JPH1140154A - Electrode and battery using it - Google Patents

Abstract

PROBLEM TO BE SOLVED: To improve battery characteristics by specifying the composition of a positive electrode active material and using a mixture of graphite, having specific Lc and carbon black, as a conductive agent for the active material. SOLUTION: At least one kind of material to be used for a positive electrode active material is a compound oxide having Formula I (in the formula, A stands for one or more metals selected form alkali metals, P is one or more elements selected form among Mg, B, P, and In, M is one or more elements selected from among Mn, Co, and Al, N for is one or more element selected from among Si, Al, Ca, Cu, Sn, Mo, Nb, Y, and Bi; and w, v, z, y, z for the numbers of respective formulas II, III, IV, V, VI) and a mixture of graphite having 150 Åor higher Lc, and a carbon block having 50 m<2> /g larger specific surface area is used as the conductive agent for the positive electrode active material. The life of the positive electrode can be extended by Mn, Co, and Al and further by B, P, and Si, and moreover by adding graphite and carbon black such as those, the electron conductivity of the electrode itself can be enhanced.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a battery that can be reversibly charged and discharged a plurality of times, and more particularly to a secondary battery using a non-aqueous electrolyte.

[0002]

2. Description of the Related Art In recent years, secondary batteries have become one of the essential components that are indispensable as power sources for personal computers and mobile phones, or as power sources for electric vehicles and power storage.

[0003] Portable computers (including those called pen computers) and personal digital assistants (Personal Digit)
al Assistant or Personal Intelligent
A demand for mobile communication (mobile computing) such as a Communicator or a handheld communicator is reduction in size and weight. However, the power consumed by the backlight and drawing control of the liquid crystal display panel is high, and the capacity of the secondary battery is still insufficient at present,
It is difficult to make the system compact and lightweight.

[0004] Further, with the increase of global environmental problems, electric vehicles that do not emit exhaust gas and noise have attracted attention.
However, current batteries have problems such as short running distance, poor acceleration, small space inside the vehicle, and poor stability of the vehicle body due to low energy density and low output density.

[0005] Among secondary batteries, lithium secondary batteries using a non-aqueous electrolyte are particularly attracting attention because of their high voltage, light weight, and high energy density. As the positive electrode material of this secondary battery, conductive polymers such as polyaniline, polyacene, polyparaphenylene and Li _x
CoO ₂ , Li _x NiO ₂ , Li _x Mn ₂ O ₄ , Li _x Fe
Representative examples are oxides of transition metals such as O ₂ , V ₂ O ₅ , Cr ₂ O ₅ , and MnO _2, and chalcogenite compounds such as TiS ₂ and MoS ₂ . In particular, the positive electrode of a secondary battery such as Li _x CoO ₂ or Li _x NiO ₂ disclosed in JP-A-55-136131 has an electromotive force of 4 V or more when Li metal is used as the negative electrode. Can be expected.

[0006] However, these are not enough performances in terms of overvoltage, self-discharge characteristics, high temperature characteristics and the like during charging and discharging, in addition to the fact that the actually usable capacity is still low or the life is short. I can not say. In addition, there is also a problem in terms of safety such that the positive electrode active material is decomposed by heat during overcharge, causing thermal runaway, and the battery ignites and explodes. Conventionally, various active material compositions have been proposed in order to achieve higher capacity and longer life of a positive electrode. For example, in order to improve the cycle characteristics, the positive electrode active material may have the chemical formula Li _x MO ₂ (M is C
one or two selected from o, Ni, Fe, Mn
The use of a lithium-containing composite oxide represented by representing the kind of element) (1 JP-A-2-306022), or the formula _{Li x M y Ge z O p} (M is chosen Co, Ni, Mn, More than one transition metal element, 0.9 ≦ x ≦ 1.3,
0.8 ≦ y ≦ 2.0, 0.01 ≦ z ≦ 0.2, 2.0 ≦ p ≦
Use of the composite oxide shown in 4.5) (Japanese Patent Laid-Open No. 7-2
No. 9603).

Further, the cycle characteristics, those for improving the self-discharge _{characteristics, A x M y N z O} 2 (A is at least one selected from alkali metal, M is a transition metal, N is the Represents at least one selected from the group consisting of Al, In, and Sn, wherein 0.05 ≦ x ≦ 1.10, 0.85 ≦ y ≦
1.00, 0.001 ≦ z ≦ 10) (JP-A-7-176302).
To improve capacity and cycle characteristics, Li _y N
i _(1-x) M _x O ₂ (M is at least one element selected from the group consisting of Cu, Zn, Nb, Mo, and W; 0 <x <1,0.
It discloses that a composite oxide represented by 9 ≦ y ≦ 1.3) is used (Japanese Patent Laid-Open No. 6-283174).

In order to improve the cycle characteristics and increase the load characteristics, a chemical formula Li _x Mg _y Co _z Ni is used.
_1-yz O _a (0.95 ≦ x ≦ 1.05, 0.02 ≦ z ≦ 0.1
5, a composite oxide represented by 0.003 <y <0.02, and if z <0.02, 0.003 <y <0.05, a = 2) is used. No. 185863).

Further, in order to reduce overvoltage during charging and discharging and to suppress capacity deterioration, as a conductive agent added to the positive electrode, carbon black having an average primary particle size of 0.1 μm or less and graphite having an average particle size of 20 μm or less are used. (Japanese Unexamined Patent Publication No. Hei 8-222206) and the like are disclosed.

[0010]

The positive electrode active material has the formula L
i _x MO ₂ (M is Co, Ni, Fe, represents one or more elements selected from among Mn) when using a lithium-containing composite oxide represented by the cycle life is improved. However, it is hard to say that the characteristics are sufficient in terms of capacity. In addition, it has disadvantages such as a decrease in voltage. A _x M _y
N _z O ₂ (A is at least one selected from alkali metals, M is a transition metal, N is at least one selected from the group consisting of Al, In and Sn, and 0.05 ≦ x
≤ 1.10, 0.85 ≤ y ≤ 1.00, 0.001 ≤ z ≤
When the composite oxide represented by 0.10) is used, the cycle life is similarly improved, but the capacity that can be actually used for charging and discharging is reduced, so that the capacity cannot be increased.

[0011] The chemical in the positive electrode active material formula _{Li x M y Ge z O p} (M
Is one or more transition metal elements selected from Co, Ni, and Mn, 0.9 ≦ x ≦ 1.3, 0.8 ≦ y ≦ 2.0, 0.01 ≦
When a composite oxide represented by z ≦ 0.2, 2.0 ≦ p ≦ 4.5) is used, the capacity and cycle life are improved.

However, the thermal runaway reaction at the time of overcharging cannot be suppressed. Li _y Ni _(1-x) M _x O ₂ (M is Cu, Zn, N
at least one element selected from the group consisting of b, Mo, and W;
0 <x <1,0.9 ≦ y ≦ 1.3) When using a composite oxide represented by or formula _{Li x Mg y Co z Ni 1} -yz O a
(If 0.95 ≦ x ≦ 1.05, 0.02 ≦ z ≦ 0.15, then 0.003 <y <0.02, if z <0.02, 0.0.
003 <y <0.05, a = 2).

By using a mixed material of carbon black having an average primary particle size of 0.1 μm or less and graphite having an average particle size of 20 μm or less as a conductive agent to be added to the positive electrode, overvoltage during charging and discharging is reduced. Thus, cycle deterioration can be suppressed. However, control of the particle size alone cannot improve the rapid discharge characteristics, that is, the rate characteristics. As described above, the capacity and the life of the positive electrode material for secondary batteries can be increased,
In addition to the reduction of the overvoltage during charging and discharging and the improvement of the rate characteristics, a sufficient improvement method in terms of safety has not been found.

An object of the present invention is to improve these battery characteristics of a secondary battery material.

[0015]

Means for Solving the Problems The battery of the present invention, at least one of the positive electrode active material has the general formula _{A w P v Ni x M y} N z O 2 ( where A
Is at least one selected from alkali metals, and P
Is at least one selected from Mg, B, P, In, M is at least one selected from Mn, Co, Al, and N is Si, Al, Ca, Cu, Sn, Mo, N
represents at least one selected from b, Y, and Bi;
w, v, x, y, z are respectively 0.05 ≦ w ≦ 1.2,
0.0001 ≦ v ≦ 0.2, 0.5 ≦ x ≦ 0.95, 0.0
05 ≦ y ≦ 0.5, 0 ≦ z ≦ 0.2), a graphite having an Lc of 150 ° or more as a conductive agent of the positive electrode active material, and a specific surface area of 50 m ² / g or more of a mixture with carbon black.

[0016] be one positive electrode active material in the novel cells of this invention represented by the general formula _{A w P v Ni x M y} N z O 2,
A is at least one selected from alkali metals, for example, Li, Na, and K, and among them, Li is preferable. The value of w varies depending on the charge state and the discharge state, and the range is 0.0.
5 ≦ w ≦ 1.2. In other words, deintercalation of A ions occurs due to charging and the value of w decreases, and intercalation of A ions occurs and discharging increases the value of w.

P is at least one selected from Mg, B, P, and In, and is preferably Mg,
More preferably, it is a combination of Mg and P. Although the value of v representing the amount of N does not fluctuate due to charging and discharging, it is 0.00
It is in the range of 01 ≦ v ≦ 0.02. The value of v is 0.0001
If it is less than N, the effect of N is not sufficiently exhibited, the cycleability in deep charge and deep discharge for obtaining a high capacity is poor, and the capacity is undesirably reduced. In addition, the value of v is set to 0.
If it exceeds 2, the capacity is undesirably reduced. Mg
The atomic ratio of Mg / P in the combination of P and P is preferably 0.1 or more and 12 or less.

The value of x representing the amount of Ni is 0.5 ≦ x
≦ 0.95. When the value of x is less than 0.5, the capacity is significantly reduced, which is not preferable. Also, if the value of x is 0.
If it exceeds 95, the cyclability in deep charge and deep discharge is poor, which is not preferable.

M is at least one selected from Mn, Co, and Al. The value of y does not vary depending on the state of charge and the state of discharge, and its range is 0.005 ≦ y ≦ 0.5. When the value of y is less than 0.005, the effect of M is not sufficiently exhibited, and the cycleability in deep charging and deep discharging is poor, which is not preferable. On the other hand, when the value of y exceeds 0.5, the capacity is reduced and the voltage is further reduced, which is not preferable.

N is Si, Al, Ca, Cu, Sn, M
It is at least one selected from o, Nb, Y, and Bi. The value of y does not vary depending on the state of charge and the state of discharge, and its range is 0 ≦ y ≦ 0.2. If the value of y exceeds 0.2, the capacity decreases and the voltage further decreases, which is not preferable.

The novel battery according to the present invention is characterized in that a mixture of graphite having an Lc of 150 ° or more and carbon black having a specific surface area of 50 m ² / g or more is used as a conductive agent of a positive electrode active material. If only graphite or only carbon black is added, the internal resistance of the electrode is high and good battery characteristics cannot be obtained. When graphite having an Lc of less than 400 ° is used, electron conductivity is low and good battery characteristics cannot be obtained. Also, when carbon black having a specific surface area of less than 50 m ² / g is used, good battery characteristics cannot be obtained because the internal resistance of the electrode becomes high.

As the negative electrode, graphite, pyrolytic graphite, carbon fiber, vapor-grown carbonaceous material, pitch-based carbonaceous material, coke-based carbonaceous material, phenol-based carbonaceous material, rayon-based carbonaceous material, polyacrylonitrile-based carbon Low-crystalline carbon and high-crystalline carbon selected from the group consisting of conductive materials, needle coke, polyacrylonitrile-based carbon fibers, glassy carbon, carbon black, furfuryl alcohol-based carbonaceous materials, and polyparaphenylene. And / or at least one carbon material selected from the group consisting of a carbon material obtained by combining at least one of the above or a plurality thereof, and / or the carbon material contains a group IIIb, IVb, or Vb group atom in the periodic table. Oxides or chalcogen compounds, carrying these amorphous materials, or plating Or at least one or more composite materials selected from the group consisting of fused materials and / or at least one or more conductive materials selected from the group consisting of polyacene, polyparaphenylene, polyaniline, polyacetylene, and disulfide compounds. Molecular material and / or Li _x Fe ₂ O ₃ , Li _x Fe ₃ O ₄ , Li _x
By using at least one inorganic material selected from the group consisting of WO ₂ , oxides containing atoms of Group IIIb, IVb and Vb of the periodic table, chalcogen compounds and amorphous materials thereof, the battery of the present invention Shows good characteristics.

Examples of the electrolyte include propylene carbonate, propylene carbonate derivatives, ethylene carbonate, butylene carbonate, vinylene carbonate, gamma-butyl lactone, dimethyl carbonate,
Diethyl carbonate, methyl ethyl carbonate,
1,2-dimethoxyethane, 2-methyltetrahydrofuran, dimethylsulfoxide, 1,3-dioxolane, formamide, dimethylformamide, dioxolane, acetonitrile, nitromethane, gisanmethyl, methyl acetate, methyl propionate, ethyl propionate,
Phosphate triester, trimethoxymethane, dioxolane derivative, diethyl ether, 1,3-propanesultone, sulfolane, 3-methyl-2-oxazolidinone,
At least one non-aqueous solvent selected from the group consisting of tetrahydrofuran, tetrahydrofuran derivative, dioxolan, 1,2-diethoxyethane, and halides thereof, and a lithium salt such as LiClO ₄ ,
LiBF ₄ , LiPF ₆ , LiCF ₃ SO ₃ , LiCF ₃ CO ₂ , Li
AsF ₆ , LiSbF ₆ , LiB ₁₀ Cl ₁₀ , LiAlCl
₄ , a mixed solution of at least one salt selected from the group consisting of LiCl, LiBr, LiI, lithium lower aliphatic carboxylate, lithium chloroborane, lithium lithium tetraphenylborate, and a mixed solution of these and a polymer For example, by using a gel electrolyte in which at least one or more selected from the group consisting of polyacrylonitrile, polyethylene oxide, polyvinylidene fluoride, polymethyl methacrylate, and hexafluoropropylene is used, the battery of the present invention is excellent. Characteristics.

The use of the reversibly chargeable / dischargeable battery of the present invention is not particularly limited. For example, notebook personal computers, pen input personal computers, pocket personal computers, notebook word processors, pocket word processors, electronic book players, mobile phones, cordless phones Phone handset, pager, handy terminal, portable copy, electronic organizer, calculator, LCD TV,
Electric shaver, power tool, electronic translator, car phone,
Power supplies for devices such as transceivers, voice input devices, memory cards, backup power supplies, tape recorders, radios, headphone stereos, portable printers, handy cleaners, portable CDs, video movies, navigation systems, refrigerators, air conditioners, televisions,
Stereo, water heater, microwave oven, dishwasher,
It can be used as a power source for washing machines, dryers, game devices, lighting devices, toys, road conditioners, medical devices, automobiles, electric vehicles, golf carts, electric carts, power storage systems, and the like. It can be used not only for civilian purposes but also for military use and space.

[0025] That is, in at least one of the positive electrode active material, the general formula _{A w P v Ni x M y} N z O 2 ( where A is at least one selected from alkali metal, P is Mg, B, P , I
n is at least one member selected from the group consisting of Mn, C
at least one selected from o and Al, and N is S
i, Al, Ca, Cu, Sn, Mo, Nb, Y, Bi, and at least one selected from w, v, x, y,
z is 0.05 ≦ w ≦ 1.2, 0.0001 ≦ v ≦
0.2, 0.5 ≦ x ≦ 0.95, 0.005 ≦ y ≦ 0.5, 0 ≦
By using a complex oxide represented by the following formula: z ≦ 0.2), it is possible to achieve high capacity, long life, low overvoltage during charge and discharge, and explosion and ignition during overcharge. A high-safety battery with no waste is obtained.

Also, Lc is 1 as a conductive agent of the positive electrode active material.
By using a mixture of graphite of 50 ° or more and carbon black having a specific surface area of 50 m ² / g or more, rapid charging characteristics are greatly improved, and a battery having particularly excellent low-temperature rate characteristics can be obtained. By using the electrode of the present invention and a battery using the same in various systems, the size and weight of the system can be reduced. In addition, it can be applied to a system that requires high-rate discharge at a low temperature.

The operation of the positive electrode active material of the present invention will be specifically described. Since Mn, Co, and Al are harder to oxidize than Ni,
The service life can be extended by these pillar effects. The pillar effect refers to the effect of suppressing the stress of the crystal structure by pinning in the crystal because the specific element itself does not participate in the oxidation-reduction reaction in charge and discharge, that is, does not involve a change. Say Mg, Mo, Cu, Al,
Since Ca and Si have the effect of increasing the electrical conductivity of the positive electrode active material, overvoltage during charging and discharging can be reduced.

Since B, P, and Si have small ionic radii, their substitution can reduce the lattice volume of the positive electrode active material, suppress the collapse due to expansion of the lattice volume during charging, and extend the life. it can. Since B and P are present at interstitial positions, the capacity does not decrease due to the replacement of B and P, and a high capacity can be maintained. Si, In, Sn, Mg, Ca, Bi
Substitution with, which tends to cause defects in the crystal, can increase the capacity and also improve the rate characteristics. M
Since g, P, Al, B, Si, Y, Nb, and Ca have low oxygen releasing ability and are stably present as oxides, safety at high temperatures can be improved.

Further, Mg, P, Si and Ca have different valences from the main constituent ions Ni and Li and are inserted at interstitial positions, so that the electronic structure in the crystal changes.
Since an improvement in electrical conductivity is expected, it is possible to achieve a reduction in overvoltage due to a reduction in internal resistance of the electrode, an improvement in rate characteristics and temperature characteristics, and a higher capacity. Mg is Li
Since the ionic radius is smaller than that of the ions, the replacement of the Li site with the Li site can reduce the lattice volume of the positive electrode active material, suppress the collapse due to expansion of the lattice volume during charging, and extend the life. Further, since Mg has a pillar effect after Li is released by substitution to the Li site,
The contraction of the grid that occurs at the end of charging is suppressed, the grid has almost no stress, and the life can be extended even when overcharging is performed.

Next, the function of the conductive agent of the present invention will be described. Lc
However, since the graphite has a high electronic conductivity of 150 ° or more, the addition of this increases the electron conductivity of the electrode itself. Further, in the case of carbon black having a specific surface area of 50 m ² / g or more, a binder used for fixing the positive electrode active material to the current collector is taken into the pores, so that the electrode is covered with a binder having a high insulating property. And the electronic conductivity is increased. By the addition of these two types of carbon, the electron conductivity is further enhanced,
High-rate discharge at low temperatures, which has been considered difficult, becomes possible.

The operation of the electrolytic solution of the present invention will be described. LiClO ₄ , LiBF ₄ , LiPF ₆ , LiCF ₃ S
_{O 3, LiCF 3 CO 2,} LiAsF 6, LiSbF 6, L
iB ₁₀ Cl ₁₀ , LiAlCl ₄ , LiCl, LiBr,
When LiI, lithium lower aliphatic carboxylate, lithium chloroborane, and lithium tetraphenylborate are used, they show excellent temperature characteristics. In particular, LiBF ₄ , LiPF ₆ ,
When at least one of LiCF ₃ SO ₃ and LiCF ₃ CO ₂ is used, the elution of the M element in the positive electrode active material of the present invention is suppressed even when left at 60 ° C., so that the effect of excellent high-temperature characteristics is obtained. Demonstrate.

Further, propylene carbonate, propylene carbonate derivative, ethylene carbonate,
Butylene carbonate, vinylene carbonate, gamma-butyl lactone, dimethyl carbonate, diethyl carbonate, methyl ethyl carbonate, 1,2-dimethoxyethane, 2-methyltetrahydrofuran, dimethyl sulfoxide, 1,3-dioxolan, formamide, dimethylformamide, dioxolan, Acetonitrile, nitromethane, gisanmethyl, methyl acetate, methyl propionate, ethyl propionate, phosphoric acid triester, trimethoxymethane, dioxolane derivative, diethyl ether, 1,3-propanesultone, sulfolane, 3-methyl-2-oxazolidinone, Tetrahydrofuran, tetrahydrofuran derivative, dioxolan,
When 1,2-diethoxyethane is used, it shows excellent life characteristics. In particular, at least propylene carbonate, propylene carbonate derivatives, ethylene carbonate, butylene carbonate, vinylene carbonate, gamma-butyl lactone, dimethyl carbonate, diethyl carbonate, methyl ethyl carbonate, 1,2-dimethoxyethane, 2-methyltetrahydrofuran, and dimethyl sulfoxide. When one is used, an irreversible reaction between the negative electrode active material of the present invention and a solvent is suppressed, so that an effect with excellent life characteristics is exhibited.

Further, when the solvent contains a halide of the above-mentioned solvent, the safety is remarkably improved. In particular, propylene carbonate, propylene carbonate derivatives,
Some of the elements of ethylene carbonate, butylene carbonate, vinylene carbonate, gamma-butyl lactone, dimethyl carbonate, diethyl carbonate, methyl ethyl carbonate, 1,2-dimethoxyethane, 2-methyltetrahydrofuran, and dimethylsulfoxide are replaced with -F, -CF _{, -CF 2, -CF 3, -Cl} , -CC
l, -CCl _2, when using at least one of those replaced by -CCl _3, exothermic reaction in overcharging condition between the positive electrode active material and the solvent is suppressed in the present invention, establishes a significantly lowering of ignition And show high security.

Gel electrolysis in which a mixed solution of the above lithium salt and a solvent is mixed with at least one selected from the group consisting of polyacrylonitrile, polyethylene oxide, polyvinylidene fluoride, polymethyl methacrylate, and hexafluoropropylene. When a liquid is used, an exothermic reaction between the positive electrode active material of the present invention and the gel electrolyte under an overcharge condition is suppressed, the establishment of ignition is significantly reduced, and high safety is exhibited. In addition, in the combination of the positive electrode active material of the present invention and the gel electrolyte, even at a high potential of 4.5 V, the positive electrode active material of the present invention can be charged, so that the capacity can be increased.

[0035]

BEST MODE FOR CARRYING OUT THE INVENTION Hereinafter, the present invention will be described in more detail with reference to specific examples, but the present invention is not limited to the examples unless it exceeds the gist of the invention.

Example 1 A material having the composition shown in Table 1 was used as a positive electrode material, and graphite of Lc shown in Table 1 and carbon black having a specific surface area of 5: 1 were used as a conductive agent and polyfluorinated as a binder. Vinylidene was weighed so as to have a weight ratio of 88: 7: 5, kneaded with a grinder for 30 minutes, and applied to both sides of a 20-micron thick aluminum foil. An artificial graphite was used as the negative electrode material, and 93% by weight thereof was used. As a binder, a mixture prepared by preparing 7% by weight of polyvinylidene fluoride was used.
It was applied to both sides of a 0 micron copper foil. The positive and negative electrodes were roll-formed by a press, and the terminals were spot-welded and then vacuum-dried at 150 ° C. for 5 hours. A positive electrode and a negative electrode were laminated with a microporous polypropylene separator interposed therebetween, spirally wound, and inserted into an aluminum battery can. The negative electrode terminal was welded to the battery can, and the positive electrode terminal was welded to the battery lid.

As an electrolytic solution, a solution prepared by dissolving 1 mol of LiPF ₆ in 1 liter of a mixed solution of ethylene carbonate and diethyl carbonate was used, and the solution was poured into a battery can.
The battery lid was swaged to produce a cylindrical battery having a capacity of 1800 mAh. After charging the battery to 4.2V at 360mA, 36
Performs constant current charging and discharging at 2.7 mA at 0 mA, capacity, life, 1.5 C rate characteristics at −20 ° C., −20
The 2C overcharge test at 0 ° C was evaluated. Table 1 shows the results.

[0038]

[Table 1]

Comparative Example 1 A battery was manufactured in the same manner as in Example 1 except that the materials shown in Table 1 were used as the positive electrode material and the conductive agent. The capacity, life, 1.5 C rate characteristics at -20 ° C, and 2C overcharge test at -20 ° C were evaluated. Table 1 shows the results. There is an extremely low characteristic as compared with the first embodiment.

[0040]

According to the present invention, it is possible to realize high safety, compactness and light weight of a battery and a system, good high-rate characteristics at a low temperature, and a long life.

Continued on the front page (72) Inventor Ren Muranaka 7-1-1, Omika-cho, Hitachi City, Ibaraki Prefecture Within Hitachi Research Laboratory, Hitachi, Ltd.

Claims (4)

[Claims] 1. A battery comprising a negative electrode, a positive electrode, and a non-aqueous electrolyte containing a lithium salt, which can be charged and discharged a plurality of times reversibly.
At least one of the positive electrode active materials has a general formula of A _w P _v Ni _x M _y N _z O
₂ (where A is at least one selected from alkali metals, P is at least one selected from Mg, B, P, In, and M is at least one selected from Mn, Co, Al And N is Si, Al, Ca, Cu, Sn,
Mo, Nb, Y, Bi represents at least one selected from the group consisting of w, v, x, y, and z, each of 0.05 ≦ w ≦ 1.
2, 0.0001 ≤ v ≤ 0.2, 0.5 ≤ x ≤ 0.95,
(Representing the number of 0.005 ≦ y ≦ 0.5, 0 ≦ z ≦ 0.2)
And a graphite having a Lc of 150 ° or more and a specific surface area of 50 m ² as a conductive agent of the positive electrode active material.
/ G and a battery using the same. 2. The negative electrode includes graphite, pyrolysis graphite, carbon fiber, vapor-grown carbonaceous material, pitch-based carbonaceous material, coke-based carbonaceous material, phenol-based carbonaceous material, rayon-based carbonaceous material, Low-crystalline carbon selected from the group consisting of conductive materials such as polyacrylonitrile-based carbonaceous material, needle coke, polyacrylonitrile-based carbon fiber, glassy carbon, carbon black, furfuryl alcohol-based carbonaceous material, and polyparaphenylene; At least one carbon material selected from the group consisting of at least one of the highly crystalline carbons or a carbon material obtained by combining a plurality of them, and / or the periodic table IIIb, IVb, Vb Oxides or chalcogen compounds containing group-atoms, carrying these amorphous materials, or plating Or at least one or more composite materials selected from the group consisting of fused materials and / or at least one or more conductive materials selected from the group consisting of polyacene, polyparaphenylene, polyaniline, polyacetylene, and disulfide compounds. Molecular material and / or Li _x Fe ₂ O ₃ , Li _x Fe ₃ O ₄ , Li _x
2. The battery according to claim 1, wherein at least one inorganic material selected from the group consisting of WO ₂ , oxides containing atoms of Group IIIb, IVb, and Vb of the periodic table, chalcogen compounds, and amorphous materials thereof is used. 3. An electrolyte comprising propylene carbonate,
Propylene carbonate derivatives, ethylene carbonate, butylene carbonate, vinylene carbonate, gamma-butyl lactone, dimethyl carbonate, diethyl carbonate, methyl ethyl carbonate, 1,2-
Dimethoxyethane, 2-methyltetrahydrofuran, dimethylsulfoxide, 1,3-dioxolane, formamide, dimethylformamide, dioxolane, acetonitrile, nitromethane, gisanmethyl, methyl acetate,
Methyl propionate, ethyl propionate, phosphoric acid triester, trimethoxymethane, dioxolane derivative,
Diethyl ether, 1,3-propane sultone, sulfolane, 3-methyl-2-oxazolidinone, tetrahydrofuran, tetrahydrofuran derivative, dioxolan,
At least one or more non-aqueous solvents selected from the group consisting of 1,2-diethoxyethane and / or halides thereof, and LiClO ₄ , LiBF ₄ , LiP
F ₆ , LiCF ₃ SO ₃ , LiCF ₃ CO ₂ , LiAsF ₆ , LiS
bF ₆ , LiB ₁₀ Cl ₁₀ , LiAlCl ₄ , LiCl, Li
A mixed solution of at least one lithium salt selected from the group consisting of Br, LiI, lithium lower aliphatic carboxylate, lithium chloroborane, lithium tetraphenylborate, and / or a mixed solution thereof; The battery according to claim 1, wherein a gel electrolyte mixed with at least one polymer selected from the group consisting of polyacrylonitrile, polyethylene oxide, polyvinylidene fluoride, polymethyl methacrylate, and hexafluoropropylene is used. 4. A notebook personal computer, a pen input personal computer, a pocket personal computer, a notebook type word processor, a pocket word processor,
E-book player, mobile phone, cordless phone handset, pager, handy terminal, mobile copy,
Electronic organizer, calculator, liquid crystal television, electric shaver, electric tool, electronic translator, car phone, transceiver, voice input device, memory card, backup power supply, tape recorder, radio, headphone stereo, portable printer, handy cleaner, portable CD, Video movie, navigation system, refrigerator, air conditioner,
TV, stereo, water heater, microwave oven, dishwasher, washing machine, dryer, game equipment, lighting equipment, toy, road conditioner, medical equipment, automobile, electric car, golf cart, electric cart, power storage system The battery according to claim 1, wherein the battery according to item 1 is used.