JPH0955203A - Nonaqueous battery - Google Patents

Abstract

PROBLEM TO BE SOLVED: To enhance storage characteristics of a battery after the storage of an electrode and charge/discharge cycle characteristics by specifying the contents of a halogen element in a positive mix and a negative mix. SOLUTION: A lithium compound having a halogen element concentration of 0.01-100ppm and a transition metal compound having a halogen element concentration of 0.01-100ppm are mixed, and the mixture is baked at 250-2000 deg.C to obtain a positive active material having a halogen element concentration of 0.01-100ppm and an average particle size of 0.1-50μm, then the positive active material, a binder, a coating auxiliary material are mixed to obtain a positive mix, and the positive mix is applied to a current collector to obtain a positive electrode sheet 8. A negative electrode material represented by formula SnM<1> a Ot (M<1> is at least two elements selected from Al, B, P, Si, group 1-3 elements of the periodic table, and halogen, a is 0.2-2, and t is 1-6), a binder material, a conductive material, a coating auxiliary material are mixed, and the mixture is applied to a current collector to obtain a negative electrode sheet 9. The positive electrode sheet 8, a separator 10, the negative electrode sheet 9, and the separator 10 are stacked, and spirally wound, then housed into a cylindrical battery can with bottom 11.

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 improved manufacturability and enhanced charge / discharge repeating characteristics.

[0002]

2. Description of the Related Art In a lithium battery or a lithium ion battery, which has recently received attention as a high-capacity battery, the positive electrode and / or the negative electrode thereof contains a positive electrode active material or a negative electrode active material, a conductive agent such as carbon, and a binder such as Teflon. Alternatively, it is used after being kneaded with an organic solvent, applied on a current collector such as aluminum foil or copper foil, and dried. After coating and drying these electrodes, they are stored until assembled into a battery, but after storage, the film quality deteriorates and the mixture is peeled off from the support and cannot be used. There was a problem of significant deterioration.

It is expected that the impurities in the mixture act as the cause of this problem, and the positive electrode is obtained by washing the positive electrode active material (Japanese Patent Laid-Open Nos. 3-64860 and 4-32).
No. 8277) was used but it could not be resolved.

[0004]

SUMMARY OF THE INVENTION An object of the present invention is to obtain a non-aqueous secondary battery having improved film quality after storage of the electrode and repeated charge / discharge performance.

[0005]

An object of the present invention is to provide a positive electrode having a positive electrode mixture applied on a current collector, a negative electrode having a negative electrode mixture applied on a current collector, and a non-containing lithium salt. Regarding a non-aqueous secondary battery comprising a water electrolytic solution, the content of halogen elements as impurities in the positive electrode mixture and / or the negative electrode mixture is 0.
This can be achieved by a non-aqueous battery characterized by having a content of 01 ppm or more and 1000 ppm or less.

[0006]

DETAILED DESCRIPTION OF THE INVENTION Aspects of the present invention will be described in more detail. First, a more preferable embodiment of the positive electrode in the present invention will be described. The positive electrode mixture referred to in the present invention is composed of a positive electrode active material, a binder, a conductive agent, and a coating aid, and the total amount of halogens as impurities in each of the formed mixture is 0.01 ppm or more and 1000 ppm or less. Is preferable, and more preferably 0.01 ppm or more and 100 pp.
m or less, particularly preferably 0.01 ppm or more and 10
It is to be below ppm. The halogen element referred to here is fluorine, bromine, chlorine or iodine, preferably bromine or chlorine, and particularly preferably chlorine.

The positive electrode active material can be synthesized by a method of mixing and firing a lithium compound and a transition metal compound or a solution reaction, but a firing method is particularly preferable. Further, in order to adjust the amount of halogen element in the positive electrode active material to a predetermined amount, the concentration of halogen element in the lithium compound and / or the transition metal compound, which is a firing raw material, is 0.01 ppm or more 100 or more.
It is preferably 0 ppm or less, more preferably 0.01 ppm or more and 100 ppm or less, and particularly preferably 0.01 ppm or more and 10 ppm or less.

Examples of the lithium compound used as a raw material include lithium hydroxide, lithium carbonate, lithium nitrate, lithium acetate, lithium oxalate and the like. Examples of the transition metal compound include cobalt carbonate, cobalt trioxide, cobalt monoxide, cobalt trioxide, cobalt hydroxide, cobalt nitrate, nickel carbonate, nickel nitrate, nickel hydroxide, nickel trioxide, nickel monoxide, nickel trioxide. , Manganese carbonate, manganese nitrate, manganese hydroxide, manganese tetraoxide, manganese monoxide, manganese trioxide, manganese dioxide, ferrous oxide, ferric oxide,
Examples include ferric tetroxide and ferric hydroxide.

A method for increasing the purity of a lithium compound and / or a transition metal compound and adjusting the concentration of halogen element to a predetermined amount is a general purification method, for example, "New Edition Inorganic Chemistry, Toshizo Chitani, Sangyo Tosho". "Publishing Co., Ltd.""New Experimental Chemistry Course, Maruzen Co., Ltd.""Inorganic Drug Manufacturing, Shoji Kametani,"
Masataka Ihara, Asakura Shoten ”can be used.

The firing temperature used in the present invention may be a temperature at which a part of the mixed compound used in the present invention is decomposed and melted. For example, 250 to 2000 ° C. is preferable, and 350 to 1500 ° C. is particularly preferable. . Further, the halogen element can be controlled to the above-mentioned predetermined amount by washing the positive electrode active material. As the cleaning liquid, either water or an organic solvent can be used, but preferably water, methanol,
Ethanol and acetone.

As the positive electrode active material, any transition metal oxide capable of releasing lithium ions or reversibly inserting / releasing lithium ions may be used, but a lithium-containing transition metal oxide is particularly preferable. Preferred lithium-containing transition metal oxide positive electrode active materials used in the present invention include lithium-containing Ti, V, Cr, Mn, Fe, Co, Ni and C.
Examples thereof include oxides containing u, Mo and W. Alkali metals other than lithium (elements IA and IIA of the periodic table), semi-metals Al, Ga, In, Ge, Sn, Pb,
B, Sb, Bi, etc. may be mixed. Mixing amount is 0 to 1
0 mol% is preferable. More preferred lithium-containing transition metal oxide cathode active materials used in the present invention include lithium compounds / transition metal compounds (where the transition metal is T
i, V, Cr, Mn, Fe, Co, Ni, Mo, W, at least one of them) in 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 positive electrode active materials for use in the present invention include lithium compounds / transition metal compounds (where transition metals are V, Cr, Mn, F
The total of at least one selected from e, Co, and Ni)
It is preferable to mix them so that the molar ratio thereof is 0.3 to 2.2. Particularly preferable lithium-containing transition metal oxide positive electrode active material used in the present invention is Lix Q.
Oy (here, M = Co, Mn, Ni, V, transition metal containing at least one selected from Fe), x = 0.2 to
1.2, y = 1.4-3).

More preferred lithium-containing metal oxide positive electrode active materials used in the present invention are Li _x CoO ₂ ,
Li _x NiO ₂ , Li _x Co _a Ni _1-a O ₂ , Li _z Co _b V
_1-b O _z , Li _x Co _b Fe _1-b O ₂ , Li _x Mn ₂ O ₄ , Li _x
Mn _c Co _2-c O ₄ , Li _x Mn _c Ni _2-c O ₄ , Li _x Mn _{c
V 2-c O z, Li} x Mn c Fe 2-c O 4, Li x Mn 2 O 4 and M
nO ₂ mixture, Li _2x MnO ₃ and MnO ₂ mixture, L
i _x Mn ₂ O ₄ , a mixture of Li _2x MnO ₃ and MnO ₂ (where x = 0.2 to 1.2, a = 0.1 to 0.9, b = 0.
8-0.98, c = 1.6-1.96, z = 2.01-
5) can be given. A more preferable lithium-containing metal oxide positive electrode active material used in the present invention is Li _x C.
oO ₂ , Li _x NiO ₂ , Li _x Co _a Ni _1-a O ₂ , Li _x C
_{o b V 1-b O z} , Li x Co b Fe 1-b O 2, Li x Mn 2 O 4,
_{Li x Mn c Co 2-c} O 4, Li x Mn c Ni 2-c O 4, Li x
Mn _c V _2-c O ₄ , Li _x Mn _c Fe _2-c O ₄ (where x =
0.7 to 1.04, a = 0.1 to 0.9, b = 0.8 to
0.98, c = 1.6-1.96, z = 2.01-2.
3) can be given. The most preferable lithium-containing transition metal oxide positive electrode active material used in the present invention is Li _x.
CoO ₂ , Li _x NiO ₂ , Li _x Co _a Ni _1-a O ₂ , Li _x
Mn ₂ O ₄ , Li _x Co _b V _1-b O _z (where x = 0.7 to
1.1, a = 0.1 to 0.9, b = 0.9 to 0.98,
z = 2.01 to 2.3). Here, the above-mentioned x value is a value before the start of charge / discharge, and increases / decreases due to charge / discharge.

The average particle size of the positive electrode active material used in the present invention is not particularly limited, but is preferably 0.1 to 50 μm. In order to obtain a predetermined particle size, a well-known pulverizer or classifier is used. For example, a mortar, a ball mill, a vibrating ball mill, a satellite ball mill, a planetary ball mill, a swirling airflow type jet mill, a sieve and the like are used. The conductive agent is
In the constructed battery, any electron conductive material that does not cause a chemical change may be used, but the content of halogen elements as impurities is preferably 0.01 ppm or more and 1000 ppm or less, more preferably 0.01 ppm or more and 100 ppm or less. And particularly preferably 0.01 p
That is, pm or more and 10 ppm or less. It is preferable to wash the positive electrode active material in the same manner as the positive electrode active material in order to adjust the halogen element content to a predetermined amount. Specific examples of the conductive agent include natural graphite (scaly graphite, flake graphite, earth graphite, etc.), artificial graphite, carbon black, acetylene black, Ketjen black, carbon fibers and metals (copper, nickel, aluminum, Silver (JP-A-63-148,554) powder, metal fiber or polyphenylene derivative (JP-A-59-2)
0,971) and the like, may be included as one kind or a mixture thereof. A combination of graphite and acetylene black is particularly preferred. The addition amount is 1 to 5
0% by weight is preferable, and 2 to 30% by weight is particularly preferable.
For carbon and graphite, 2 to 15% by weight is particularly preferred.

The content of halogen elements as impurities in the binder is preferably 0.01 ppm or more and 1000 ppm or less, and more preferably 0.01 ppm or more and 10 ppm or less.
It is 0 ppm or less, and particularly preferably 0.01 ppm or more and 10 ppm or less. It is preferable to wash the positive electrode active material in the same manner as the positive electrode active material in order to adjust the halogen element content to a predetermined amount. Specifically as the binder, starch,
Polyvinyl alcohol, carboxymethyl cellulose,
Hydroxypropyl cellulose, regenerated cellulose, diacetyl cellulose, polyvinyl chloride, polyvinylpyrrolidone, tetrafluoroethylene, polyvinylidene fluoride, polyethylene, polypropylene, ethylene-propylene-diene terpolymer (EPDM), sulfonated E
PDM, styrene-butadiene rubber, polybutadiene, fluororubber, polysaccharides such as polyethylene oxide, thermoplastic resins, polymers having rubber elasticity and the like are used alone or as a mixture thereof. When a compound containing a functional group that reacts with lithium, such as a polysaccharide, is used, for example, it is preferable to add a compound such as an isocyanate group to deactivate the functional group. The addition amount of the binder is preferably 1 to 50% by weight, and particularly 2 to
30% by weight is preferred.

The negative electrode mixture referred to in the present invention comprises a negative electrode material, a binder, a conductive agent and a coating aid. The content of halogen elements in each of the impurities in the negative electrode material used in the present invention is preferably 0.01 ppm or more and 1000 ppm or less, more preferably 0.01 ppm or more and 100 ppm or less.
It is ppm or less, and particularly preferably 0.01 ppm or more and 10 ppm or less. The halogen element referred to here is fluorine, bromine, chlorine or iodine, preferably bromine or chlorine, and particularly preferably chlorine.

The negative electrode material used in the present invention may be any compound that can occlude and release light metal ions. In particular, light metals, light metal alloys, carbonaceous compounds, inorganic oxides,
Inorganic chalcogenides, metal complexes, and organic polymer compounds are preferred. These may be used alone or in combination. For example, a light metal and a carbonaceous compound, a light metal and an inorganic oxide, a combination of a light metal and a carbonaceous compound and an inorganic oxide, and the like can be given. These negative electrode materials are preferable because they provide high capacity, high discharge potential, high safety, and high cycle properties. Lithium is preferred as the light metal ion.

As the light metal, lithium is preferable. Examples of the light metal alloy include a metal forming an alloy with lithium or an alloy containing lithium. Al, Al-Mn, A
1-Mg, Al-Sn, Al-In, and Al-Cd are particularly preferred. The carbonaceous compound is selected from natural graphite, artificial graphite, vapor grown carbon, calcined organic material, and the like, and preferably contains a graphite structure. Further, the carbonaceous compounds, in addition to carbon, a heterologous compound, e.g. B, P, N, S, SiC, B 4 C and may comprise 0 to 10 wt%.

The element forming the oxide or chalcogenide is preferably a transition metal or a metal or metalloid element belonging to Group 13 to Group 15 of the periodic table.

As the transition metal compound, in particular, V, Ti,
A single or composite oxide of Fe, Mn, Co, Ni, Zn, W, and Mo, or a chalcogenide is preferable. Further preferred compounds of JP-A 6-44,972 No. claimed _{Li p Co q V 1-q} O r ( wherein p = 0.1 to 2.5, q =
0 to 1, z = 1.3 to 4.5).

Compounds of metals and semimetals other than transition metals include elements belonging to Groups 13 to 15 of the periodic table, Al, Ga,
Oxides and chalcogenides selected from Si, Sn, Ge, Pb, Sb and Bi alone or in combination of two or more thereof are selected. For example, Al ₂ O ₃ , Ga ₂ O ₃ , Si
O, SiO ₂ , GeO, GeO ₂ , SnO, SnO ₂ , S
nSiO ₃ , PbO, PbO ₂ , Pb ₂ O ₃ , Pb ₂ O ₄ , P
_{b 3 O 4, Sb 2 O} 3, Sb 2 O 4, Sb 2 O 5, Bi 2 O 3, B
i ₂ O ₄ , Bi ₂ O ₅ , SnSiO ₃ , GeS, GeS ₂ , S
nS, SnS ₂ , PbS, PbS ₂ , Sb ₂ S ₃ , Sb
₂ S ₅ and SnSiS ₃ are preferred. These are complex oxides with lithium oxide, such as Li ₂ GeO ₃ and Li ₂
It may be SnO ₂ .

The above-described composite chalcogen compound and composite oxide are preferably mainly amorphous when incorporated in a 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 2θ value is 40 ° or more and 70
The strongest of the crystalline diffraction lines seen below ° is
It is preferably 500 times or less, more preferably 100 times or less, particularly preferably 5 times or less, of the intensity of the diffraction line at the apex of the broad scattering band observed in the 2θ value of 20 ° or more and 40 ° or less. Most preferably, it has no crystalline diffraction line.

The above complex chalcogen compounds and complex oxides are B, Al, Ga, In, Tl, Si, Ge, Sn and P.
It is a complex chalcogen compound or complex oxide of three or more kinds of elements among b, P, As, Sb and Bi, and more preferably a complex oxide. Particularly preferably B, Al, Si, G
It is a composite oxide composed of three or more elements of e, Sn, and P. These complex oxides may contain an element of Group 1 to 3 or a halogen element of the periodic table mainly for modifying the amorphous structure.

Among the above-mentioned negative electrode materials, an amorphous composite oxide containing tin as a main component is particularly preferable, and the following general formulas (1) to (1)
It is represented by (3). SnM ¹ _a O _t General formula (1) In the formula, M ¹ is two or more selected from Al, B, P, Si, Group 1 element, Group 2 element, Group 3 element, and halogen element of the periodic table. A represents a number of 0.2 or more and 2 or less, and t represents a number of 1 or more and 6 or less.

SnM ² _b O _t General formula (2): In the formula, M ² is Al, B, P, a Group 1 element of the periodic table, a second group
It represents two or more kinds of elements selected from group elements, group 3 elements and halogen elements, b represents a number of 0.2 or more and 2 or less, and t represents a number of 1 or more and 6 or less.

SnM ³ _c M ⁴ _d O _t General Formula (3) In the formula, M ³ is at least two kinds of Al, B, P and Si,
M ⁴ is a group 1 element, a group 2 element, a group 3 element of the periodic table,
Represents at least one kind of halogen element, c is a number of 0.2 or more and 2 or less, d is a number of 0.01 or more and 1 or less,
0.2 <c + d <2, t represents a number from 1 to 6. M
³ and M ⁴ are elements for amorphizing the compound of the general formula (3) as a whole, M ³ is an element which can be made amorphous, and contains two or more kinds of Al, B, P and Si. It is preferable to use them in combination. M ⁴ is an element that can be modified to be amorphous, and is a Group 1 element, a Group 2 element, a Group 3 element, or a halogen element of the periodic table.

In the formulas (1) to (3), the periodic tables 1 to 3 are shown.
Among group and halogen, K, Na, Cs, Mg, Ca, B
Preferred are a, Y and F.

For the amorphous composite oxide of the present invention, any of a firing method and a solution method can be adopted, but the firing method is more preferable. In the baking method, it is preferable to mix well the oxides or compounds of the elements described in the general formula (1) and then bake to obtain an amorphous composite oxide.

As the firing conditions, the heating rate is preferably 5 ° C. to 200 ° C./min, the firing temperature is preferably 500 ° C. to 1500 ° C., and the firing time is Is more than 1 hour 10
It is preferably 0 hours or less. And, it is preferable as the descending rate of temperature or less per minute 2 ℃ least 10 ⁷ ° C.. In the present invention, the heating rate is defined as “the firing temperature (° C.)
Is the average rate of temperature rise from "50% of the firing temperature (expressed in ° C)" to "80% of the firing temperature (expressed in ° C)." It is the average rate of temperature drop until it reaches "50% (in ° C)". The temperature may be cooled in a firing furnace, or may be taken out of the firing furnace and put into, for example, water for cooling. Also 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. Also, the single roller method described in page 172 of the New Glass Handbook (Maruzen 1991),
Cooling may be performed using a twin roller method. 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 most preferred inert gas is pure argon.

The compound represented by the present invention preferably has an average particle size of 0.1 to 60 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 vibrating ball mill, a satellite ball mill, a planetary ball mill, a swirling airflow type jet mill, a sieve and the like are used. At the time of pulverization, wet pulverization in 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, or the like can be used as necessary. Classification can be performed both in a dry type and a wet type.

Examples of the negative electrode material of the present invention are shown below.
The invention is not limited to these. SnAl_0.1
B_0.3P_0.4K_0.2O_2.7, SnAl_0.1B_0.3P_0.4Na_0.2
O_2.7, SnAl_0.1B_0.3P_0.4Rb_0.2O_2.7, SnAl
_0.1B_0.3P_0.4Cs_0.2O_2.7, SnAl_0.1B_0.5P_0.5M
g_0.1F_0.2O_3.15, SnAl_0.1B_0.5P_0.5Ba_0.08F
_0.08O _3.19, SnAl_0.2B_0.4P_0.4O_2.9, SnAl
_0.3B_0.5P_0.2O_2.7, SnAl_{0. Three}B_0.7O_2.5, SnB
_0.2P_0.6Ba_0.08F_0.08O_2.84, SnB_0.4P_0.4Ba
_0.1F _0.1O_2.65, SnB_0.5P_0.5O_Three, SnB_0.5P_0.5
Mg_0.1O_3.1,

SnB_0.5P_0.5Mg_0.1F_0.2O_Three, SnB
_0.5P_0.5Li_0.1Mg_0.1F_0.2O_3.05, SnB_0.5P_0.5
K_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_0.2
O_3.03, SnB_0.5P_0.5Cs_0.1Mg_0.1F_0.2O_3.05,
SnB_0.5P_0.5Cs_0.05Mg_0.05F_0.1O_3.03, SnB
_0.5P _0.5Mg_0.1F_0.1O_3.05, SnB_0.5P_0.5Mg_0.1
F_0.2O_Three, SnB_0.5P_0.5Mg _0.1F_0.06O_3.07, Sn
B_0.5P_0.5Mg_0.1F_0.14O_3.03, SnPBa_0.08O
_3.58, SnPK_0.1O_3.55, SnPK_0.05Mg_0.05O
_3.58, SnPCs_0.1O_3.55, SnPBa_0.08F_0.08O
_3.54, SnPK_0.1Mg_0.1F_0.2O_3.55, SnPK_0.05
Mg_0.05F_0.1O_3.53, SnPCs_0.1Mg_0.1F_0.2O
_3.55, SnPCs_0.05Mg_{0. 05}F_0.1O_3.53,

[0033] Sn_1.1B_0.2P_0.6Ba_0.08F
_0.08O_2.94, Sn_1.1B_0.2P_0.6Li_0.1K_0.1Ba _0.1F
_0.1O_3.05, Sn_1.1B_0.4P_0.4Ba_0.08O_2.74, Sn
_1.1PCs_0.05O_3.63, Sn_1.1PK_0.05O_3.63, Sn
_1.2Al_0.1B_0.3P_0.4Cs_0.2O_2.9, Sn_1.2B _0.2P
_0.6Ba_0.08O_3.08, Sn_1.2B_0.2P_0.6Ba_0.08F_0.08
O_3.04, Sn_1.2B _0.2P_0.6Mg_0.04Ba_0.04O_3.08,
Sn_1.2B_0.3P_0.5Ba_0.08O_2.98, Sn_1.3Al_0.1B
_0.3P_0.4Na_0.2O_Three, Sn_1.3B_0.4P_0.4Ca
_0.2O_3.1, Sn_1.3B_0.4P_0.4Ba_0.2O_3.1, Sn_1.4P
K_0.2O_Four, Sn_1.4Ba_0.1PK_0.2O_4.15, Sn_{1 .Four}Ba
_0.2PK_0.2O_4.3, Sn_1.4Ba_0.2PK_0.2Ba_0.1F_0.2
O_4.3, Sn_1.4PK_0.3O_4.05, Sn_1.5PK_0.2O_4.1,
Sn_1.5PK_0.1O_4.05, Sn_1.5PCs_{0.0 Five}O_4.03, S
n_1.5PCs_0.05Mg_0.1F_0.2O_4.03, Sn₂P₂O₇

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 , SnSi _0.5 Al
_0.2 B _0.1 P _0.1 Mg _0.1 O _2.8 , SnSi _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 , SnS
i _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 , SnSi _0.6 Al _0.1 B _0.1 P _0.1 Ba
_0.2 O _2.95 . SnSi _0.6 Al _0.1 B _0.1 P _0.1 Ca _0.2 O
_{2.95, SnSi 0.6 Al 0.1 B 0} .2 Mg 0.2 O 2.85, SnS
i _0.6 Al _0.1 B _0.3 P _0.1 O _3.05 , SnSi _0.6 Al _0.2 M
g _0.2 O _2.7 , SnSi _0.6 Al _0.2 Ca _0.2 O _2.7 , SnS
i _0.6 Al _0.2 P _0.2 O ₃ , SnSi _0.6 B _0.2 P _0.2 O ₃ , S
nSi _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_0.1Rb_0.1
O_2.95, Sn_0.9Fe_0.3B_0.4P_0.4Ca_0.1Rb_0.1O
_2.95, Sn_0.8Pb_0.2Ca_0.1P_0.9O_3.35, Sn_0.3G
e_0.7Ba _0.1P_0.9O_3.35, Sn_0.9Mn_0.1Mg_0.1P
_0.9O_3.35, Sn_0.2Mn_0.8Mg_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. 9}O_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 from the weight difference between before and after calcining as a simple method.

The amount of light metal to be inserted into the negative electrode material of the present invention may be a value close to 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.

The negative electrode material of the present invention can contain various elements. For example, lanthanoid metals (Hf, T
a, W, Re, Os, Ir, Pt, Au, Hg) and various compounds that increase electron conductivity (for example, Sb, In, N
b) may be included. The amount of the compound to be added is preferably 0 to 5 mol%.

Further, the halogen element concentration is preferably 0.01 ppm or more and 1000 ppm or less, and more preferably 0.01 ppm or more and 100 p or more, as a firing raw material so that the amount of halogen element in the negative electrode material is a predetermined amount.
pm or less, particularly preferably 0.01 ppm or more 1
It is 0 ppm or less.

The halogen element can be controlled to the above-mentioned predetermined amount by washing the negative electrode material. As the cleaning liquid, either water or an organic solvent can be used, but water, methanol, ethanol or acetone is preferable.

The conductive agent and the binder have the same meanings as used in the positive electrode mixture.

In the present invention, a positive electrode active material, a negative electrode material other than lithium metal or a lithium aluminum alloy, is kneaded with a conductive agent and a binder using water as a coating aid and / or an organic solvent as a medium to obtain a slurry. The electrode sheet is obtained by coating, drying, pressing and cutting on both sides of the current collector, and the content of halogen elements as impurities in the present slurry is preferably 0.01 ppm or more and 1000 ppm or less, and more preferably 0.01ppm or more 10
It is 0 ppm or less, and particularly preferably 0.01 ppm or more and 10 ppm or less. Water is preferred as the coating aid.

As an electrolyte, an organic solvent such as propylene carbonate, ethylene carbonate, butylene carbonate, dimethyl carbonate, diethyl carbonate, γ-butyrolactone, 1,2-dimethoxyethane, tetrahydrofuran, 2-methyltetrahydrofuran is used. , Dimethyl sulfoxide, 1,3-dioxolane,
Formamide, dimethylformamide, dioxolan,
Acetonitrile, nitromethane, methyl formate, methyl acetate, methyl propionate, ethyl propionate, phosphoric acid triester, trimethoxymethane, dioxolane derivative, sulfolane, 3-methyl-2-oxazolidinone,
A solvent in which at least one kind of aprotic organic solvent such as a propylene carbonate derivative, a tetrahydrofuran derivative, diethyl ether, and 1,3-propanesulfone is mixed, and a lithium salt soluble in the solvent, for example, Li
ClO ₄ , LiBF ₆ , LiPF ₆ , LiCF ₃ SO ₃ , L
_{iCF 3 CO 2, LiAsF 6,} LiSbF 6, LiB 10 C
l ₁₀ , lower aliphatic lithium carboxylate, LiAlC
It is composed of at least one salt such as l ₄ , LiCl, LiBr, LiI, lithium chloroborane, and lithium tetraphenylborate. Above all, Li is added to a mixed solution of propylene carbonate or ethylene carbonate and 1,2-dimethoxyethane and / or diethyl carbonate.
An electrolyte containing CF ₃ SO ₃ , LiClO ₄ , LiBF ₄ and / or LiPF ₆ is preferred. The amount of these electrolytes to be added to the battery is not particularly limited, but the required amount can be used depending on the amounts of the positive electrode active material and the negative electrode active material and the size of the battery. The concentration of the supporting electrolyte is preferably 0.2 to 3 mol per liter of the electrolytic solution.

In addition to the electrolytic solution, the following solid electrolytes can be used. Solid electrolytes are classified into inorganic solid electrolytes and organic solid electrolytes. Well-known inorganic solid electrolytes include nitrides, halides, and oxyacid salts of Li. Among them, Li ₃ N, LiI, Li ₅ NI
_{2, Li 3 N-LiI-} LiOH, Li 4 SiO 4, Li 4
_{SiO 4 -LiI-LiOH, xLi 3} PO 4 - (1-
x) Li ₄ SiO ₄ , Li ₂ SiS ₃ , phosphorus sulfide compounds, etc. are effective. In the organic solid electrolyte, a polyethylene oxide derivative or a polymer containing the derivative, a polypropylene oxide derivative or a polymer containing the derivative, a polymer containing an ionic dissociative group, a polymer containing an ionic dissociative group, and the aprotic electrolyte solution are used. Mixtures, phosphate ester polymers are effective. Furthermore, there is a method of adding polyacrylonitrile to the electrolytic solution. In addition, a method of using an inorganic and an organic solid electrolyte in combination is also known.

As the separator, an insulating thin film having a large ion permeability and a predetermined mechanical strength is used. Sheets or nonwoven fabrics made of olefin polymers such as polypropylene or glass fibers or polyethylene are used because of their resistance to organic solvents and hydrophobicity. The pore size of the separator is in a range generally used for batteries. For example, 0.01-10 μ
m is used. The thickness of the separator is generally used in the range for batteries. For example, a thickness of 5 to 300 μm is used.

Further, it is known to add the following compounds to the electrolyte for the purpose of improving discharge and charge / discharge characteristics. For example, pyridine, triethylphosphite, triethanolamine, cyclic ether, ethylenediamine, n-glyme, hexaphosphoric acid triamide, nitrobenzene derivative, sulfur, quinone imine dye, N-substituted oxazolidinone and N, N′-substituted imidazolidinone,
Ethylene glycol dialkyl ether, quaternary ammonium salt, polyethylene glycol, pyrrole, 2-methoxyethanol, AlCl ₃ , conductive polymer-monomer of electrode active material, triethylenephosphoramide, trialkyl Examples include phosphine, morpholine, aryl compounds having a carbonyl group, hexamethylphosphoric triamide and 4-alkylmorpholine, bicyclic tertiary amines, oils, quaternary phosphonium salts, and tertiary sulfonium salts. .

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. In addition, carbon dioxide gas can be included in the electrolytic solution in order to provide suitability for high-temperature storage. Further, the mixture of the positive electrode and the negative electrode can contain an electrolytic solution or an electrolyte. For example, a method is known in which the ion-conductive polymer, nitromethane, and an electrolyte are included.

Further, the surface of the positive electrode active material can be modified. For example, the surface of the metal oxide may be treated with an esterifying agent, a chelating agent, a conductive polymer or polyethylene oxide. Further, the surface of the negative electrode material can be modified.
For example, it is possible to provide an ion conductive polymer or polyacetylene layer, or to treat with LiCl or the like.

The collector of the electrode active material may be any electron conductor as long as it does not undergo a chemical change in the constructed battery. For example, for the positive electrode, in addition to materials such as stainless steel, nickel, aluminum, titanium, and calcined carbon, the surface of aluminum or stainless steel has carbon,
Nickel, titanium or silver treated, negative electrode, 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. The current collector is preferably stainless steel, nickel, aluminum or copper, and particularly preferably aluminum or copper. Oxidizing the surface of these materials is also used. The shape is preferably a thin film shape. The thickness is not particularly limited, but a thickness of 1 to 500 μm is used. In the present invention, the positive electrode mixture is preferably applied on an aluminum foil current collector, and the negative electrode mixture is preferably applied on a copper foil current collector.

The shape of the battery can be applied to any of sheet, cylinder, corner and the like. At that time, the mixture of the positive electrode active material and the negative electrode material is mainly used after being coated, dried and compressed on the current collector. The coat thickness, length and width are determined by the size of the battery, but the coat thickness in the compressed state after drying is particularly preferably 1 to 2000 μm.

The application of the non-aqueous secondary battery of the present invention is not particularly limited. For example, when it is mounted on an electronic device, a color notebook computer, a black and white notebook computer, a pen input computer, a pocket (palmtop) computer, a notebook computer. Type word processor, pocket word processor, e-book player, mobile phone, cordless phone handset, pager, handy terminal, mobile fax, mobile copy, mobile printer, headphone stereo, video movie, LCD TV, handy cleaner, portable CD, mini disk, Electric shaver, electronic translator, car phone,
Examples include a transceiver, a power tool, an electronic organizer, a calculator, a memory card, a tape recorder, a radio, a backup power supply, and a memory card. For other consumer use, automobiles, electric vehicles, motors, lighting equipment, toys,
Game devices, road conditioners, irons, watches, strobes, cameras, medical devices (pacemakers, hearing aids, shoulder massagers, etc.). Furthermore, it can be used for various military purposes and space applications. Further, it can be combined with a solar cell.

[0052]

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

Synthesis Example-1 Cobalt oxide having a chlorine content of 1 ppm and lithium carbonate having a chlorine content of 1 ppm are mixed so that the atomic ratio of cobalt and lithium is equal, and the mixture is baked at 900 ° C. for 4 hours. LiCoO ₂ was obtained (Compound Example A-1). When this compound was dissolved and the chlorine content was measured by an ion chromatogram, it was 0.8 ppm.

Synthesis Example-2 Nickel nitrate having a chlorine content of 1 ppm and lithium nitrate having a chlorine content of 1 ppm are mixed so that the atomic ratio of nickel and lithium is the same, and the mixture is mixed in an oxygen atmosphere at 600.
LiNiO ₂ was obtained by firing at 8 ° C. for 8 hours (Compound Example A-
2). When this compound was dissolved and the chlorine content was measured by an ion chromatogram, it was 0.9 ppm.

Synthesis Example-3 Manganese oxide having a chlorine content of 1.7 ppm and lithium carbonate having a chlorine content of 1 ppm were mixed so that the atomic ratio of manganese to lithium was 2: 1 and the mixture was heated at 800 ° C. for 4 hours.
It was baked for 8 hours to obtain LiMn ₂ O ₄ (Compound Example A-3).
When this compound was dissolved and the chlorine content was measured by an ion chromatogram, it was 1.5 ppm.

Synthesis Example-4 Cobalt oxide having a chlorine content of 1.9 ppm, nickel hydroxide having a chlorine content of 1.3 ppm, and lithium carbonate having a chlorine content of 1 ppm have an atomic ratio of cobalt, nickel and lithium. And mix to give 1: 1 and 2:
It was baked at 00 ° C. for 48 hours to obtain LiCo _0.5 Ni _0.5 O ₂ (Compound Example A-4). After dissolving this compound, the chlorine content was measured by an ion chromatogram and found to be 1.5 ppm.
Met.

Synthesis Example-5 Cobalt oxide having a chlorine content of 1550 ppm and lithium carbonate having a chlorine content of 200 ppm were mixed at an atomic ratio of cobalt to lithium of 900 ° C.
Then, it was baked for 4 hours to obtain LiCoO ₂ . 10 by weight
Washed three times with twice the amount of purified water and having a chlorine content of 7 ppm L
iCoO ₂ was obtained (Compound Example A-5).

Comparative Synthesis Example-1 Cobalt oxide having a chlorine content of 2750 ppm and lithium carbonate having a chlorine content of 200 ppm were mixed at an atomic ratio of cobalt to lithium of 900 ° C.
Li with a chlorine content of 1970 ppm after firing for 4 hours
CoO ₂ (Compound Example B-1) was obtained.

Example 1 87% by weight of compound A-1 as a positive electrode active material, 6% by weight of flake graphite, 3% by weight of acetylene black, and 3% by weight of polytetrafluoroethylene aqueous dispersion as a binder. 1% by weight of sodium polyacrylate was added, and a slurry obtained by kneading with water as a medium was applied on both sides of an aluminum foil having a thickness of 20 μm, dried, pressed and cut.
The scale-like graphite, acetylene black, polytetrafluoroethylene and sodium polyacrylate used here had a chlorine ion content of 1 ppm or less as determined by a mass spectrometer of a spark ion source. Also, the chlorine concentration content in water was 1 ppm or less. This sheet was stored in a constant temperature and humidity room at a humidity of 70% and 25 ° C. for 5 days and then wound around a core having a diameter of 4 mm, and peeling of the coating material from the aluminum foil was observed, but peeling was not observed. Similarly, no peeling was observed using the compounds A-2, A-3, A-4, and A-5.

Comparative Example-1 The peeling of the coated material was observed in the same manner as in Example-1 except that B-1 was used in place of the compound A-1, but 30% of all coated surfaces were peeled off. .

Example 2 90% by weight of a layered graphite compound (compound C-1) having a chlorine content of 0.5 ppm (compound C-1) and 10% by weight of polyvinylidene fluoride as a negative electrode active material were obtained by kneading in water as a medium. Prepared slurry. The slurry was applied on both sides of a copper foil having a thickness of 18 μm by an extrusion method, dried, compression-molded by a calender press, and cut into a predetermined width and length to prepare a strip-shaped negative electrode sheet. The thickness of the negative electrode sheet was 75 μm. Humidity of this sheet 70%, 2
After storage in a constant temperature and humidity room at 5 ° C. for 5 days, it was wound around a direct core of 1 mm, and peeling of the coating material from the copper foil was observed, but peeling was not observed.

Comparative Example-2 A layered graphite compound (compound D-1) having a chlorine content of 1540 ppm instead of the compound C-1 in Example-2.
The peeling of the coated material was observed in the same manner except that the above was used, but 70% of all coated surfaces peeled off.

Example 3 As a negative electrode material, SnA having a chlorine content of 0.8 ppm
_{l 0.1 B 0.5 P 0.5 Mg 0} .1 F 0.2 O 3.15 ( compound C-2)
In an amount of 86% by weight, scaly graphite 6% by weight, and acetylene black 3% by weight. Further, 4% by weight of an aqueous dispersion of styrene-butadiene rubber as a binder and 1% by weight of carboxymethyl cellulose are added, and water is added. Was mixed as a medium to prepare a slurry. The slurry has a thickness of 18 μm
Apply to both sides of the copper foil by the extrusion method,
After drying, it was compression-molded by a calendar press and cut into a predetermined width and length to prepare a strip-shaped negative electrode sheet. The thickness of the negative electrode sheet was 124 μm. Humidity of this sheet 7
Stored in 0%, 25 ° C constant temperature and humidity room for 5 days, then 1m straight line
It was wound around the core of m, and peeling of the coating material from the copper foil was observed, but peeling was not observed.

[0064] a chlorine content 1820ppm in place of compound C-2 Comparative Example -3 Example _{-3 SnAl 0.1 B 0.5 P 0.5 Mg} 0.1 F
Peeling of the coated material was observed in the same manner except that _0.2 O _3.15 (Compound D-2) was used.
Peeled off.

Example 4 Nickel was added to the edges of the sheet made of the compound A-1 prepared in Example 1 after storage and the sheet made of the compound D-1 prepared in Example 3 after storage. , Aluminum lead plate after spot welding, dew point -40
It was dehydrated and dried at 150 ° C. for 2 hours in a dry air at a temperature of ≦ ° C. Furthermore, the dehydrated and dried positive electrode sheet (8), a microporous polypropylene film separator (Celguard 240
0), the dehydrated and dried negative electrode sheet (9) and the separator (10) were laminated in this order, and this was spirally wound with a winding machine.

This roll was housed in a bottomed cylindrical battery can (11) made of iron and plated with nickel, which also serves as a negative electrode terminal. Furthermore, as an electrolyte, 1 mol / l LiPF ₆
(2: 2: 6 volume mixture of ethylene carbonate, butylene carbonate and dimethyl carbonate) was injected into the battery can. The battery lid (12) having the positive electrode terminal was caulked via a gasket (13) to produce a cylindrical battery. The positive electrode terminal (12) was connected to the positive electrode sheet (8), and the battery can (11) was connected to the negative electrode sheet (9) by a lead terminal in advance. FIG. 1 shows a cross section of a cylindrical battery. Incidentally, (14) is a safety valve. Charge / discharge conditions are 4.3-
The voltage was 2.7 V and 1 mA / cm ² . The charge / discharge repetition test was performed. As a result, after 500 cycles, 84% of the initial capacity was maintained. In addition, compounds A-2, A-3, A
When -4 and A-5 are used, 81%, 83%,
It was 83% and 84%. Moreover, when B-1 was used, it was 50%.

[0067]

EFFECTS OF THE INVENTION According to the present invention, it is possible to provide an electrode having excellent storability after formation of an electrode sheet and excellent charge / discharge repeating characteristics.

[Brief description of drawings]

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

[Explanation of symbols]

 8 Positive electrode sheet 9 Negative electrode sheet 10 Separator 11 Battery can 12 Battery lid 13 Gasket 14 Safety valve

─────────────────────────────────────────────────── ─── Continuation of the front page (51) Int.Cl. ⁶ Identification code Internal reference number FI Technical indication H01M 10/40 H01M 10/40

Claims (10)

[Claims] 1. A non-aqueous secondary battery comprising a positive electrode having a positive electrode mixture applied on a current collector, a negative electrode having a negative electrode mixture applied on a current collector, and a non-aqueous electrolytic solution containing a lithium salt. In relation to the positive electrode mixture and / or the negative electrode mixture, the content of halogen elements as impurities in the positive electrode mixture and the negative electrode mixture is 0.01 ppm or more and 1000 ppm or less. 2. The content of halogen element as an impurity in each of the positive electrode active material, the conductive agent, the binder, and the coating aid which is the positive electrode mixture component is 0.01 ppm or more and 1000 ppm.
The non-aqueous battery according to claim 1, wherein: 3. The content of halogen element as an impurity in each of the negative electrode material which is the negative electrode mixture component, the conductive agent, the binder, and the coating aid is 0.01 ppm or more and 1000 ppm.
It is the following, The nonaqueous battery of Claim 1 or 2 characterized by the above-mentioned. 4. The positive electrode mixture and the negative electrode mixture having a halogen element content as an impurity of 0.01 ppm or more and 1000 ppm or less are obtained by washing. Non-aqueous battery according to item. 5. The method for obtaining the positive electrode and the negative electrode uses a positive electrode active material and / or a raw material of a negative electrode material having a halogen element impurity content of 0.01 ppm or more and 1000 ppm or less. The non-aqueous battery according to claim 4. 6. The nonaqueous battery according to claim 1, wherein the halogen element as the impurity is chlorine. 7. The positive electrode material mixture is applied onto an aluminum foil current collector, and the positive electrode material mixture is applied onto the aluminum foil current collector.
5. The non-aqueous battery according to any one of 5 and 6. 8. The non-aqueous battery according to claim 1, wherein the negative electrode mixture is applied onto a copper foil current collector. 9. The nonaqueous battery according to claim 1, wherein the positive electrode active material is a lithium-containing transition metal oxide. 10. The nonaqueous battery according to claim 1, wherein the negative electrode material is represented by the general formula (1). SnM ¹ _a O _t General formula (1) In the formula, M ¹ is two or more selected from Al, B, P, Si, Group 1 element of the periodic table, Group 2 element, Group 3 element, and halogen element. A represents a number of 0.2 or more and 2 or less, and t represents a number of 1 or more and 6 or less.