples include color notebook computers, black and white notebook computers, pen input computers, pocket (palmtop) computers, notebook word processors, and pockets. Word processor, e-book player, mobile phone, cordless phone handset, pager, handy terminal, mobile fax, mobile copy, mobile printer, headphone stereo, video movie, LCD TV, handy cleaner, power tool, electronic organizer, calculator, memory card , Electronic tape recorders, watches, cameras, hearing aids.

[0060]

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

Example 1 LiCoO 2 as a positive electrode active material₂, Graphite as conductive agent,
86.3 parts by weight of acetylene black and 9.1 parts by weight, respectively
Mix 3 parts by weight, and mix as a binder.
1.6 parts by weight of ethyl acrylate, ethylene,
A maleic anhydride copolymer compound was added as a toluene solution.
After kneading, collect aluminum foil with a thickness of 20 microns
It was applied to both sides of the body. After drying the above coating,
Compression molding with a press machine and then cutting it into strips
A positive electrode sheet was created. Size of the positive electrode sheet after cutting
Is 39 mm wide and 255 mm long
It was. The thickness can be changed appropriately to adjust the molar ratio of the positive electrode and the negative electrode.
It was CoVO as negative electrode active material_3.7(The active material is 8 degrees Celsius
(Fired in air at 00 degrees for 6 hours), black as conductive agent
85 parts by weight of lead and acetylene black, 6 parts by weight, respectively
Parts, 6 parts by weight, and mixed as a binder.
3 parts by weight of ethyl acrylate, ethylene, anhydrous
Add the maleic acid copolymer compound as a toluene solution and mix.
After kneading, apply to both sides of 20 micron thick copper foil current collector
did. After drying the above coated product, press it with a roller press.
It is compression molded and then cut to make a strip negative electrode sheet.
I made it. The size of the negative electrode sheet after cutting is 40.5 width.
Mm, length 265 mm, thickness is positive electrode
It was changed as appropriate to adjust the molar ratio of the negative electrode. Microporous polypro
Pyrene separator, the above negative electrode sheet, microporous polyp
Lapylene separator and the above positive electrode sheet are stacked in this order.
Layered, and wound this in a spiral shape,
Nickel-plated iron bottomed cylindrical battery that doubles as a battery
Can (outer diameter 13.8 mm, length 49.9 mm)
I put it in a tor). Furthermore, 1 mol / liter as electrolyte
Tol lithium hexafluorophosphate (with ethylene carbonate
Butylene carbonate and diethyl carbonate 2:
2 ml of 2: 6 volume ratio mixed solution) in a battery can
Injected. In addition, the battery lid that doubles as a safety valve has a gasket
The cylindrical battery of FIG. 1 was produced by caulking. Still positive
The electrode terminal is the positive electrode sheet, the negative electrode can is the negative electrode sheet, and the battery
Connected internally with lead tabs. Positive in this battery
The molar ratio of the pole and the negative electrode is 1, 1.75, 2.5, 3.25,
Samples 1-1-1-1 to 4.0 and 5.5, respectively
It is set to 1-1-6. Replace the negative electrode active materials of Samples 1-1-1 to 6
LiTiO_3.8, LiVO_3.1, LiFe _0.5Mn_0.5
O_2.1, LiCoVO_FourChanged to
Samples 1-2 to 5-1 to 6 were used. Here, for each battery sample
Value obtained by dividing the total volume of the positive and negative electrodes by the volume of each battery
Is 0.52, the facing area of the positive and negative electrodes is the volume of each battery sample
The value divided by is 26, and the difference between the electrode body diameter and the inner diameter of the battery can is 1.
It was 75 microns. Cycleability for these samples
Was tested. Repeated charge and discharge cycles, maximum discharge
The cycle number is 60% of the capacity
Compared. The results are shown in Table 1. Books as shown in this table
Samples in the range of the molar ratio of positive electrode and negative electrode according to the invention are
You can see that it has excellent rolling performance.

[0062]

[Table 1]

Example 2 A sample was prepared by changing the value obtained by dividing the total volume of the positive electrode and the negative electrode by the volume of the battery with respect to Samples 1-5-4. Table 2 shows the results of a cycleability test performed on these materials in the same manner as in Example 1. Further, samples were prepared in which the opposing areas of the positive electrode and the negative electrode were changed with respect to Samples 1-5-4. Table 3 shows the results of a cycleability test performed on these materials in the same manner as in Example 1. As shown in these tables, the total volume of the positive electrode and the negative electrode according to the present invention divided by the volume of the battery is a sample in the range of 0.4 to 0.7, and the facing area of the positive electrode and the negative electrode is It can be seen that the sample having a value divided by the volume of the battery in the range of 15 to 50 cm 2 / cm 3 has excellent cycleability.

[0064]

[Table 2]

[0065]

[Table 3]

Example 3 Samples were prepared in which the difference between the electrode diameter and the battery can inner diameter was changed with respect to Samples 1-5-4. Table 4 shows the results of the cycleability test performed on these materials in the same manner as in Example 1.

[0067]

[Table 4]

As shown in this table, it can be seen that the samples according to the present invention in which the difference between the electrode pair diameter and the battery can inner diameter is in the range of 30 to 300 μm have excellent cycleability.

[Brief description of drawings]

FIG. 1 is a cross-sectional view of a cylinder type battery used in the present invention.

[Explanation of symbols]

 1 Synthetic resin (polypropylene) insulating sealing body 2 Negative electrode can that also serves as a negative electrode terminal 3 Negative electrode 4 Separator 5 Positive electrode 6 Electrolyte 7 Safety valve 8 Positive electrode cap that also serves as a positive electrode terminal

Claims (5)

[Claims] 1. A nonaqueous secondary battery comprising a positive electrode active material, a negative electrode active material, and a nonaqueous electrolyte containing a lithium salt, wherein the molar ratio of the positive electrode active material to the negative electrode active material is 1.6 or more and 5 or less, The non-aqueous secondary battery, wherein the negative electrode active material contains a transition metal oxide. 2. A state in which the negative electrode active material is a transition metal oxide capable of changing the basic crystal structure by inserting lithium ions, and the basic crystal structure after the change does not change due to charge and discharge. And the negative electrode active material is Li _p MO _j (where M is Ti, V, Mn, C).
o represents at least one transition metal selected from Fe, Ni, Cr, Nb and Mo, p is 0 or more and 3.1 or less, and j is 1.6 or more and 4.1 or less) The non-aqueous secondary battery according to claim 1, comprising a transition metal oxide. 3. The negative electrode active material is Li _x M _q V _1-q O _j
(However, M represents a transition metal, x is 0.17 or more 1
The ratio of 1.25 or less, q is 0 or more and 0.7 or less, and j is 1.3 or more and 4.1 or less). Water secondary battery. 4. The value obtained by dividing the total volume of the positive electrode and the negative electrode by the volume of the battery is 0.4 or more and 0.7 or less, and the facing area of the positive electrode and the negative electrode of the battery is The non-aqueous secondary battery according to claim 3, wherein the value divided by the volume is 15 cm ² / ml or more and 50 cm ² / ml or less. 5. The difference between the electrode body diameter and the battery can inner diameter is 30 μm.
The non-aqueous secondary battery according to claim 3, wherein the non-aqueous secondary battery has a thickness of 300 μm or more.