JPH1040958A - Non-aqueous electrolyte secondary battery and manufacturing method - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain a non-aqueous electrolyte secondary battery having superior charge and discharge characteristics and less deterioration of discharge capacity due to charge and discharge repetition by containing a specific material in a negative pole and containing carbon dioxide in a nonaqueous electrolyte. SOLUTION: In a non-aqueous secondary battery made of negative and positive poles containing a material capable of reversibly storing and discharging lithium, a non-aqueous electrolyte containing a lithium salt, and a separator, the negative pole contains a material made mainly of a non-crystal charcogen compound and/or non-crystal oxide including an atom of three or more types to be selected from 14 and 15 groups of periodic table and contains carbon dioxide in the non-aqueous electrolyte. Carbon dioxide contained in the non- aqueous electrolyte is 0.005mol/liter or more and 2mol/liter or less.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a high-capacity non-aqueous electrolyte secondary battery having excellent charge-discharge cycle characteristics, wherein the negative electrode material is mainly composed of an amorphous chalcogen compound and
Also, the present invention relates to improvement of charge / discharge characteristics such as charge / discharge cycle life of a nonaqueous electrolyte secondary battery having a large discharge capacity, which is an amorphous oxide.

[0002]

2. Description of the Related Art As a negative electrode material for a non-aqueous electrolyte secondary battery, lithium metal and lithium alloy are typical, but when they are used, so-called dendrite in which lithium metal grows in a dendritic manner during charge and discharge is generated. However, dangers such as ignition were caused due to the internal short circuit or the high activity of the dendrite itself. On the other hand, fired carbonaceous materials capable of reversibly inserting and releasing lithium have come into practical use. Since the carbonaceous material itself has conductivity, lithium metal may be deposited on the carbonaceous material during overcharging or rapid charging, and since the carbonaceous material has a relatively small density, There is a disadvantage that the discharge capacity is limited in the double sense that the capacity per volume is low.

In recent years, Sn, V, Si, B, Zr have been used as a negative electrode material to achieve a high capacity nonaqueous electrolyte secondary battery having a high discharge potential with an average discharge voltage of 3 to 3.6 V class. It has been proposed to use oxides such as these and composite oxides thereof (JP-A-5-174818, JP-A-6-6-18).
0867, 6-275267, 6-32576
Nos. 5, 6-338324 and EP-615296. By combining these oxides such as Sn, V, Si, B, and Zr, and their composite oxides with a positive electrode of a transition metal compound containing a certain kind of lithium, the average discharge voltage is 3 to 3.6 V class. As a result, it was found that a non-aqueous electrolyte secondary battery having high discharge capacity, very little dendrite generation in a practical area, and extremely high safety was obtained. However, these batteries also have a problem that the charge / discharge cycle is restricted depending on the handling of the negative electrode material, and it is desired to stably manufacture the battery and further improve the charge / discharge cycle characteristics.

[0004]

SUMMARY OF THE INVENTION An object of the present invention is to improve the charge / discharge cycle characteristics of a non-aqueous electrolyte secondary battery having a large discharge capacity, and to improve the stability of such a non-aqueous electrolyte secondary battery. It is to provide a manufacturing method.

[0005]

SUMMARY OF THE INVENTION An object of the present invention is to provide a non-aqueous secondary battery comprising a negative electrode and a positive electrode containing a material capable of reversibly inserting and extracting lithium, a non-aqueous electrolyte containing a lithium salt, and a separator. The negative electrode is a periodic table 1, 2, 1
A material mainly containing an amorphous chalcogen compound and / or an amorphous oxide containing three or more kinds of atoms selected from Group 3, 14, and 15 atoms, and carbon dioxide being contained in the non-aqueous electrolyte. The present invention has been attained by a non-aqueous electrolyte secondary battery and a method for producing the same.

[0006]

DESCRIPTION OF THE PREFERRED EMBODIMENTS Preferred embodiments of the present invention will be described below, but the present invention is not limited to these. (1) In a non-aqueous secondary battery including a negative electrode and a positive electrode containing a material capable of reversibly inserting and extracting lithium, a non-aqueous electrolyte containing a lithium salt, and a separator, the negative electrode is made of a periodic table 1, 2, 13, A material mainly comprising an amorphous chalcogen compound and / or an amorphous oxide containing three or more kinds of atoms selected from Group 14 and 15 atoms, and carbon dioxide being contained in the non-aqueous electrolyte. Non-aqueous electrolyte secondary battery. (2) The carbon dioxide contained in the non-aqueous electrolyte is 0.005 m
Item 2. The non-aqueous electrolyte secondary battery according to Item 1, wherein the amount is from ol / liter to 0.2 mol / liter. (3) The non-aqueous electrolyte secondary battery according to item 1 or 2, wherein the supporting salt contained in the non-aqueous electrolyte is at least LiPF ₆ and / or LiBF ₄ . (4) The nonaqueous electrolyte secondary battery according to any one of items 1 to 3, wherein the negative electrode material is represented by the general formula (1). M ¹ M ² pM ⁴ qM ⁶ r General formula (1) (where M ¹ and M ² are different from each other, Si, Ge, Sn, P
at least one selected from b, P, B, Al, and Sb;
M ⁴ is Li, Na, K, Rb, Cs, Mg, Ca, S
at least one selected from r and Ba, M ⁶ is O, S,
At least one selected from Te, p and q are each 0.0
01 to 10, r represents a number of 1.00 to 50. )

(5) In a non-aqueous secondary battery comprising a negative electrode and a positive electrode containing a material capable of reversibly storing and releasing lithium, a non-aqueous electrolyte containing a lithium salt, and a separator, the negative electrode is made of a periodic table , Containing a material mainly composed of an amorphous chalcogen compound and / or an amorphous oxide containing three or more atoms selected from Group 13, 14, 15 atoms, and allowing the non-aqueous electrolyte to contain carbon dioxide A method for producing a non-aqueous electrolyte secondary battery, comprising: (6) The method for producing a non-aqueous electrolyte secondary battery according to item 5, wherein the non-aqueous electrolyte is brought into contact with a carbon dioxide-containing gas in advance before being injected into the non-aqueous secondary battery. . (7) Item 5 or 6 wherein the battery is brought into contact with a carbon dioxide-containing gas after the nonaqueous electrolyte is injected and before sealing.
3. The method for producing a non-aqueous electrolyte secondary battery according to item 1. (8) A carbon dioxide-containing gas is sealed in the battery when the non-aqueous electrolyte secondary battery is sealed, and the carbon dioxide-containing gas is contained in the battery after the sealing. 13. The method for producing a nonaqueous electrolyte secondary battery according to item 10.

[0008] It is conventionally known to enclose carbon dioxide gas in a battery. For example, JP-A-7-176323 discloses that it is useful for preventing the formation of a lithium hydroxide film which is a battery reaction inhibitor formed on the surface of a lithium metal or lithium alloy negative electrode.
No. 431, No. 6-140077, and the like, it is effective to incorporate carbon dioxide or a compound generating carbon dioxide in order to reliably open the safety valve when an abnormality such as heat generation occurs in the battery. Have been described. The present inventors have conducted intensive studies and found that the variation in charge / discharge cyclability when the amorphous chalcogen compound and / or amorphous oxide of the present invention is used as a negative electrode material is caused by carbon dioxide gas in an electrolytic solution or the like. Is found to be improved by including
The above invention has been reached. When the above-described negative electrode material is used, the cycle characteristics vary as fine powder of the negative electrode material promotes decomposition of the electrolytic solution, or unreacted raw material during firing is deposited on the negative electrode material particles to deteriorate the cycle characteristics. However, the mechanism by which the presence of carbon dioxide gas prevents these is unknown.

In the present invention, by including carbon dioxide in the nonaqueous electrolyte, the charge / discharge cycle characteristics can be improved without impairing the high capacity of the nonaqueous electrolyte secondary battery. In the present invention, as a method of containing (dissolving) carbon dioxide in the non-aqueous electrolyte, a method of contacting a non-aqueous electrolyte with a carbon dioxide-containing gas before injecting it into a battery, and then injecting the solution, Any method of contacting and containing a carbon dioxide-containing gas before the battery is sealed, a method of enclosing the carbon dioxide-containing gas in the battery at the time of sealing the battery, and a method of containing the carbon dioxide-containing gas in the battery after the sealing may be used. Can be used in combination.

As a method of bringing the nonaqueous electrolytic solution into contact with the carbon dioxide gas in advance, a method of introducing a carbon dioxide-containing gas into the nonaqueous electrolytic solution through a diffuser or the like in a batch manner;
Any of the methods of continuous introduction through a wet wall tower, a packed tower, or a bubble tower can be used. Further, a method of contacting with a pressurized carbon dioxide-containing gas in a pressure vessel is also effective.

[0011] As a method of bringing the carbon dioxide gas into contact with the non-aqueous electrolyte in the battery after the injection and before closing the battery, a method of introducing the carbon dioxide-containing gas directly into the non-aqueous electrolyte solution and a method of bringing the carbon dioxide-containing gas into the upper part of the battery are provided. And a method of introducing and contacting a carbon dioxide-containing gas on the surface of the electrolyte solution, or a method of contacting with a pressurized carbon dioxide-containing gas in a pressure vessel.

[0012] A method of filling a carbon dioxide-containing gas into a battery at the time of closing the battery is achieved by sealing the battery in a carbon dioxide-containing gas atmosphere. The carbon dioxide-containing gas used for these may be any of pure carbon dioxide gas and a mixed gas containing carbon dioxide, but preferably contains no water as much as possible, and preferably has a dew point of -40 ° C or less, It is particularly preferred that the temperature is lower than or equal to ° C. As the mixed gas, a mixed gas with air, oxygen or the like, a mixed gas with an inert gas such as nitrogen or argon, or the like can be used. The amount of carbon dioxide contained in the non-aqueous electrolyte
It is preferably from 0.005 mol / l to 0.2 mol / l, particularly preferably from 0.01 mol / l / l to 0.1 mol / l. The concentration of carbon dioxide in the electrolytic solution can be measured by a GC method (gas chromatography method). If the amount of carbon dioxide is too small, the effect of improving the charge / discharge cycle characteristics is not sufficient, and if it is too large, problems such as an increase in the internal pressure of the battery due to an increase in the outside air temperature when the battery is used are not preferable.

The electrolytic solution generally comprises a solvent and a supporting salt dissolved in the solvent, and is preferably a lithium salt (anion and lithium cation). Solvents for the electrolytic solution that can be used in the present invention include propylene carbonate, ethylene carbonate, butylene carbonate, dimethyl carbonate, diethyl carbonate, methyl ethyl carbonate, γ-butyrolactone, methyl formate, methyl acetate, 1,2-dimethoxyethane, and tetrahydrofuran. , 2-methyltetrahydrofuran, dimethyl sulfoxide, 1,3-dioxolan, formamide, dimethylformamide, dioxolan, dioxane, acetonitrile, nitromethane, ethyl monoglyme, phosphoric acid triester, trimethoxymethane, dioxolan derivative,
Examples include aprotic organic solvents such as sulfolane, 3-methyl-2-oxazolidinone, propylene carbonate derivatives, tetrahydrofuran derivatives, ethyl ether, and 1,3-propane sultone. To use. Of these, carbonate-based solvents are preferred, and cyclic carbonates and / or
Alternatively, those containing an acyclic carbonate are preferable.
As the cyclic carbonate, ethylene carbonate and propylene carbonate are preferable. In addition, the non-cyclic carbonate preferably contains diethyl carbonate, dimethyl carbonate, and methyl ethyl carbonate.

Examples of the lithium salt soluble in these solvents which can be used in the present invention include, for example, LiClO ₄ , LiB
F ₄ , LiPF ₆ , LiCF ₃ SO ₃ , LiCF ₃ CO
₂ , LiAsF ₆ , LiSbF ₆ , LiB ₁₀ Cl ₁₀ , lithium lower carboxylate, LiAlCl ₄ , LiC
l, LiBr, LiI, lithium chloroborane, lithium salts such as lithium tetraphenylborate can be raised,
These may be used alone or in combination of two or more. Among them, LiBF ₄ , LiPF ₆ , LiCF ₃
It is preferable that one or two or more kinds of SO ₃ are mixed and dissolved. A mixture of one or two of LiBF ₄ and LiCF ₃ SO ₃ and LiPF ₆ is particularly preferred. The concentration of the supporting salt is not particularly limited, but is preferably 0.2 to 3 mol per liter of the electrolytic solution. Examples of the electrolytic solution that can be used in the present invention include LiCF ₃ SO ₃ , LiClO ₄ , LiBF ₄ and / or LiPF ₆ in which an electrolyte solution obtained by appropriately mixing ethylene carbonate, propylene carbonate, 1,2-dimethoxyethane, dimethyl carbonate, or diethyl carbonate is used. An electrolytic solution containing Particularly, a mixed solvent of propylene carbonate or ethylene carbonate and 1,2-dimethoxyethane and / or diethyl carbonate is used as a mixture of LiCF ₃ SO ₃ and LiC.
An electrolyte containing 10 ₄ , LiBF ₄ and / or LiPF ₆ is preferred, and an electrolyte containing at least ethylene carbonate and LiPF ₆ is particularly preferred. The amount of these electrolytes to be added to the battery is not particularly limited, but can be used in a required amount depending on the amounts of the positive electrode active material and the negative electrode material and the size of the battery.

Hereinafter, other materials and a method of manufacturing the non-aqueous electrolyte secondary battery of the present invention will be described in detail. The positive and negative electrodes used in the non-aqueous electrolyte secondary battery of the present invention can be prepared by applying a positive electrode mixture or a negative electrode mixture on a current collector. The positive electrode or negative electrode mixture can contain a conductive agent, a binder, a dispersant, a filler, an ionic conductive agent, a pressure enhancer, and various additives, respectively, in addition to the positive electrode active material or the negative electrode material.

The negative electrode material used in the present invention is preferably mainly amorphous at the time of assembling the battery. The term “amorphous” as used herein refers to a substance having a broad scattering band having a peak at 20 ° to 40 ° in 2θ value by X-ray diffraction using CuKα ray, and having a crystalline diffraction line. Is also good. Preferably, the strongest intensity of the crystalline diffraction lines observed at 40 ° to 70 ° in 2θ value is 20 ° in 2θ value.
It is preferably 500 times or less, more preferably 100 times or less, particularly preferably 5 times or less, and most preferably the crystallinity of the diffraction line intensity at the peak of the broad scattering band observed at 40 ° or more. Has no diffraction line.

The negative electrode material used in the present invention has the following general formula:
It is preferable to be represented by (1). M¹M^TwopM^FourqM⁶r General formula (1) where M¹, M^TwoAre different from Si, Ge, Sn, Pb,
At least one selected from P, B, Al, and Sb
And preferably Si, Ge, Sn, P, B, and Al.
And particularly preferably Si, Sn, P, B and Al.
M^FourIs Li, Na, K, Rb, Cs, Mg, Ca, S
r, at least one selected from Ba, preferably
Is K, Cs, Mg, Ca, particularly preferably Cs, Mg
It is. M⁶Is at least one selected from O, S, and Te
Species, preferably O, S, particularly preferably O
It is. p and q are each 0.001 to 10, preferably
From 0.01 to 5, particularly preferably from 0.01 to 2
It is. r is 1.00 to 50, preferably 1.0
0 to 26, and particularly preferably 1.02 to 6.
M ¹, M^TwoThe valence of is not particularly limited.
It may be a number or a mixture of each valence. Also M
¹, M^Two, M^FourThe ratio is M^TwoAnd M^FourIs M¹Against
Changes continuously within the range of 0.001 to 10 molar equivalents
And M⁶Quantity (general formula (1)
, The value of r) also changes continuously.

Among the compounds mentioned above, in the present invention, it is preferable that M ¹ is Sn, and the compound represented by the general formula (2)
It is represented by SnM ³ pM ⁵ qM ⁷ r General formula (2) In the formula, M ³ is at least one kind selected from Si, Ge, Pb, P, B, and Al, preferably Si, Ge,
P, B, Al, particularly preferably Si, P, B, A
l. M ⁵ is Li, Na, K, Rb, Cs, Mg,
At least one selected from Ca, Sr, and Ba;
Preferably, it is Cs or Mg, particularly preferably Mg.
M ⁷ is at least one selected from O and S, and is preferably O. p and q are each 0.001 to 10, preferably 0.01 to 5, more preferably 0.01 to 1.5, and particularly preferably 0.7 to 1.0.
5 r is 1.00 to 50, preferably 1.r
00 to 26, particularly preferably 1.02 to 6.

Examples of the negative electrode material of the present invention are shown below.
The invention is not limited to these. SnAl_0.4
B_0.5P_0.5K_0.1O_3.65, SnAl_0.4B_0.5P_0.5
Na_0.2O _3.7, SnAl_0.4B_0.3P_0.5Rb_0.2O
_3.4, SnAl_0.4B_0.5P_0.5Cs_0.1O_3.65, Sn
Al_0.4B_0.5P_0.5K_0.1Ge_0.05O_3.85, SnAl
_0.4B_0.5P_0.5K_0.1Mg_0.1Ge_0.02O_3.83, Sn
Al_0.4B_0.4P_0.4O_3.2, SnAl_0.3B_0.5P
_0.2O_2.7, SnAl _0.3B_0.5P_0.2O_2.7, SnA
l_0.4B_0.5P_0.3Ba_0.08Mg_0.08O_3.26, SnAl
_0.4B_0.4P_0.4Ba_0.08O_3.28, SnAl_0.4B_0.5
P_0.5O_3.6, SnAl_0.4B_0.5P_0.5Mg_0.1O
_3.7.

SnAl_0.5B_0.4P_0.5Mg_0.1F_0.2
O_3.65, SnB_0.5P_0.5Li_0.1Mg_0.1F_0.2O
_3.05, SnB_0.5P_0.5K_0.1Mg_0.1F_0.2O_3.05,
SnB_0.5P_0.5K_0.05Mg_0.05F_0.1O_3.03, SnB
_0.5P_0.5K_0.05Mg_0.1F_0.2O_3.03, SnAl_0.4
B_0.5P_0.5Cs_0.1Mg_0.1F_0.2O_3.65, SnB
_0.5P_0.5Cs_0.05Mg_0.05F_0.1O_3.03, SnB_0.5
P_0.5Mg_0.1F_0.1O_3.05, SnB_0.5P_0.5Mg
_0.1F_0.2O_Three, SnB_0.5P_0.5Mg_0.1F_0.06O
_3.07, SnB_0.5P_0.5Mg_0.1F_0.14O _3.03, SnP
Ba_0.08O_3.58, SnPK_0.1O_3.55, SnPK_0.05M
g_0.05O_3.58, SnPCs_0.1O_3.55, SnPBa_0.08
F_0.08O_3.54, SnPK_0.1Mg_0.1F_{0. Two}O_3.55, S
nPK_0.05Mg_0.05F_0.1O_3.53, SnPCs_0.1Mg
_0.1F_0.2O_3.55, SnPCs_0.05Mg_0.05F_0.1O
_3.53.

Sn_1.1Al_0.4B_0.2P_0.6Ba_0.08F
_0.08O_3.54, Sn_1.1Al_0.4B_0.2P_0.6Li_0.1K
_0.1Ba_0.1F_0.1O_3.65, Sn_1.1Al_0.4B_0.4P
_0.4Ba_0.08O_3.34, Sn_1.1Al_0.4PCs_0.05O
_4.23, Sn_1.1Al_0.4PK_0.05O_4.23, Sn_1.2Al
_0.5B_0.3P_0.4Cs_0.2O_3.5, Sn_1.2Al_0.4B
_0.2P_0.6Ba_0.08O_3.68, Sn_1.2Al_0.4B_0.2P
_0.6Ba_0.08F_0.08O_3.64, Sn_1.2Al_0.4B_0.2P
_0.6Mg_0.04Ba_0.04O_3.68, Sn_1.2Al_0.4B_0.3
P_0.5Ba_0.08O_3.58, Sn_1.3Al_0.3B_0.3P_0.4
Na_0.2O_3.3, Sn_1.3Al_0.2B_0.4P_0.4Ca
_0.2O_3.4, Sn_1.3Al_0.4B_0.4P_0.4Ba_0.2O
_3.6, Sn_1.4Al_0.4PK_0.2O_{Four. 6}, Sn_1.4Al
_0.2Ba_0.1PK_0.2O_4.45, Sn_1.4Al_0.2Ba
_0.2PK _0.2O_4.6, Sn_1.4Al_0.4Ba_0.2PK
_0.2Ba_0.1F_0.2O_4.9, Sn_1.4Al_0.4PK_0.3
O_4.65, Sn_1.5Al_0.2PK_0.2O_4.4, Sn_1.5A
l_0.4PK_0.1O_4.65, Sn_1.5Al_0.4PCs_0.05O
_4.63, Sn_1.5Al_0.4PCs_0.05Mg_0.1F_0.2O
_4.63.

SnSi _0.5 Al _0.1 B _0.2 P _0.1 Ca
_{0.4 O 3.1, SnSi 0.4 Al 0.2} B 0. 4 O 2.7, Sn
Si _0.5 Al _0.2 B _0.1 P _0.1 Mg _0.1 O _2.8 , SnS
i _0.6 Al _0.2 B _0.2 O _2.8 , SnSi _0.5 Al _0.3 B
_0.4 P _0.2 O _3.55 , SnSi _0.5 Al _0.3 B _0.4 P _0.5
O _4.30 , SnSi _0.6 Al _0.1 B _0.1 P _0.3 O _3.25 , S
_{nSi 0.6 Al 0.1 B 0. 1 P} 0.1 Ba 0.2 O 2.95, Sn
Si _0.6 Al _0.1 B _0.1 P _0.1 Ca _0.2 O _2.95 , SnS
i _0.6 Al _0.4 B _0.2 Mg _0.1 O _3.2 , SnSi _0.6 A
_{l 0.1 B 0.3 P 0. 1 O} 3.05, SnSi 0.6 Al 0.2 Mg
_{0.2 O 2.7, SnSi 0.6 Al 0.2} Ca 0. 2 O 2.7, S
nSi _0.6 Al _0.2 P _0.2 O ₃ , SnSi _0.6 B _0.2 P
_0.2 O ₃ , SnSi _0.8 Al _0.2 O _2.9 , SnSi _0.8
Al _0.3 B _0.2 P _0.2 O _3.85 , SnSi _0.8 B _0.2 O
_2.9 , SnSi _0.8 Ba _0.2 O _2.8 , SnSi _0.8 Mg
_{0. 2 O 2.8, SnSi 0.8 Ca} 0.2 O 2.8, SnSi
_0.8 P _0.2 O _3.1 .

Sn_0.9Mn_0.3B_0.4P_0.4Ca_0.1R
b_0.1O_2.95, Sn_0.9Fe_0.3B_0.4P_0.4Ca_0.1
Rb_0.1O_2.95, Sn_0.8Pb_0.2Ca_0.1P_0.9O
_3.35, Sn_0.3Ge_0.7Ba_0.1P_0.9O_{3. 35}, Sn
_0.9Mn_0.1Mg_0.1P_0.9O_3.35, Sn_0.2Mn_0.8
Mg_0.1P_0.9O_3.35, Sn_0.7Pb_0.3Ca_0.1P
_0.9O_3.35, Sn_0.2Ge_0.8Ba_0.1P _0.9O_3.35

The chemical formula of the compound obtained by calcining can be calculated by inductively coupled plasma (ICP) emission spectroscopy as a measuring method, and can be calculated from the difference in weight of powder before and after calcining as a simple method. The amount of light metal inserted into the negative electrode material of the present invention may be up to approximating the deposition potential of the light metal.
The amount is preferably from 50 to 700 mol%, more preferably from 100 to 600 mol%, per negative electrode material. It is preferable that the release amount be larger than the insertion amount. How to insert light metal
Electrochemical, chemical and thermal methods are preferred. As the electrochemical method, a method of electrochemically inserting a light metal contained in the positive electrode active material or a method of directly electrochemically inserting a light metal or an alloy thereof from a light metal is preferable. As a chemical method, there is a method of mixing or contacting with a light metal or a method of reacting with an organic metal such as butyllithium. Electrochemical and chemical methods are preferred. The light metal is particularly preferably lithium or lithium ion.

In the present invention, the general
The compound represented by the formula (1) or (2) is mainly used as a negative electrode material.
By using as
High discharge voltage, high capacity, high safety,
A non-aqueous electrolyte secondary battery with excellent flow characteristics can be obtained.
You. In the present invention, particularly excellent effects can be obtained.
Is a compound containing Sn and the valence of Sn is divalent.
The compound is used as a negative electrode material. The valence of Sn is
It can be determined by a chemical titration operation. For example, Phys
ics and Chemistry of Glasses Vol.8 No.4 (1967)
It can be analyzed by the method described on page 65. Also, S
shift by solid state nuclear magnetic resonance (NMR) measurement of n
It is also possible to determine from. For example, for wide measurement
And the metal Sn (zero-valent Sn) is Sn (CH_Three)_FourAgainst
Peak appears at an extremely low magnetic field around 7000 ppm
On the other hand, SnO (= divalent) is around 100 ppm,
SnO_Two(= Tetravalent) appears around -600 ppm
You. Thus, when the same ligand is used, the night shift is
Since it largely depends on the valence of Sn, which is the central metal,¹¹⁹
Determination of valence at peak position determined by Sn-NMR measurement
Becomes possible.

Various compounds can be included in the negative electrode material of the present invention. For example, transition metals (Sc, Ti, V, C
r, Mn, Fe, Co, Ni, Cu, Zn, Y, Zr,
Nb, Mo, Tc, Ru, Rh, Pd, Ag, Cd, lanthanoid metal, Hf, Ta, W, Re, Os, I
r, Pt, Au, Hg) and Group 17 elements of the periodic table (F, C
l) can be included. Further, it may contain dopants of various compounds (for example, compounds of Sb, In, and Nb) that increase electron conductivity. The amount of the compound to be added is 0 to 2
0 mol% is preferred.

In the present invention, the method for synthesizing the composite oxide mainly composed of the oxides represented by the general formulas (1) and (2) is a firing method,
Any of the solution methods can be employed. For example, the firing method will be described in detail. M ¹ compound, M ² compound and M ⁴ compound (M ¹ and M ² are different from Si, Ge, S
n, Pb, P, B, Al, Sb and M ⁴ are Mg, Ca, S
r and Ba) may be mixed and fired. Examples of the Sn compound include SnO, SnO ₂ , Sn ₂ O ₃ , and Sn.
₃ O ₄ , Sn ₇ O ₁₃ .H ₂ O, Sn ₈ O ₁₅ , stannous hydroxide, stannic oxyhydroxide, stannic acid, stannous oxalate, stannous phosphate, orthostannic acid, meta Stannic acid, parastannic acid, stannous fluoride,
Examples thereof include stannic fluoride, stannous chloride, stannic chloride, stannous pyrophosphate, tin phosphide, stannous sulfide, and stannic sulfide. Examples of the Si compound include SiO ₂ , S
Organic silicon compounds such as iO, tetramethylsilane and tetraethylsilane, alkoxysilane compounds such as tetramethoxysilane and tetraethoxysilane, and hydrosilane compounds such as trichlorohydrosilane can be exemplified. Examples of the Ge compound include GeO ₂ , GeO, alkoxy germanium compounds such as germanium tetramethoxide and germanium tetraethoxide.

Examples of the Pb compound include PbO ₂ , P
bO, Pb ₂ O ₃ , Pb ₃ O ₄ , lead nitrate, lead carbonate, lead formate, lead acetate, lead tetraacetate, lead tartrate, lead diethoxide, lead di (isopropoxide) and the like can be mentioned. Examples of the P compound include phosphorus pentoxide, phosphorus oxychloride, phosphorus pentachloride, phosphorus trichloride, phosphorus tribromide, trimethyl phosphate, triethyl phosphate, tripropyl phosphate, stannous pyrophosphate, boron phosphate and the like. Can be mentioned. As the B compound, for example, boron trioxide, boron trichloride,
Examples thereof include boron tribromide, boron carbide, boric acid, trimethyl borate, triethyl borate, tripropyl borate, tributyl borate, boron phosphide, and boron phosphate. Examples of the Al compound include aluminum oxide (α-alumina, β-alumina), aluminum silicate, aluminum tri-iso-propoxide, aluminum tellurite, aluminum chloride, aluminum boride, aluminum phosphide, aluminum phosphate, and lactic acid. Examples include aluminum, aluminum borate, aluminum sulfide, aluminum sulfate, and aluminum boride. Examples of the Sb compound include diantimony trioxide and triphenylantimony. Examples of the Mg, Ca, Sr, and Ba compounds include respective oxides, hydroxides, carbonates, phosphates, sulfates, nitrates, and aluminum compounds.

As the firing conditions, the heating rate is preferably 4 ° C. or more and 2000 ° C. or less per minute.
More preferably, it is 6 ° C. or more and 2000 ° C. or less. It is particularly preferably 10 ° C or more and 2000 ° C or less, and the firing temperature is preferably 250 ° C or more and 1500 ° C or less, more preferably 350 ° C or more and 1500 ° C or less.
Or less, particularly preferably 500 ° C. or more and 1500 ° C.
Or less, and the firing time is 0.01 hour or more and 1
The heating time is preferably not more than 00 hours, more preferably not less than 0.5 hours and not more than 70 hours, particularly preferably not less than 1 hour and not more than 20 hours, and the temperature decreasing rate is not less than 2 ° C. and not more than 107 ° C. per minute. The temperature is more preferably 4 ° C to 107 ° C, particularly preferably 6 ° C to 107 ° C, particularly preferably 1 ° C to 107 ° C.
0 ° C or more and 107 ° C or less. The rate of temperature rise in the present invention is an average rate of temperature rise from “50% of firing temperature (displayed in ° C)” to “80% of firing temperature (displayed in ° C)”. "Firing temperature (℃
80% of the display) to “50% of the firing temperature (° C)”
Is the average rate of temperature drop to reach.

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

The average particle size of the compounds represented by formulas (1) and (2) used in the present invention is preferably from 1.0 to 30 μm, particularly preferably from 2.0 to 20 μm. In order to obtain a predetermined particle size, a well-known pulverizer or classifier is used. For example, a mortar, a ball mill, a sand mill, a vibration ball mill, a satellite ball mill, a planetary ball mill, a swirling air jet mill, a sieve, and the like are used. At the time of pulverization, wet pulverization in the presence of water or an organic solvent such as methanol can also be performed as necessary. Classification is preferably performed to obtain a desired particle size. The classification method is not particularly limited, and a sieve, an air classifier, a drainage, and the like can be used as necessary. Classification can be performed both in a dry type and a wet type. In particular, in the present invention, it is preferable to remove fine powder of 1 μm or less as much as possible. The fine fraction to be mixed is 3% or less by volume fraction, more preferably 1% or less. In order to remove unreacted raw materials and the like from the negative electrode material particles, the particles may be washed with water, or with an organic solvent or a water-containing organic solvent. The pH of water or an organic solvent may be adjusted with an appropriate salt.

More preferred lithium-containing transition metal oxide cathode materials used in the present invention include lithium compounds / transition metal compounds (where transition metals are Ti, V, C
It is preferable to mix and synthesize so that the total molar ratio of r, Mn, Fe, Co, Ni, Mo, and W) is 0.3 to 2.2. Particularly preferred lithium-containing transition metal oxide cathode materials used in the present invention include lithium compounds / transition metal compounds (where the transition metal is at least one selected from V, Cr, Mn, Fe, Co, and Ni). Is a total molar ratio of 0.3 to
It is preferable to synthesize them by mixing them to 2.2.
Particularly preferred lithium-containing transition metal oxide cathode material used in the present invention is Li _x QO _y (where Q is mainly, at least one of which is Co, Mn, Ni, V, F
e), x = 0.2-1.2, y = 1.4
To 3). As Q, besides transition metals, Al, Ga, In, Ge, Sn, Pb, Sb, Bi,
Si, P, B, etc. may be mixed. The mixing amount is preferably 0 to 30 mol% based on the transition metal.

More preferred lithium used in the present invention
Li-containing metal oxide cathode materials include Li_xCoO_Two,
Li_xNiO_Two, Li_xMnO_Two, Li_xCo_aNi
_1-aO _Two, Li_xCo_bV_1-bO_z, Li_xCo_bFe
_1-bO_Two, Li_xMn_TwoO_Four, Li_xMn_cCo_2-cO
_Four, Li_xMn_cNi_2-cO_Four, Li_xMn_cV_2-cO
_Four, Li_xMn_cFe_2-cO_Four(Where x = 0.7-
1.2, a = 0.1-0.9, b = 0.8-0.98,
c = 1.6 to 1.96, z = 2.01 to 2.3).
Can be Most preferred lithium containing used in the present invention
As the transition metal oxide cathode material, Li_xCoO_Two, L
i_xNiO_Two, Li_xMnO_Two, Li_xCo_aNi_1-a
O_Two, Li_xMn_TwoO_Four, Li_xCo_bV_1-bO_z(This
Where x = 0.7-1.2, a = 0.1-0.9, b =
0.9 to 0.98, z = 2.01 to 2.3).
You. Here, the above x value is a value before the start of charging and discharging,
It increases or decreases due to charge and discharge.

The conductive carbon compound that can be used in the present invention is not particularly limited as long as it is an electron conductive material that does not cause a chemical change in the constructed battery. Specific examples include flake graphite, flake graphite, natural graphite such as earthy graphite, petroleum coke, coal coke, celluloses, sugars, high-temperature fired bodies such as mesophase pitch, and graphite such as artificial graphite such as vapor-grown graphite. Carbon blacks such as acetylene black, furnace black, ketjen black, channel black, lamp black and thermal black, asphalt pitch, coal tar, activated carbon, meso fuse pitch, polyacene and the like. Among these, graphite and carbon black are preferred. Non-carbon conductive agents include conductive fibers such as metal fibers, metal powders such as copper, nickel, aluminum, and silver; conductive whiskers such as zinc oxide and potassium titanate; and conductive metals such as titanium oxide. An oxide or the like may be included alone or a mixture thereof as necessary. The amount of the conductive agent added to the mixture layer is preferably 6 to 50% by weight, and more preferably 6 to 30% by weight, based on the negative electrode material or the positive electrode material. In the case of carbon or graphite, the content is particularly preferably 6 to 20% by weight.

As the binder for holding the electrode mixture used in the present invention, a polysaccharide, a thermoplastic resin and a polymer having rubber elasticity or a mixture thereof can be used. Preferred binders are starch, carboxymethylcellulose, cellulose, diacetylcellulose, methylcellulose, hydroxyethylcellulose, hydroxypropylcellulose, sodium alginate,
Water-soluble polymers such as polyacrylic acid, sodium polyacrylate, polyvinylphenol, polyvinylmethylether, polyvinylalcohol, polyvinylpyrrolidone, polyacrylamide, polyhydroxy (meth) acrylate, styrene-maleic acid copolymer, polyvinyl chloride, polytetra Fluoroethylene, polyvinylidene fluoride, tetrafluoroethylene-hexafluoropropylene copolymer, vinylidene fluoride-tetrafluoroethylene-hexafluoropropylene copolymer, polyethylene, polypropylene, ethylene-propylene-diene terpolymer (EPDM), sulfone (Meth) acrylates containing (meth) acrylic esters such as activated EPDM, polyvinyl acetal resin, methyl methacrylate, and 2-ethylhexyl acrylate Acrylic acid ester copolymer, (meth) acrylic acid ester - acrylonitrile copolymer,
Polyvinyl ester copolymer containing vinyl ester such as vinyl acetate, styrene butadiene copolymer, acrylonitrile butadiene copolymer, polybutadiene, neoprene rubber, fluoro rubber, polyethylene oxide, polyester polyurethane resin, polyether polyurethane resin, polycarbonate Emulsions (latex) or suspensions of polyurethane resins, polyester resins, phenol resins, epoxy resins and the like can be given. In particular, polyacrylate latex, carboxymethyl cellulose, polytetrafluoroethylene, and polyvinylidene fluoride are preferred. These binders can be used alone or as a mixture. If the amount of the binder added is small, the holding power and cohesive force of the electrode mixture is weak and the cycleability is poor, and if too large, the electrode volume increases and the volume per electrode unit volume or unit weight decreases, and further, The conductivity decreases and the capacity decreases. The amount of the binder added is not particularly limited, but is 1 to 30.
% By weight, and particularly preferably 2 to 10% by weight.

The preparation of the negative electrode mixture or the positive electrode mixture paste of the present invention is preferably carried out in an aqueous system. The mixture paste is prepared by first mixing the active material and the conductive agent, adding a binder (resin powder suspension or emulsion (latex)) and water and kneading and mixing. The dispersion can be carried out by a homogenizer, a dissolver, a planetary mixer, a paint shaker, a stirring mixer such as a sand mill, or a disperser. The prepared mixture paste of the positive electrode active material and the negative electrode active material is mainly used after being coated (coated) on a current collector, dried, and compressed. Coating can be performed by various methods, for example, 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. I can do it. The blade method, the knife method and the extrusion method are preferred. The coating is preferably performed at a speed of 0.1 to 100 m / min. At this time, by selecting the above-mentioned coating method in accordance with the liquid physical properties and drying properties of the mixture paste, a good surface state of the coating layer can be obtained. The thickness, length and width of the coating layer are determined depending on the size of the battery. The thickness of the coating layer is particularly preferably 1 to 2000 μm in a compressed state after drying.

As a drying or dehydrating method for removing moisture from the pellets and sheets, generally employed methods can be used, and hot air, vacuum, infrared rays, far infrared rays, electron beams and low humidity air can be used alone or in combination. Can be used. The temperature is preferably in the range of 80 to 350C, particularly preferably in the range of 100 to 250C. The water content is preferably 2000 ppm or less for the whole battery, and is preferably 500 ppm or less for each of the positive electrode mixture, the negative electrode mixture and the electrolyte from the viewpoint of charge / discharge cycle characteristics.

The compression of the sheet-shaped electrode mixture can be performed by a commonly used pressing method, but a die pressing method and a calender pressing method are particularly preferable. The pressing pressure is not particularly limited, but is 10 kg / cm ^{2 to 3} t / c.
m ² is preferred. The press speed of the calendar press method is
0.1 to 50 m / min is preferred. Press temperature is from room temperature
200 ° C. is preferred.

The support or current collector for the positive electrode and the negative electrode that can be used in the present invention is made of aluminum, stainless steel, nickel, titanium, or an alloy thereof for the positive electrode, and copper, stainless steel, or the like for the negative electrode. Nickel, titanium,
Or, these are alloys, and are in the form of foil, expanded metal, punching metal, or wire mesh. Especially,
Aluminum foil is preferable for the positive electrode, and copper foil is preferable for the negative electrode.

The separator which can be used in the present invention may be any thin film having a high ion permeability, a predetermined mechanical strength, and an insulating thin film.
Fluorine polymer, cellulose polymer, polyimide, nylon, glass fiber, alumina fiber is used,
As the form, a nonwoven fabric, a woven fabric, or a microporous film is used. In particular, the material is preferably polypropylene, polyethylene, a mixture of polypropylene and polyethylene, a mixture of polypropylene and Teflon, a mixture of polyethylene and Teflon, and the form is preferably a microporous film. In particular, a microporous film having a pore size of 0.01 to 1 μm and a thickness of 5 to 50 μm is preferable.

The shape of the battery can be applied to any of buttons, coins, sheets, cylinders, corners and the like. A battery is formed by inserting an electrode wound with a pellet, a sheet, or a separator into a battery can, electrically connecting the can and the electrode, injecting an electrolyte, and sealing the battery. At this time, a safety valve can be used as a sealing plate. Further, it is preferable to use a PTC element in order to guarantee the safety of the battery.

The bottomed battery outer can that can be used in the present invention is made of iron-plated stainless steel plate or stainless steel plate (SUS304, SUS304L, SUS304N, S).
US316, SUS316L, SUS430, SUS4
44, etc.), a nickel-plated stainless steel plate (same as above), aluminum or its alloy, nickel, titanium, and copper.
It has a square tubular shape and a rectangular tubular shape. In particular, when the outer can also serves as the negative electrode terminal, a stainless steel plate or a nickel-plated iron steel plate is preferable, and when the outer can also serves as the positive electrode terminal, a stainless steel plate, aluminum or an alloy thereof is preferable.

The sheet-shaped mixture electrode is wound or folded and inserted into a can, the can and the sheet are electrically connected, an electrolyte is injected, and a battery can is formed using a sealing plate. . At this time, a safety valve can be used as a sealing plate. In addition to the 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, as a countermeasure against an increase in the internal pressure of the battery can, a method of making a cut in the battery can, a gasket cracking method or a sealing plate cracking method can be used. Further, the charger may be provided with a circuit incorporating measures for overcharging and overdischarging.

The entire amount of the electrolytic solution may be injected at one time, but it is preferable to perform it in two or more steps. In the case of injecting in two or more steps, each liquid may have the same composition but different compositions (for example, after injecting a non-aqueous solvent or a solution in which a lithium salt is dissolved in a non-aqueous solvent, a non-aqueous solution having a higher viscosity than the solvent) A solution in which a lithium salt is dissolved in a solvent or a non-aqueous solvent is injected). Further, in order to shorten the injection time of the electrolyte solution, the pressure of the battery can is reduced (preferably 500 to 1).
torr, more preferably 400 to 10 torr) or
Centrifugal force or ultrasonic waves may be applied to the battery can, but in any case, it is preferable that carbon dioxide dissolved in the electrolytic solution is not excessively diffused. In particular, when the injection is performed under reduced pressure, it is preferable to use a method of contacting with a carbon dioxide-containing gas after the injection as described above.

For the can or the lead plate, a metal or an 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. A conventionally known compound or mixture such as asphalt can be used as the sealing agent for sealing.

The gaskets usable in the present invention are olefin polymers, fluorine polymers, cellulose polymers, polyimides and polyamides, and olefin polymers are preferred from the viewpoint of organic solvent resistance and low moisture permeability. Propylene-based polymers are preferred. Further, it is preferably a block copolymer of propylene and ethylene.

The battery of the present invention is covered with an exterior material if necessary. Examples of the exterior material include a heat-shrinkable tube, an adhesive tape, a metal film, paper, cloth, paint, a plastic case, and the like. Further, at least a part of the exterior may be provided with a portion that changes color by heat so that the heat history during use can be recognized. The battery of the present invention is assembled in a battery pack in a plural number in series and / or parallel as required. In addition to safety elements such as positive temperature coefficient resistors, thermal fuses, fuses and / or current interrupting elements, battery packs have safety circuits (voltage, temperature, current, etc. of each battery and / or assembled battery as a whole, Then, a circuit having a function of interrupting the current may be provided. In addition to the positive and negative terminals of the whole battery pack, the positive and negative terminals of each battery, the temperature detection terminals of the whole battery pack and each battery, the current detection terminals of the whole battery pack, etc. shall be provided as external terminals on the battery pack. Can also. The battery pack may have a built-in voltage conversion circuit (such as a DC-DC converter). The connection of each battery may be fixed by welding a lead plate, or may be fixed by a socket or the like so that it can be easily detached. Further, the battery pack may be provided with a display function of the remaining battery capacity, the presence or absence of charging, the number of times of use, and the like.

The battery of the present invention is used for various devices.
In particular, video movies, portable VCRs with built-in monitors, movie cameras with built-in monitors, compact cameras,
It is preferably used for a single-lens reflex camera, a film with a lens, a notebook computer, a notebook word processor, an electronic organizer, a mobile phone, a cordless phone, a razor, a power tool, a power mixer, a car, and the like.

[0049]

The present invention will be described in more detail with reference to specific examples, but the present invention is not limited to the examples unless it exceeds the gist of the invention.

[Example of preparation of positive electrode mixture paste] Positive electrode active material: LiCoO ₂ (a mixture of lithium carbonate and tricobalt tetroxide at a molar ratio of 3: 2 was placed in an alumina crucible and placed in air at 2 ° C./min.). After heating for 4 hours at 750 ° C. and calcining for 4 hours, the temperature is further raised to 900 ° C. at a rate of 2 ° C. per minute, and calcination is performed for 8 hours at that temperature. The dispersion has a conductivity of 0.6 mS / m, a pH of 10.1 and a specific surface area of 0.42 m ² / g by a nitrogen adsorption method when dispersed in water.
g and 10 g of acetylene black are mixed with a homogenizer, followed by 8 g of an aqueous dispersion of a copolymer of 2-ethylhexyl acrylate, acrylic acid and acrylonitrile (solids concentration: 50% by weight) as a binder, and a concentration of 2% by weight. %
Was added and kneaded and mixed, and 50 g of water was further added, followed by stirring and mixing with a homogenizer to prepare a positive electrode mixture paste. [Example of preparing negative electrode mixture paste] Negative electrode active material A; SnGe _0.1 B _0.5 P _0.58 Mg _0.1 K
_0.1 O _3.35 (6.7 g of tin monoxide, 10.3 of tin pyrophosphate)
g, 1.7 g of boron trioxide, 0.7 g of potassium carbonate, 0.4 g of magnesium oxide, 1.0 g of germanium dioxide
Were dry-mixed, placed in an alumina crucible, heated to 1000 ° C. at 15 ° C./min in an argon atmosphere, fired at 1100 ° C. for 12 hours, cooled to room temperature at 10 ° C./min, and taken out of the firing furnace. What was collected and pulverized by a jet mill, the average particle size was 4.5 μm, the volume fraction of particles having a particle size of 1 μm or less was 0.1% or less, and the X-ray diffraction method using CuKα ray showed a 2θ value of around 28 °. It was a substance having a broad peak with a peak, and no crystalline diffraction line was observed at a 2θ value of 40 ° or more and 70 ° or less. ), 30 g of a conductive agent (artificial graphite) and 30 g of a carboxymethylcellulose aqueous solution having a concentration of 2% by weight and 10 g of polyvinylidene fluoride as a binder, and 30 g of water, and further kneading and mixing. And
A negative electrode mixture paste was prepared.

[Preparation of Positive and Negative Electrode Sheets] The positive electrode mixture paste prepared above was coated on both sides of a 30 μm-thick aluminum foil current collector with a blade coater at a coating amount of 40 μm.
The coated sheet was applied at 0 g / m ² so that the thickness of the sheet after compression became 280 μm, dried, and then compression-molded by a roller press and cut into a predetermined size to prepare a belt-shaped positive electrode sheet. Further, it was sufficiently dehydrated and dried with a far-infrared heater in a dry box (dew point: dry air having a temperature of -50 ° C. or less) to prepare a positive electrode sheet. Similarly, paste the negative electrode mixture paste into 20
A negative electrode sheet having a coating amount of 70 g / m ² and a compressed sheet thickness of 90 μm was prepared in the same manner as in the preparation of the positive electrode sheet described above. [Example of electrolytic solution preparation] In an argon atmosphere, put 65.3 g of diethyl carbonate in a 200 cc narrow-necked polypropylene container, and add a small amount of 22.2 g of ethylene carbonate to this solution while taking care that the solution temperature does not exceed 30 ° C. Each was dissolved. Next, 0.4 g of LiBF ₄ and 12.1 g of LiPF ₆ were dissolved little by little in the polypropylene container in order, respectively, while being careful not to exceed a liquid temperature of 30 ° C.
The obtained electrolyte was a colorless and transparent liquid having a specific gravity of 1.135. The water content was 18 ppm. (Measured by Karl Fischer moisture meter)
It was less than 0.001 mol / liter. [Example of Making a Cylinder Battery] A positive electrode sheet, a separator made of a microporous polypropylene film, a negative electrode sheet and a separator were laminated in this order, and this was spirally wound.
The wound body was housed in a nickel-plated iron bottomed cylindrical battery can also serving as a negative electrode terminal. The designated electrolyte was injected into the battery can in the injection booth, and the battery lid having the positive electrode terminal was caulked through a gasket in the sealing booth to seal the battery, thereby producing a cylindrical battery.

Examples 1 to 3 The above-mentioned electrolytic solution was brought into contact with air containing carbon dioxide at a predetermined gas / liquid ratio shown in Table 1 using a diffuser tube. Using this electrolyte, a cylinder battery was prepared according to the above procedure.

Table 1 Carbon dioxide in the electrolyte Example Gas used Gas-liquid ratio Number of carbon dioxide concentration Carbon dioxide content (volume / volume) mol / liter Example 1 1% by volume 1000/1 0.006 Example 2 10 volumes % 100/1 0.02 Example 3 99% by volume 100/1 0.05

Example 4 An electrolyte was placed in a wide-mouthed container, and the entire container was placed in a pressure vessel.
A gas containing carbon dioxide (99%) was introduced into the pressure vessel and pressurized to 3 atm. The pressure in the pressure vessel was returned to normal pressure, the electrolytic solution was taken out, and a cylinder battery was prepared according to the above procedure. Example 5 A cylindrical battery can containing a wound body, into which an electrolyte was injected, was left for 10 hours in a booth in which a carbon dioxide-containing gas (99%) was circulated before sealing, and then sealed. Battery was created. Example 6 A cylindrical battery can containing a wound body in which an electrolytic solution was injected was placed in a pressure vessel before sealing, and a gas containing carbon dioxide (99%) was introduced into the pressure vessel to 3 atm. Pressurized. The pressure inside the pressure vessel was returned to normal pressure, the battery can was taken out, and a cylinder battery was prepared according to the above procedure. Example 7 A gas containing carbon dioxide (99%) was circulated in a sealing booth, and the battery was sealed therein, thereby producing a cylinder battery.

Comparative Example 1 A cylinder battery was prepared in the same manner as in Example 1, except that the electrolyte was not subjected to a contact operation with a carbon dioxide-containing gas and the electrolyte was injected and sealed in a usual manner. Comparative Examples 2 to 4 Instead of an oxide-based negative electrode active material, a carbon-based active material (graphite powder) was used.
And a negative electrode sheet was prepared in the same manner as in the preparation of the negative electrode sheet, and a cylindrical battery was prepared by using the electrolyte solution subjected to the same operation as in Examples 1 to 3. Comparative Example 5 Instead of an oxide-based negative electrode active material, a carbon-based active material (graphite powder) was used.
A negative electrode sheet was prepared in the same manner as in the preparation of the negative electrode sheet, and injected in a usual manner using an electrolytic solution which did not perform a contact operation with a carbon dioxide-containing gas as in Comparative Example 1.
Sealing was performed to produce a cylinder battery. Examples 8 to 10 A negative electrode active material B was prepared in the same manner as in A except that the volume fraction of the fine powder having a particle size of 1 μm or less of the negative electrode active material A was 3%. went. Comparative Example 6 The same experiment as in Comparative Example 1 was performed using the negative electrode active material B.

The battery prepared by the above method was charged and discharged under the conditions of a current density of 5 mA / cm ² , a charge end voltage of 4.1 V, and a discharge end voltage of 2.8 V, and the discharge capacity and cycle life were determined. The ratio of the capacity (Wh) of each battery,
Table 2 shows the cyclability (the ratio of the 300th capacity to the first charge / discharge).

Table 2 Results of Experiment Experiment No. Carbon Dioxide Introduced Negative Electrode Active Material Initial Capacity Cycle Property (%) Example 1 Liquid before Injection Oxide A 100 83 Example 2 Liquid Before Injection Oxide A 101 85 Example 3 Liquid before injection Liquid A 9988 Example 4 Liquid before injection Liquid A 99 91 Example 5 After liquid injection and before sealing Oxide A 100 85 Example 6 After liquid injection and before sealing Oxide A 98 89 Example 7 At the time of sealing Oxide A 98 88 Comparative Example 1 None Oxide A 100 74 Comparative Example 2 Liquid before injection Carbon-based 80 78 Comparative Example 3 Liquid before injection Carbon-based 81 79 Comparative Example 4 Liquid before injection Carbon-based 80 80 Comparative Example 5 None Carbon-based 79 75 Example 8 Liquid Before Injection Oxide B 100 80 Example 9 Liquid Before Injection Oxide B 101 83 Example 10 Liquid Before Injection Oxide B 99 87 Comparative Example 6 None Oxidation Object B 100 69

The battery using the oxide-based negative electrode active material of the present invention had a larger capacity than the battery using the carbon-based negative electrode active material, and was subjected to a contact operation between the electrolyte and a carbon dioxide-containing gas. The battery has improved cycleability, and the rate of improvement is greater than that using a carbon-based negative electrode active material.

[0059]

According to the present invention, the negative electrode contains a material comprising an amorphous chalcogen compound and / or an amorphous oxide,
In addition, by including carbon dioxide in the non-aqueous electrolyte, a non-aqueous electrolyte secondary battery having excellent charge / discharge characteristics and having less deterioration in discharge capacity due to repeated charge / discharge can be obtained.

[Brief description of the drawings]

FIG. 1 is a sectional view of a cylinder type battery used in Examples.

[Explanation of symbols]

 REFERENCE SIGNS LIST 1 Battery outer can also serving as negative electrode terminal 2 Electrode group 3 Insulator 4 Positive lead plate 5 Gasket 6 Battery lid (positive terminal) 61 Explosion-proof valve body 62 Current interrupter 63 PTC element

Claims (8)

[Claims] 1. A negative electrode and a positive electrode containing a material capable of reversibly inserting and extracting lithium, a non-aqueous electrolyte containing a lithium salt,
In a non-aqueous secondary battery comprising a separator, the negative electrode contains three or more atoms selected from Group 1, 2, 13, 14, and 15 atoms of the periodic table, and is mainly an amorphous chalcogen compound and / or an amorphous oxide. A non-aqueous electrolyte secondary battery comprising a material made of a material, and carbon dioxide being contained in the non-aqueous electrolyte. 2. Carbon dioxide contained in the non-aqueous electrolyte is
2. The non-aqueous electrolyte secondary battery according to claim 1, wherein the content is 0.005 mol / liter or more and 0.2 mol / liter or less. 3. The non-aqueous electrolyte secondary battery according to claim 1, wherein the supporting salt contained in the non-aqueous electrolyte is at least LiPF ₆ and / or LiBF ₄ . 4. The non-aqueous electrolyte secondary battery according to claim 1, wherein the negative electrode material is represented by the general formula (1). M ¹ M ² pM ⁴ qM ⁶ r General formula (1) (where M ¹ and M ² are different from each other, Si, Ge, Sn, P
at least one selected from b, P, B, Al, and Sb;
M ⁴ is Li, Na, K, Rb, Cs, Mg, Ca, S
at least one selected from r and Ba, M ⁶ is O, S,
At least one selected from Te, p and q are each 0.0
01 to 10, r represents a number of 1.00 to 50. ) 5. A negative electrode and a positive electrode containing a material capable of reversibly inserting and extracting lithium, a non-aqueous electrolyte containing a lithium salt,
In a non-aqueous secondary battery comprising a separator, the negative electrode contains three or more atoms selected from Group 1, 2, 13, 14, and 15 atoms of the periodic table, and is mainly an amorphous chalcogen compound and / or an amorphous oxide. A method for producing a non-aqueous electrolyte secondary battery, comprising a material comprising a substance, and including carbon dioxide in the non-aqueous electrolyte. 6. The non-aqueous electrolyte secondary battery according to claim 5, wherein the non-aqueous electrolyte is used by being brought into contact with a carbon dioxide-containing gas before being injected into the non-aqueous secondary battery. Manufacturing method. 7. The method for producing a non-aqueous electrolyte secondary battery according to claim 5, wherein, after the non-aqueous electrolyte is injected, the battery is brought into contact with a carbon dioxide-containing gas before sealing. 8. The method according to claim 5, wherein a carbon dioxide-containing gas is sealed in the battery when the non-aqueous secondary battery is sealed, and a carbon dioxide-containing gas is contained in the battery after the sealing. A method for manufacturing a non-aqueous electrolyte secondary battery.