JP3482733B2 - Non-aqueous secondary battery - Google Patents

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 high capacity, improved charge / discharge characteristics, and enhanced safety.

[0002]

2. Description of the Related Art Japanese Unexamined Patent Publication (Kokai) No. 4-328278 describes that lithium carbonate is added to the positive electrode to suppress a rapid temperature rise during overcharge. Also, US Pat. No. 446
No. 5747 describes adding an inorganic acid salt such as a silicate to suppress decomposition of the electrolyte.

On the other hand, JP-A-6-275268 discloses Sn.
O, silicon oxide in JP-A-6-325765, particularly silicon oxide in which silicon has a valence of 4 or less, JP-A-6-33.
No. 8325 describes the use of a composite oxide of tin and another element as a negative electrode material. Some of these negative electrode materials have a high discharge potential and a high capacity, but those having excellent cycle life have not been developed, and the performance of the secondary battery is insufficient.

In order to improve the capacity per volume,
It is necessary to increase the density of the electrode sheet. However, if the press pressure is increased to increase the density, charge / discharge cycle characteristics are deteriorated and safety is deteriorated, which is not preferable. Further, since the wettability of the electrode sheet is insufficient, it takes a long time to inject the electrolyte solution, resulting in poor productivity.

[0005]

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

[0006]

Means for Solving the Problems The above-mentioned problems are solved by the positive electrode material,
In a non-aqueous secondary battery comprising a negative electrode material and a non-aqueous electrolyte containing a lithium salt, at least one of the negative electrode material, the positive electrode material and the electrolyte contains a nonionic surfactant, and the negative electrode material has the following general formula (1 ) Is achieved by being an amorphous complex oxide represented by. Sn _x M ¹ _1-x M ² _a M ³ _b O _z General formula (1) Here, Sn and M ¹ are functional elements, and their valences change with occlusion and release of lithium ions. , An element that can contribute to the charge and discharge capacity. M ¹ represents a transition metal element, more preferably Fe, Mn, lead or germanium. x is 0 . It is a number of 5 or more and 1 or less. M ² is an element that can be made amorphous and contains at least one of Al, B, P and Si.
Seed, M ³ represents a Group 1 element, a Group 2 element, a Group 3 element, or a halogen element of the periodic table. a is a number of 0.2 or more and 2 or less, b is a number of 1 or less, 0.2 <a + b <2, and z is 1
Represents a number of 6 or more.

Further, it is achieved in a non-aqueous secondary battery using a material containing ethylene oxide as the nonionic surfactant.

The positive and negative electrodes used in the non-aqueous secondary battery of the present invention can be prepared by coating a positive electrode mixture or a negative electrode mixture on a current collector. The positive electrode or the negative electrode mixture can contain a positive electrode active material or a negative electrode material, as well as a conductive agent, a binder, a dispersant, a filler, an ion conductive agent, a pressure enhancer or various additives, respectively.

As the nonionic surfactant used in the present invention, polyoxyethylene alkyl ether, polyoxyethylene alkylphenyl ether, polyoxyethylene-polyoxyalkylene (propylene etc.) glycol, polyoxyethylene-polyoxyalkylene ( Propylene etc.) Alkyl ether, polyhydric alcohol fatty acid partial ester, polyoxyethylene polyhydric alcohol fatty acid partial ester, polyoxyethylene fatty acid ester, polyglycerin fatty acid ester, fatty acid diethanolamide, polyoxyethylene alkylamine, triethanolamine fatty acid partial ester , Trialkylamine oxides, N.I. SURF by Schonfeldt
ACE ACTIVE ETHYLENE OXIDE
ADDUCTS (PERGAMON PRESS 1
969) The compound of P719-807 is mentioned.

Preferred are polyoxyethylene alkyl ether, polyoxyethylene alkylphenyl ether, polyoxyethylene-polyoxyalkylene glycol, polyoxyethylene-polyoxyalkylene alkyl ether. Particularly preferred are polyoxyethylene-polyoxypropylene glycol and polyoxyethylene-polyoxypropylene alkyl ether.

Specific examples are shown below, but the invention is not limited thereto. W-1 Pluronic R 31R1 (manufactured by BASF) W-2 Pluronic R 17R2 (manufactured by BASF) W-3 Pluronic R 25R4 (manufactured by BASF) W-4 Pluronic L121 (manufactured by BASF) W-5 Pluronic L61 (BASF) W-6 Pluronic L64 (manufactured by BASF) W-7 Tetronic 1501 (manufactured by BASF) W-8 Pluronic 702 (manufactured by BASF) W-9 Tetronic R 130R2 (manufactured by BASF) W-10 nonylphenyl- _{O- (CH 2 CH 2 O)} n H n = 50 W-11 C 9 H 19 O (CH 2 CH 2 O) n H n = 40

The nonionic surfactant of the present invention may be contained in any of the positive electrode sheet, the negative electrode sheet and the electrolytic solution.
It is preferably contained in the positive electrode sheet and the negative electrode sheet. When the content is included in each sheet, it is 0.1 with respect to the mixture.
% To 10% by weight is preferable, 0.3% to 5% by weight is more preferable, and 0.3% to 2% by weight is more preferable. When it is contained in the electrolyte, it is 0.1 with respect to the electrolyte.
% By weight to 10% by weight is preferable, 0.2% by weight to 3% by weight is more preferable, and 0.2% by weight to 2% by weight is more preferable.

[0013]

[0014]

[0015]

[0016]

The negative electrode material used in the present invention is
It is an amorphous composite oxide mainly composed of tin and is represented by the following general formula (1). Sn _x M ¹ _1-x M ² _a M ³ _b O _z General formula (1) Here, Sn and M ¹ are functional elements, and their valences change with occlusion and release of lithium ions. , An element that can contribute to the charge and discharge capacity. M ¹ represents a transition metal element, more preferably Fe, Mn, lead or germanium. x is 0 . It is a number of 5 or more and 1 or less. M ² and M ³ are elements for amorphizing the compound of the general formula (1) as a whole, M ² is an element that can be amorphized, and Al,
At least one of B, P, and Si, and M ³ is an element that can be modified amorphously, and represents a Group 1 element, a Group 2 element, a Group 3 element, or a halogen element of the periodic table. a is a number of 0.2 or more and 2 or less, b is a number of 1 or less, and 0.2 <a + b
<2, z represents a number of 1 or more and 6 or less.

The negative electrode material of the present invention is preferably mainly amorphous when incorporated in a battery. The term “mainly amorphous” used herein means an X-ray diffraction method using CuKα rays and a 2θ value of 2
It is a product having a broad scattering band having an apex at 0 ° to 40 ° and may have a crystalline diffraction line. Preferably, the strongest intensity of the crystalline diffraction lines observed at a 2θ value of 40 ° or more and 70 ° or less is 5 of the diffraction line intensity at the apex of the broad scattering band observed at a 2θ value of 20 ° or more and 40 ° or less.
It is preferably 00 times or less, more preferably 1
It is 00 times or less, particularly preferably 5 times or less, and most preferably it has no crystalline diffraction line.

The amorphous composite oxide of the present invention may employ either a calcination method or a solution method, but the calcination method is more preferable. In the calcination method, it is preferable that the oxide or compound of the element described in the general formula (1) is well mixed and then calcined to obtain an amorphous composite oxide.

The firing conditions are preferably a heating rate of 5 ° C. or more and 200 ° C. or less per minute, a firing temperature of 500 ° C. or more and 1500 ° C. or less, and a firing time. Is more than 1 hour 10
It is preferably 0 hours or less. Further, the rate of temperature decrease is preferably 2 ° C. or more and 10 ⁷ ° C. or less per minute. The rate of temperature rise in the present invention refers to "calcination temperature (displayed in ° C)"
Is the average rate of temperature increase from "50% of the firing temperature (expressed in ° C)" to "80% of the firing temperature (expressed in ° C)". It is the average speed of the temperature drop until it reaches 50% (in degrees Celsius). The temperature may be lowered in the firing furnace or may be taken out of the firing furnace and put in water for cooling. Also, ceramics processing (Gihodo Publishing 1
987) page 217, the Gun method Hammer-An.
It is also possible to use ultra-quenching methods such as the vil method, the slap method, the gas atomizing method, the plasma spray method, the centrifugal quenching method, and the melt drag method. The single roller method described in New Glass Handbook (Maruzen 1991), page 172,
The twin roller method may be used for cooling. In the case of a material that melts during firing, the fired product may be continuously taken out while supplying the raw material 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 average particle size of the compound of the present invention is preferably 0.1 to 60 μm. A well-known crusher or classifier is used to obtain a predetermined particle size. 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 which water or an organic solvent such as methanol is allowed to coexist can be performed as necessary. In order to obtain the desired particle size, it is preferable to carry out classification. The classification method is not particularly limited, and a sieve, an air classifier, or the like can be used as necessary. Classification can be carried out both dry and wet.

Examples of the negative electrode material of the present invention are shown below.
The invention is not limited to these. SnB_0.5P
_0.5O₃, SnAl_0.3B_0.5P_0.2O_2.7, SnAl
_0.3B_0.7O_2.5, SnSi_0.8P_0.2O_3.1, SnS
i_0.8B_0.2O_2.9, SnSi_0.8Al_0.2O_2.9, S
nSi_0.6Al_0.2B_0.2O_2.8, SnSi_0.6Al
_0.2P _0.2O₃, SnSi_0.6B_0.2P_0.2O₃, Sn
Si_0.4Al_0.2B_0.4O_2.7, SnSi_0.6Al_0.1
B_0.1P_0.3O_3.25, SnSi_0.6Al_0.1B_0.3P_0.
1O_3.05, SnSi_0.5Al_0.3B_0.4P_0.2O_3.55,
SnSi_0.5Al_0.3B _0.4P_0.5O_4.30, SnSi
_0.8Al_0.3B_0.2P_0.2O_3.85

SnSi_0.8Mg_0.2O_2.8, SnSi
_0.6Al_0.2Mg_0.2O_2.7, SnSi _0.6Al_0.1B
_0.1P_0.1Mg_0.2O_2.95, SnSi_0.8Ca_0.2O
_2.8, SnSi_0.6Al_0.2Ca_0.2O_2.7, SnSi
_0.6Al_0.1B_0.1P_0.1Ca_0.2O_2.95, SnSi
_0.5Al_0.2B_0.1P_0.1Mg_0.1O_2.8, SnSi
_0.5Al _0.1B_0.2P_0.1Ca_0.4O_3.1, SnSi
_0.8Ba_0.2O_2.8, SnSi_0.6Al_0.1B_0.1P
_0.1Ba_0.2O_2.95.

Sn_0.9Mn_0.3B_0.4P_0.4Ca_0.1R
b_0.1O_2.95, Sn_0.9Fe_0.3B_{0. Four}P_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.

Sn _1.6 B _0.4 P _0.4 Ca _0.2 O _3.4 ,
Sn _1.3 B _0.4 P _0.4 Ca _0.2 O _3.1 , Sn _1.6 B _0.4
P _0.4 Ba _0.2 O _3.4 , Sn _1.3 B _0.4 P _0.4 Ba _0.2
O _3.1 , Sn _1.6 B _0.4 P _0.4 Mg _0.2 O _3.4 , Sn
_{1.6 Al 0.1 B 0.3 P 0.4 Ca} 0. 2 O 3.4,

Sn_1.3Al_0.1B_0.3P_0.4K
_0.2O₃, Sn_1.0Al_0.1B_0.3P_0.4K
_{0. 2}O_2.7, Sn_1.6Al_0.1B_0.3P_0.4Na_0.2O
_3.3, Sn_1.3Al_0.1B _0.3P_0.4Na_0.2O₃, S
n_1.0Al_0.1B_0.3P_0.4Na_0.2O_2.7, Sn _1.6
Al_0.1B_0.3P_0.4Rb_0.2O_3.3, Sn_1.3Al
_0.1B_0.3P_0.4Rb _0.2O₃, Sn_1.0Al_0.1B
_0.3P_0.4Rb_0.2O_2.7, Sn_1.6Al_0.1B _0.3P
_0.4Cs_0.2O_3.3, Sn_1.2Al_0.1B_0.3P_0.4C
s_0.2O_2.9, Sn_1.0Al_0.1B_0.3P_0.4Cs_0.2
O_2.7, Sn_1.3Al_0.1B_0.3P_0.4Ba_0.1K_0.1
O_3.05.

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

The amount of the light metal to be inserted into the negative electrode material of the present invention may be close to the deposition potential of the light metal.
50 to 700 mol% is preferable, and 100 to 600 mol% is particularly preferable, based on the negative electrode material. It is preferable that the amount released is larger than the amount inserted. The light metal insertion method is
Electrochemical, chemical and thermal methods are preferred. The electrochemical method is preferably a method in which a light metal contained in the positive electrode active material is electrochemically inserted or a method in which a light metal or an alloy thereof is directly electrochemically inserted. As a chemical method, there is a method of mixing with a light metal, contacting with it, or reacting with an organic metal such as butyllithium. The electrochemical method and the chemical method are preferable. The light metal is particularly preferably lithium or lithium ion.

The positive electrode active material used in the present invention may be any compound capable of inserting and extracting light metal ions, and is particularly selected from transition metal oxides and transition metal chalcogenides. A transition metal oxide is particularly preferable, and a transition metal oxide containing lithium is particularly preferable.

Preferred transition metals used in the present invention are Ti, V, Cr, Mn, Fe, Co, Ni, Cu,
Nb, Mo and W can be mentioned. Among these transition metal compounds, manganese dioxide, vanadium pentoxide,
Iron oxide, molybdenum oxide, molybdenum sulfide, cobalt oxide, iron sulfide, titanium sulfide and the like are preferable. These compounds can be used alone or in combination of two or more kinds. It can also be used as a transition metal oxide containing lithium.

In addition to lithium compounds and transition metal compounds,
In general, compounds that enhance ionic conductivity, such as Ca ²⁺ ,
Alternatively, an amorphous network forming agent containing P, B or Si (for example, P ₂ O ₅ , Li ₃ PO ₄ , H ₃ BO ₃ , B ₂
O _3, etc. SiO ₂₎ and may be fired by mixing. In addition, alkali metal ions such as Na, K and Mg and /
Or Si, Sn, Al, Ga, Ge, Ce, In, B
You may mix with a compound containing i etc., and may bake. The transition metal oxide containing lithium is, for example, a lithium compound,
It can be synthesized by firing a mixture of transition metal compounds.

Specific examples of preferred positive electrode active materials used in the present invention include JP-A-61-2562, US Pat. Nos. 4,302,518, and JP-A-63-29905.
6, JP-A-1-294364, JP-B-4-3014
6, U.S. Pat. Nos. 5,240,794 and 5,15.
3,081, JP-A-4-328,258, JP-A-5
-54, 889 and the like. Representative compounds are shown below, but the present invention is not limited thereto.

Li _x CoO ₂ , Li _x NiO ₂ , Li _x
Co _a Ni _1-a O ₂ , Li _x Co _b V _1-b O _z , Li _x
Co _b Fe _1-b O _z , Li _x Mn ₂ O ₄ , Li _x Mn
O ₂ , Li _x Mn ₂ O ₃ , Li _x Mn _b Co _2-b O _z ,
_{Li x Mn b Ni 2-b} O z, Li x Mn b V 2-b O z,
Li _x Mn _b Fe _1-b O _z , Li _x Co _c B _1-c O
₂ (where x = 0.05 to 1.2, a = 0.1 to 0.
9, b = 0.8 to 0.98, c = 0.85 to 0.99,
z = 1.5 to 5).

The positive electrode active material used in the present invention 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. Details for firing are described in paragraph 35 of JP-A-6-60,867, JP-A-7-14,579 and the like, and these methods can be used. The positive electrode active material obtained by firing may be used after being washed with water, an acidic aqueous solution, an alkaline aqueous solution, or an organic solvent. Further, the method of chemically inserting lithium ions into the transition metal oxide may be a method of synthesizing lithium metal, a lithium alloy, or butyl lithium by reacting with the transition metal oxide.

The average particle size of the positive electrode active material used in the present invention
The size is not particularly limited, but 0.1 to 50 μm is preferable.
Yes. The volume of particles of 0.5 to 30 μm is 95% or more.
It is preferable. The specific surface area is not particularly limited
But 0.01 to 50m by BET method ²/ G is preferred. Well
When 5g of positive electrode active material was dissolved in 100ml of distilled water
The pH of the clear liquid is preferably 7 or more and 12 or less.

The surface of the oxide positive electrode active material or negative electrode material used in the present invention can be coated with an oxide having a chemical formula different from those of the positive electrode active material or negative electrode material used. This surface oxide is preferably an oxide containing a compound that is soluble in both acidity and alkalinity. Further, a metal oxide having high electron conductivity is preferable. For example, PbO ₂ , Fe
₂ O ₃ , SnO ₂ , In ₂ O ₃ , ZnO and the like or oxides thereof preferably contain a dopant (for example, a metal having a different valence in the oxide, a halogen element, etc.). Particularly preferably, SiO ₂ , SnO ₂ , Fe ₂
O _3, ZnO, is a PbO _2.

The amount of the surface-treated metal oxide is preferably 0.1 to 10% by weight based on the positive electrode active material or the negative electrode material. Further, 0.2 to 5% by weight is particularly preferable,
Most preferred is 0.3-3% by weight.

In addition to this, the surface of the positive electrode active material or the negative electrode material can be modified. For example, the surface of the metal oxide is treated with an esterifying agent, a chelating agent,
Treatment with a conductive polymer, polyethylene oxide, etc. may be mentioned. Also, the surface of the negative electrode material can be modified. For example, the treatment may be performed by providing an ion conductive polymer or a polyacetylene layer. Further, the positive electrode active material and the negative electrode material may be subjected to a purification step such as washing with water.

As the electrode mixture, a conductive agent, a binder, a filler, a dispersant, an ionic conductive agent, a pressure enhancer and various other additives can be used. The conductive agent may be any electron-conductive material that does not cause a chemical change in the constructed battery. Usually, natural graphite (scaly graphite, flake graphite, earthy graphite, etc.), graphite such as artificial graphite, acetylene black, Ketjen black, channel black, furnace black, lamp black,
Carbon blacks such as thermal black, conductive fibers such as carbon fibers and metal fibers, metal powders such as copper, nickel, aluminum and silver, conductive whiskers such as zinc oxide and potassium titanate, titanium oxide, etc. The organic conductive material such as the conductive metal oxide or the polyphenylene derivative can be contained alone or as a mixture thereof. Among these conductive agents, acetylene black, and the combined use of graphite and acetylene black are particularly preferable. The amount added is not particularly limited, but is 1
-50% by weight is preferable, and 1-30% by weight is particularly preferable. For carbon and graphite, 2 to 15% by weight is particularly preferable.

As the binder, one kind or a mixture of a polysaccharide, a thermoplastic resin and a polymer having rubber elasticity can be used. Preferred examples are starch, polyvinyl alcohol, carboxymethyl cellulose, hydroxypropyl cellulose, regenerated cellulose,
Diacetyl cellulose, polyvinyl chloride, polyvinylpyrrolidone, polytetrafluoroethylene, polyvinylidene fluoride, polyethylene, polypropylene, ethylene-propylene-diene terpolymer (EPDM), sulfonated EPDM, styrene butadiene rubber, polybutadiene, fluororubber and polyethylene oxide. Can be mentioned. When a compound containing a functional group that reacts with lithium, such as a polysaccharide, is used, it is preferable to add a compound such as an isocyanate group to deactivate the functional group. The amount of the binder added is not particularly limited, but is preferably 1 to 50% by weight, and particularly 2
-30% by weight is preferred. The distribution of the binder in the mixture may be uniform or non-uniform.

As the filler, any fibrous material which does not cause a chemical change in the constructed battery can be used. Generally, olefin polymers such as polypropylene and polyethylene, fibers such as glass and carbon are used. The amount of the filler added is not particularly limited, but is 0
-30% by weight is preferred.

As the ionic conductive agent, those known as inorganic and organic solid electrolytes can be used, and the details are described in the section of the electrolytic solution. The pressure enhancer is a compound that increases the internal pressure described later, and a typical example is carbonate.

The electrolyte is generally a solvent and a solvent dissolved in the solvent.
Lithium salt (anion and lithium cation) to be solved
It is composed of As the solvent, propylene carbonate
, Ethylene carbonate, butylene carbonate,
Dimethyl carbonate, diethyl carbonate, methyl
Ethyl carbonate, γ-butyrolactone, methyl formate
, Methyl acetate, 1,2-dimethoxyethane, tetrahi
Drofuran, 2-methyltetrahydrofuran, dimethyl
Sulfoxide, 1,3-dioxolane, formamide,
Dimethylformamide, dioxolane, acetonitril
, Nitromethane, ethyl monoglyme, triphosphate
Stell, trimethoxymethane, dioxolane derivative, suture
Luforane, 3-methyl-2-oxazolidinone, propyi
Len carbonate derivative, tetrahydrofuran derivative,
Non-preservatives such as ethyl ether and 1,3-propane sultone
Examples include rotonic organic solvents, one of these
Or, two or more kinds are mixed and used. Soluble in these solvents
As the cation of the lithium salt to be used, for example, ClO_Four
^-, BF_Four ^-, PF₆ ^-, CF₃SO₃ ^-, CF₃CO
₂ ^-, AsF₆ ^-, SbF₆ ^-, (CF₃SO₂)₂N
^-, B_TenCl_Ten ^2-, (1,2-dimethoxyethane)₂C
10_Four ^-, Lower aliphatic carboxylate ion, AlCl4
 ^-, Cl^-, Br^-, I^-, A chloroborane compound
Nion, tetraphenyl borate ion can be mentioned,
These 1 type (s) or 2 or more types can be used.
Among them, cyclic carbonate and / or acyclic carbon
It is preferable to include a sheet. For example, diethyl car
Bonate, dimethyl carbonate, methyl ethyl carbo
It is preferable to include a nate. Also, ethylene car
It is preferable to include bonates and propylene carbonate
Good In addition to ethylene carbonate,
Carbonate, 1,2-dimethoxyethane, dimethyl
Carbonate or diethyl carbonate are mixed appropriately
LiCF in the electrolyte₃SO₃, LiClO_Four, LiB
F_FourAnd / or LiPF₆Electrolytes containing are preferred
Yes. In those supporting salts, LiPF₆Can be included
Particularly preferred.

The amount of these electrolytes added to the battery is not particularly limited, but can be used in the required amount depending on the amount of the positive electrode active material or the negative electrode material and the size of the battery. The concentration of the supporting electrolyte is not particularly limited, but is preferably 0.2 to 3 mol per liter of the electrolytic solution.

Other compounds may be added 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, A
lCl ₃ , a conductive polymer electrode active material monomer, triethylenephosphoramide, trialkylphosphine, morpholine, an aryl compound having a carbonyl group, 12-
Crown ethers such as Crown-4, hexamethylphosphoric triamide and 4-alkylmorpholine,
Examples include 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. Further, the electrolytic solution may contain carbon dioxide gas in order to have 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 electrolytic solution are contained.

As the separator, an insulating microporous thin film having a large ion permeability and a predetermined mechanical strength is used. Further, it is preferable to have a function of closing the holes at 80 ° C. or higher to increase resistance. A sheet or non-woven fabric made of olefin polymer such as polypropylene and / or polyethylene or glass fiber is used because of its resistance to organic solvent and hydrophobicity. The pore size of the separator is within the range generally used as a battery separator. For example, 0.01 to 10 μm is used. The thickness of the separator is generally within the range of battery separators. For example, 5 to 300 μm is used. After the polymer is synthesized,
The method for forming the holes may be a dry method, a drawing method, a solution or solvent removing method, or a combination thereof.

The collector of the electrode active material may be any electron conductor that does not cause a chemical change in the constructed battery. For example, for the positive electrode, in addition to stainless steel, nickel, aluminum, titanium, carbon, or the like, a material obtained by treating the surface of aluminum or stainless steel with carbon, nickel, titanium, or silver is used. Particularly, aluminum or aluminum alloy is preferable. For the negative electrode, in addition to stainless steel, nickel, copper, titanium, aluminum, carbon, etc. as a material, a material obtained by treating the surface of copper or stainless steel with carbon, nickel, titanium or silver, or an Al-Cd alloy is used. To be Particularly, copper or copper alloy is preferable. It is also used to oxidize the surface of these materials. Further, it is desirable to make the surface of the current collector uneven by surface treatment. As the shape, in addition to the foil, a film, a sheet, a net, a punched product, a lath body, a porous body, a foamed body, a molded body of a fiber group and the like are used. The thickness is not particularly limited, but 1
Those having a thickness of up to 500 μm are used.

The shape of the battery can be any of coins, buttons, sheets, cylinders, flats, corners and the like. When the shape of the battery is a coin or a button, the mixture of the positive electrode active material and the negative electrode material is mainly used after being compressed into a pellet shape.
The thickness and diameter of the pellet are determined by the size of the battery. When the shape of the battery is a sheet, a cylinder, or a corner, the mixture of the positive electrode active material and the negative electrode material is applied (coated) on the current collector, dried, and compressed, and is mainly used. As a coating method, a general method can be used. For example,
Reverse roll method, direct roll method, blade method,
Knife method, extrusion method, curtain method, gravure method, bar method, dip method and squeeze method can be mentioned. Among them, the blade method, the knife method and the extrusion method are preferable. Application is 0.1-10
It is preferably carried out at a speed of 0 m / min. On this occasion,
By selecting the above coating method according to the solution physical properties and drying properties of the mixture, a good surface state of the coating layer can be obtained. The coating may be performed one by one or simultaneously on both sides. The coating may be continuous, intermittent or striped. The thickness, length and width of the coating layer are determined depending on the size of the battery, but the thickness of the coating layer on one side is particularly preferably 1 to 2000 μm in a compressed state after drying.

As a method for drying or dehydrating the pellets or sheets, a generally adopted method can be used. In particular, it is preferable to use hot air, vacuum, infrared rays, far infrared rays, electron beams, and low humidity air alone or in combination. The temperature is preferably in the range of 80 to 350 ° C, particularly 10
The range of 0 to 250 ° C. is preferable. The water content of the whole battery is preferably 2000 ppm or less, and the content of each of the positive electrode mixture, the negative electrode mixture and the electrolyte is preferably 500 ppm or less from the viewpoint of cycleability. As a pellet or sheet pressing method, a generally adopted method can be used, but a die pressing method or a calendar pressing method is particularly preferable. The pressing pressure is not particularly limited, but is 0.2 to 3 t /
cm ² is preferred. The press speed of the calendar press method is preferably 0.1 to 50 m / min. The pressing temperature is preferably room temperature to 200 ° C. The width ratio of the negative electrode sheet to the positive electrode sheet is preferably 0.9 to 1.1. In particular,
0.95-1.0 is preferable. Since the content ratio of the positive electrode active material and the negative electrode material differs depending on the compound type and mixture formulation,
Although not limited, it can be set to an optimum value in terms of capacity, cycleability, and safety.

Stacked with the mixture sheet via a separator
After being fitted, the sheets can be rolled or folded.
Insert it into the can, connect the can and the sheet electrically, and
Inject and use the sealing plate to form a battery can. At this time,
The safety valve can be used as a sealing plate. Safety valve
In addition, equipped with various conventionally known safety elements
Is also good. For example, fuses,
Immetal, PTC element, etc. are used. Also, the safety valve
In addition to the above, cut into the battery can as a measure to increase the internal pressure of the battery can
Inserting method, gasket cracking method or sealing plate cracking
Method or cutting method with lead plate can be used.
Wear. In addition, the charger has built-in measures against overcharge and overdischarge.
Either have a protection circuit or connect it independently
Good. Also, as a measure against overcharge, increase the internal pressure of the battery.
It is possible to provide a method of cutting off the electric current. This and
A compound that raises the internal pressure in the mixture or in the electrolyte.
Can be included in. As a compound that increases internal pressure
Is Li₂CO₃, LiHCO ₃, Na₂CO₃, Na
HCO₃, CaCO₃, MgCO₃Such as carbonate
can give. Cans and lead plates are made of metal or
Alloys can be used. For example, iron, nickel, chi
Gold such as tan, chrome, molybdenum, copper, aluminum
A genus or an alloy thereof is used. Caps, cans,
Welding methods for sheets and lead plates are known methods (eg, direct current or
Is AC electric welding, laser welding, ultrasonic welding)
You can Sealing agents for sealing are asphalt, etc.
It is possible to use conventionally known compounds and mixtures of
it can.

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 sub notebook computer, a pen input computer, a pocket (palm top). PC, notebook 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 disks, electric shavers, electronic translators, car phones, transceivers, power tools, electronic organizers, calculators, memory cards, tape recorders, radios, backup power supplies, memory cards, etc. Other consumer products include automobiles, electric vehicles, motors, lighting equipment, toys, game machines, road conditioners, irons, watches, strobes, cameras, medical equipment (pacemakers, hearing aids, shoulder massagers, etc.) and the like. Furthermore, it can be used for various military purposes and for space. It can also be combined with other secondary batteries, solar cells, or primary batteries.

The preferred combination of the present invention is preferably a combination of the above-mentioned nonionic surfactant and the above-mentioned chemical materials and battery components . The negative electrode current collector is made of stainless steel or copper, net, sheet,
It is shaped like a foil or lath.

As a positive electrode active material, Li_xCoO₂, Li
_xNiO₂, Li_xMnO₂, Li _xMn₂O_Four(here
And at least one selected from x = 0.05 to 1.2)
Acetylene black as a conductive agent
Included in. Whether the positive electrode current collector is stainless steel or aluminum
Shapes such as nets, sheets, foils, laths made from
Are doing

The mixture used with the positive electrode active material or the negative electrode material may be mixed with a carbon material such as acetylene black or graphite as an electron conductive agent. As the binder, fluorine-containing thermoplastic compounds such as polyvinylidene fluoride and polyfluoroethylene, polymers containing acrylic acid, elastomers such as styrene butadiene rubber and ethylene propylene terpolymer can be used alone or in combination.

As the electrolytic solution, a combination of ethylene carbonate, a cyclic carbonate such as diethyl carbonate and dimethyl carbonate, or an ester compound such as ethyl acetate, a supporting electrolyte,
Contains LiPF ₆ , and further includes LIBF ₄ , LiCF ₃ S
It is preferable to use a lithium salt such as O ₃ as a mixture. Further, as the separator, polypropylene or polyethylene is preferably used alone or in combination thereof. The form of the battery may be any of coin, button, cylinder, flat, and square type. It is preferable that the battery is provided with means (eg, internal pressure release type safety valve, current cutoff type safety valve, separator that increases resistance at high temperature) capable of ensuring safety even when malfunctioning. The battery of the present invention is used in various devices. In particular, video movies, portable VCRs with built-in monitors, movie cameras with built-in monitors, compact cameras, single-lens reflex cameras, disposable cameras, films with lenses, laptop computers, notebook word processors, electronic notebooks, mobile phones, cordless phones, beards, Electric tool,
It is preferably used in electric mixers, automobiles and the like.

[0057]

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 Tin monoxide (13.5 g), silicon dioxide (3.6 g), magnesium oxide (0.64 g) and boron oxide (0.69 g) were dry-mixed, placed in an alumina crucible and placed under an argon atmosphere at 15 ° C.
The temperature was raised to 1000 ° C./min. After firing at 1200 ° C. for 10 hours, the temperature was lowered to room temperature at 10 ° C./min, the product was taken out from the firing furnace, coarsely crushed, and further crushed by a jet mill to obtain SnSi _0.6 Mg _0.2 having an average particle diameter of 4.5 μm. B
_0.2 O _2.7 was obtained. (Compound 1-A) Further, it has a broad peak having an apex at a 2θ value of about 28 ° in an X-ray diffraction method using CuKα rays, and has a crystalline property at a 2θ value of 40 ° to 70 °. No diffraction line was observed.

In a similar manner, each stoichiometric amount of raw material
Were mixed, fired and pulverized to obtain the following compound. SnSi
_0.8Mg_0.2O_2.8(1-B), SnSi_0.6Al_0.2
Mg _0.2O_2.7(1-C), SnSi_0.6P_0.2Mg
_0.2O_2.9(1-D), SnSi_0.6Al_0.1B_0.2M
g_0.1O_2.75(1-E), SnSi_0.5P_0.1B_0.1C
a_0.3O_2.7(1-F).

Example-1 As a negative electrode material, the compound 1-A synthesized in Synthesis Example-1 was used, and mixed in a proportion of 86% by weight, flake graphite 6% by weight, and acetylene black 3% by weight, Furthermore, 4% by weight of an aqueous dispersion of polyvinylidene fluoride and 1% by weight of carboxymethyl cellulose were added as a binder, and the mixture was kneaded with water as a medium to prepare a slurry. The slurry is applied to both sides of a copper foil having a thickness of 18 μm by the extrusion method, dried and compression-molded by a calender press.
A strip-shaped negative electrode sheet was produced by cutting into a predetermined width and length. The thickness of the negative electrode sheet was 124 μm. As the positive electrode material, 87% by weight of LiCoO ₂ , 6% by weight of scaly graphite, 3% by weight of acetylene black, 3% by weight of an aqueous dispersion of polytetrafluoroethylene and 1% by weight of sodium polyacrylate as a binder were added, The slurry obtained by kneading with water as a medium was applied, dried, pressed and cut on both sides of an aluminum foil having a thickness of 20 μm in the same manner as above. Then, a 240 μm band-shaped positive electrode sheet was produced. After spot welding nickel and aluminum lead plates to the respective ends of the negative electrode sheet and the positive electrode sheet, 150 ° C. in dry air with a dew point of −40 ° C. or less.
It was dehydrated and dried for 2 hours. Further, the dehydrated and dried positive electrode sheet (8), the microporous polypropylene film separator (Celgard 2400), the dehydrated and dried negative electrode sheet (9) and the separator (10) were laminated in this order, and wound in a spiral shape with a winding machine. Turned

This wound body was housed in a nickel-plated iron bottomed cylindrical battery can (11) which also served as a negative electrode terminal. LiPF ₆ and LiBF ₄ were each added to 1 L.
An electrolyte containing 9,0.1 mol and a solvent of ethylene carbonate, a 2: 2: 6 volume mixture of butylene carbonate and dimethyl carbonate, was poured into a battery can. A battery lid (12) having a positive electrode terminal is attached to a gasket (1
A cylindrical battery was produced by caulking through 3). The positive electrode terminal (12) includes a positive electrode sheet (8) and a battery can (11).
Was connected to the negative electrode sheet (9) by a lead terminal in advance. FIG. 1 shows a cross section of the cylindrical battery. In addition, (1
4) is a safety valve. This battery is referred to as Sample-1.
A cylindrical battery was manufactured in the same manner as in Sample 1 except that the surfactant of the present invention was added to the negative electrode sheet as described below and the pressing pressure was changed to change the negative electrode film thickness as described below. The charge / discharge conditions were 4.2 to 2.8 V and 1 mA / cm ² . The results are shown below.

Description of characteristics below: Capacity; first discharge capacity (discharge capacity per 1 g of negative electrode material), cycleability; charge / discharge cycleability (cycle number at which 85% of the first capacity), Li deposition Check the presence of Li metal deposition by charging the battery to 4.4V and disassembling (Li metal deposition increases the possibility of internal short circuit and reduces safety)

No. Negative electrode film thickness of the present invention Capacity Cycle property Li surfactant Surfactant μm mAh / g times Precipitated compound example Addition amount 1 127 501 390 Yes 2 110 489 260 Yes 3 W-1 0.3% 127 503 396 None 4 4 110 501 380 None 5 W-1 0.5% 127 505 394 None 6 110 503 390 None 7 W-2 0.4% 127 501 392 None 8 W-3 0.4% 127 499 392 None 9 W-4 0.6% 127 499 393 None Addition amount; wt% relative to the negative electrode material. Samples 3 to 9 containing the surfactant of the present invention did not deposit Li metal as compared with Samples 1 and 2 of Comparative Examples, and were preferable in terms of safety. Further, even if the pressing pressure was increased to reduce the film thickness of the negative electrode, the decrease in capacity and cycleability was smaller than that in Comparative Example. A thinner film is preferable because a large amount of material can be packed in a cylindrical can of the same size.

Example 2 Instead of 1-A as the negative electrode material, 1-B, 1-C, 1-
Samples 1 to 6 of the example were repeated except that D, 1-E and 1-F were used, and the same results as in example-1 were obtained.

Example-3 Example-3 except that the surfactant of the present invention was added to the positive electrode sheet as follows and the press pressure was changed to the following film thickness.
Sample 1 of 1 was repeated to prepare Samples 10 to 14. Description of characteristics below: Capacity; first discharge capacity (discharge capacity per 1 g of positive electrode material), cycleability; charge / discharge cycleability (number of cycles that makes up 80% of the first capacity), safety; current 1 mA / The maximum temperature reached when the battery was charged at cm ² for 4 hours was shown. The lower the temperature, the better the safety.

[0066]   No. Positive electrode thickness of the present invention Capacity Cycling Safety           Surfactant μm mAh / g times ℃           Compound example Addition amount   10 240 135 420 420   11 196 125 350 350 210   12 W-1 0.5% 240 136 428 120   13 195 132 420 420   14 W-2 0.5% 240 135 437 125   15 196 133 430 130   16 W-3 0.4% 240 136 445 124   17 W-7 0.8% 240 132 440 134       Addition amount: wt% relative to the positive electrode active material.

Sample Containing Surfactant of the Present Invention-
12 to Sample-17 are Comparative Samples-10 and 1
Compared with 1, the temperature rise during overcharge was small and the safety was good, which was preferable. Further, even if the pressing pressure was increased to reduce the film thickness of the positive electrode, the decrease in capacity, cycleability and safety was smaller than that in Comparative Example. A thinner film is preferable because a large amount of material can be packed in a cylindrical can of the same size.

Example-4 The injection time of the electrolytes of Samples-1 and 5 of Example-1 and Sample-14 of Example-3 was 0.6 times that of Sample-1 in Samples 5 and 14, I liked it.

[0069]

As in the present invention, when a lithium-containing transition metal oxide is used as the positive electrode material and a compound capable of absorbing and releasing lithium ions is used as the negative electrode material and a nonionic surfactant is contained, a high discharge operating voltage and a large discharge operating voltage are obtained. It is possible to obtain a non-aqueous secondary battery having a discharge capacity, excellent charge / discharge cycle characteristics, and a small temperature increase during overcharge and good safety.

[Brief description of drawings]

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

[Explanation of symbols]

8 Positive electrode sheet 9 Negative electrode sheet 10 separator 11 battery cans 12 Battery lid 13 gasket 14 Safety valve

─────────────────────────────────────────────────── ─── Continuation of the front page (56) References JP-A-8-287913 (JP, A) JP-A-8-162155 (JP, A) JP-A-7-263027 (JP, A) JP-A-7- 37578 (JP, A) JP-A-7-29605 (JP, A) JP-A-6-60877 (JP, A) JP-A-2-12776 (JP, A) JP-A-58-173142 (JP, A) JP-A-6-275268 (JP, A) JP-A-6-338325 (JP, A) (58) Fields investigated (Int. Cl. ⁷ , DB name) H01M 10/40 H01M 4/38-4/62

Claims (3)

(57) [Claims] 1. A non-aqueous secondary battery comprising a positive electrode material, a negative electrode material, and a non-aqueous electrolyte containing a lithium salt.
Non-aqueous secondary containing at least one of a positive electrode material and an electrolyte containing a nonionic surfactant, and the negative electrode material being an amorphous complex oxide represented by the following general formula (1). battery. Sn _x M ¹ _1-x M ² _a M ³ _b O _z General formula (1) Here, Sn and M ¹ are functional elements, and their valences change with occlusion and release of lithium ions. , An element that can contribute to the charge and discharge capacity. M ¹ represents a transition metal element, more preferably Fe, Mn, lead or germanium. x is 0 . It is a number of 5 or more and 1 or less. M ² is an element that can be made amorphous and contains at least one of Al, B, P and Si.
Seed, M ³ represents a Group 1 element, a Group 2 element, a Group 3 element, or a halogen element of the periodic table. a is a number of 0.2 or more and 2 or less, b is a number of 1 or less, 0.2 <a + b <2, and z is 1
It represents a number of not less than 6 and not more than 6. 2. The non-ionic surfactant is contained in the negative electrode material and / or the positive electrode material.
The non-aqueous secondary battery described in. 3. The non-aqueous secondary battery according to claim 1, wherein the nonionic surfactant contains polyoxyethylene.