KR20050052268A - Negative active material for lithium secondary battery, method of preparing same, and lithium secondary battery comprising same - Google Patents

Abstract

The present invention relates to a negative electrode active material for a lithium secondary battery including the oxide of the formula (1) and graphite, a method for manufacturing the same, and a lithium secondary battery including the negative electrode active material.

[Formula 1]

Li _x M _y V _z O _{2 + d}

In the above formula, 0.1 ≦ x ≦ 2.5, 0 ≦ y ≦ 0.5, 0.5 ≦ z ≦ 1.5, 0 ≦ d ≦ 0.5, and M is one selected from the group consisting of Al, Cr, Mo, Ti, W, and Zr. It is the above metal. The negative electrode active material for a lithium secondary battery of the present invention is a mixture of a metal oxide and graphite having an excellent energy density per unit volume, and overcomes the low capacity and efficiency of the metal oxide and maintains a high density of the high density high capacity lithium secondary battery. It is possible to manufacture, and to improve the life characteristics and high rate charge and discharge characteristics excellent.

Description

A negative electrode active material for a lithium secondary battery, a method of manufacturing the same, and a lithium secondary battery including the same TECHNICAL FIELD

The present invention relates to a negative electrode active material for a lithium secondary battery, a method for manufacturing the same, and a lithium secondary battery including the same. More specifically, a negative electrode active material for a lithium secondary battery excellent in lifespan characteristics and high rate charge-discharge characteristics, a method for producing the same, and the same It relates to a lithium secondary battery.

[Prior art]

Lithium secondary batteries, which are in the spotlight as power sources of recent portable small electronic devices, exhibit high energy density by showing a discharge voltage that is twice as high as that of a battery using an alkaline aqueous solution using an organic electrolyte solution.

As a cathode active material of a lithium secondary battery, an oxide composed of lithium and a transition metal having a structure capable of intercalating lithium, such as LiCoO ₂ , LiMn ₂ O ₄ , and LiNi _1-x Co _x O ₂ (0 <X <1) Was mainly used.

As the negative electrode active material, various types of carbon-based materials including artificial, natural graphite, and hard carbon capable of inserting / desorbing lithium have been applied. The graphite of the carbon series has a low discharge voltage of -0.2 V compared to lithium, and the battery using this negative electrode active material exhibits a high discharge voltage of 3.6 V, providing an advantage in terms of energy density of the lithium battery and excellent reversibility in lithium secondary. It is most widely used to ensure the long life of the battery. However, the graphite active material has a problem of low capacity in terms of energy density per unit volume of the electrode plate due to the low graphite density (theoretical density of 2.2 g / cc) when manufacturing the electrode plate, and easily reacts with the organic electrolyte used at high discharge voltage. There is a risk of fire or explosion due to battery malfunction or overcharging.

In order to solve this problem, oxide cathodes have recently been developed. The amorphous tin oxide researched and developed by FUJIFILM exhibits a high capacity of 800 mAh / g per weight, but has a fatal problem with an initial irreversible capacity of about 50%, a discharge voltage of 0.5 V or more, and an amorphous characteristic unique soft voltage profile. (smooth voltage profile) has a problem that is difficult to be implemented as a battery. In addition, incidental problems such as reduction of some tin oxides from oxides to tin metals due to charging and discharging have been seriously occurring, making the use of batteries even more difficult.

In addition, as an oxide cathode, Japanese Laid-Open Patent Publication No. 2002-216753 (Sumitomo) discloses Li _a Mg _b VO _c (0.05 <= a <= 3, 0.12 <= b <= 2, 2 <= 2c-a-2b <= 5) A negative electrode active material is described. In addition, a Japanese battery debate in 2002 Main Publication No. 3B05 published a lithium secondary battery negative electrode of Li _1.1 V _0.9 O ₂ .

However, the oxide negative electrode does not yet exhibit satisfactory battery performance, and research on it is ongoing.

An object of the present invention is to provide a negative electrode active material for a lithium secondary battery excellent in lifespan characteristics and high rate charge-discharge characteristics and a method of manufacturing the same.

Another object of the present invention is to provide a lithium secondary battery containing the negative electrode active material.

The present invention provides a negative electrode active material for a lithium secondary battery in which metal oxide and graphite of Formula 1 are mixed.

[Formula 1]

Li _x M _y V _z O _{2 + d}

In the above formula, 0.1 ≦ x ≦ 2.5, 0 ≦ y ≦ 0.5, 0.5 ≦ z ≦ 1.5, 0 ≦ d ≦ 0.5, and M is one selected from the group consisting of Al, Cr, Mo, Ti, W, and Zr. It is the above metal.

The present invention also comprises the steps of: a) vanadium raw material, a lithium raw material and a metal raw material mixed in a solid phase, and heat treating the mixture at a temperature of 500 to 1400 ℃ in a reducing atmosphere to produce a metal oxide of the formula (1); And b) provides a method for producing a negative electrode active material for a lithium secondary battery comprising the step of mixing the metal oxide and graphite.

The present invention also provides a positive electrode comprising a positive electrode active material capable of intercalating and deintercalating lithium ions; A negative electrode including the negative electrode active material; And it provides a lithium secondary battery comprising an electrolyte.

Hereinafter, the present invention will be described in detail.

The negative electrode active material of the present invention may be prepared by mixing the metal oxide and graphite represented by the formula (1).

The metal oxide used in the present invention is synthesized by substituting Co in a LiCoO ₂ structure with V, which is a transition metal element different from Li, and Al, Mo, W, Ti, Cr, Zr, which is another second metal element, It exhibits similar discharge potential and lifetime characteristics to graphite. Particularly, when the compound represented by Chemical Formula 1 is used as the metal oxide of the negative electrode, a capacity per unit volume of 1000 mAh / cc or more can be obtained. As the substituent represented by M in Formula 1, Mo and W are preferable among the metal elements.

When x, y, z and d in the above formula 1 is out of the above-described range, since the average potential is 1.0 V or more compared to lithium metal, the discharge voltage of the battery is too high when used as a negative electrode active material. There is a problem of being lowered. Specifically, a metal vanadium oxide cathode which does not contain Li in Solid State Ionics, 139, 57-65, 2001 and Journal of Power Source, 81-82, 651-655, 1999, using a compound with x less than 0.1. Active materials are described. However, the active material disclosed in the paper is different from the crystal structure of the active material of the present invention, the average discharge potential is also 1.0V or more there is a problem to use as a negative electrode.

In the present invention, graphite is mixed to improve conductivity of the negative electrode active material. The graphite is preferably contained in 1 to 99% by weight based on the entire negative electrode active material.

The negative electrode active material of the present invention is the area of the X-ray diffraction peak of the (003) plane of the metal oxide (hereinafter referred to as M (003)) and the area of the X-ray diffraction peak of the (002) plane of the graphite (hereinafter The M (003) / G (002) value, which is the ratio of G (002).), Is preferably 0.01 to 100, and more preferably the M (003) / G (002) value is 1 to 50. If the M (003) / G (002) value is less than 0.01, there is a problem that the capacity per volume is lowered, if it exceeds 100 there is a problem that the life characteristics are lowered.

Examples of the graphite mixed with the metal oxide may be plate-like, spherical or fibrous natural graphite or artificial graphite.

When the metal oxide of the negative electrode active material of the present invention has a theoretical energy density of 4.2 g / cc per unit volume, an electrode plate density of about 3.0 g / cc can be obtained in actual electrode plate production, and the capacity per unit weight is 300 mAh / g. Theoretically, the theoretical capacity per unit volume is 1200 mAh / cc or more, and an energy density of 900 mAh / cc or more can be obtained. Therefore, when only graphite, which is a conventional anode active material, is used, the theoretical energy density per unit volume is 2.0 g / cc, actual. With an energy density of 1.6 g / cc and 360 mAh / g, the energy density can be more than doubled compared to the actual capacity of 570 mAg / cc per unit volume.

In addition, the negative electrode active material of the present invention is also superior in stability with the organic electrolyte solution compared with the conventional carbon-based negative electrode active material.

The manufacturing process of the metal oxide of Chemical Formula 1 is as follows. First, vanadium raw material, lithium raw material and metal raw material are mixed in solid phase. At this time, the mixing ratio of the vanadium raw material, the lithium raw material and the metal raw material can be appropriately adjusted in a range where a desired composition of the formula (1) is obtained. As the vanadium raw material, vanadium metal, VO, V ₂ O ₃ , V ₂ O ₄ , V ₂ O ₅ , V ₄ O ₇ , VOSO ₄ nH ₂ O or NH ₄ VO ₃ may be used.

The lithium raw material may be selected from the group consisting of lithium carbonate, lithium hydroxide, lithium nitrate and lithium acetate, and the metal raw material is Al, Cr, Mo, Ti, W and Zr. It may be used selected from the group consisting of oxides or hydroxides containing a metal selected from. Examples thereof include Al (OH) ₃ , Al ₂ O ₃ , Cr ₂ O ₃ , MoO ₃ , TiO ₂ , WO ₃ or ZrO ₂ .

The mixture is heat-treated at a temperature of 500 to 1400 ° C., preferably 900 to 1200 ° C. under a reducing atmosphere, to prepare a negative active material for a non-aqueous electrolyte secondary battery including the lithium-vanadium oxide of Chemical Formula 1. When the heat treatment temperature is outside the range of 500 to 1400 ° C., an impurity phase (for example, Li ₃ VO _4, etc.) may be formed, and the impurity phase may cause a decrease in capacity and life, which is not preferable.

The reducing atmosphere is carried out in a nitrogen atmosphere, an argon atmosphere, an N ₂ / H ₂ mixed gas atmosphere, a CO / CO ₂ mixed gas atmosphere, or a helium atmosphere. At this time, the oxygen partial pressure in the reducing atmosphere is preferably less than 2 × 10 ⁻¹ atm. When the oxygen partial pressure of the reducing atmosphere is 2 × 10 ⁻¹ atm or more, since it is an oxidizing atmosphere, it is not preferable because the metal oxide may be synthesized in an oxidized state, that is, synthesized in another phase rich in oxygen, or a mixture with two or more other impurity phases in which oxygen is present. not.

The metal oxide and graphite are mixed to prepare a negative electrode active material for a lithium ion battery of the present invention. In this case, the metal oxide and graphite are preferably in a weight ratio of 99: 1 to 1:99, and more preferably 90:10 to 10:90. The mixed weight ratio M is the ratio of the area of the X-ray diffraction peaks (M (003)) of the (003) plane of the metal oxide and the area of the X-ray diffraction peaks (G (002)) of the (002) plane of the graphite. It is preferable that the value of (003) / G (002) is 0.01 to 100, and more preferably such that the value of M (003) / G (002) is 1 to 50.

The metal oxide and graphite may be mixed in a solid phase or a liquid phase. In the case of mixing in a solid phase, a mechanical mixing method may be mainly used. As an example of the mechanical mixing method, a kneading method and a blade structure of the mixer are changed to take shear stress during mixing. Mechanical mixing or mechanically applying a shear force between particles to induce fusion between particle surfaces; and a method using a mechanochemical method. In the case of mixing in a liquid phase, as in the case of mixing in a solid phase, mechanical mixing, spray drying, spray pyrolysis, or freeze drying may be performed. In the case of liquid mixing, water, an organic solvent, or a mixture thereof may be used as the solvent, and as the organic solvent, ethanol, isopropyl alcohol, toluene, benzene, hexane, tetrahydrofuran, or the like may be used.

The lithium secondary battery of the present invention includes a negative electrode made of the negative electrode active material. The negative electrode may be prepared as a negative electrode by applying a negative electrode mixture prepared by mixing the negative electrode active material, the conductive material, and the binder according to the present invention to a current collector such as copper.

1 shows a lithium secondary battery 1 which is an embodiment of the present invention. The lithium secondary battery 1 includes a negative electrode 2, a positive electrode 3, a separator 4 disposed between the negative electrode 2 and the positive electrode 3, the negative electrode 2, the positive electrode 3, and the separator 4. ), And the sealing member 6 which encloses the electrolyte, the battery container 5, and the battery container 5 impregnated as the main part is comprised. The shape of the lithium secondary battery illustrated in FIG. 1 may be in a cylindrical shape, but in addition, various shapes such as a cylindrical shape, a square shape, a coin shape, a sheet shape, and the like.

The positive electrode includes a positive electrode active material capable of intercalating and deintercalating lithium ions. Representative examples of the cathode active material may be selected from the group consisting of the following formula (2) to (13).

[Formula 2]

Li _x Mn _1-y M _y A ₂

[Formula 3]

Li _x Mn _1-y M _y O _2-z X _z

[Formula 4]

Li _x Mn ₂ O _4-z X _z

[Formula 5]

Li _x Co _1-y M _y A ₂

[Formula 6]

Li _x Co _1-y M _y O _2-z X _z

[Formula 7]

Li _x Ni _1-y M _y A ₂

[Formula 8]

Li _x Ni _1-y M _y O _2-z X _z

[Formula 9]

Li _x Ni _1-y Co _y O _2-z X _z

[Formula 10]

Li _x Ni _1-yz Co _y M _z A _a

[Formula 11]

Li _x Ni _1-yz Co _y M _z O _2-a X _a

[Formula 12]

Li _x Ni _1-yz Mn _y M _z A _a

[Formula 13]

Li _x Ni _1-yz Mn _y M _z O _2-a X _a

(Wherein 0.90 ≦ x ≦ 1.1, 0 ≦ y ≦ 0.5, 0 ≦ z ≦ 0.5, 0 ≦ a ≦ 2, M is Al, Ni, Co, Mn, Cr, Fe, Mg, Sr, V and At least one element selected from the group consisting of rare earth elements, A is an element selected from the group consisting of O, F, S and P, and X is F, S or P.)

The lithium secondary battery of the present invention includes a positive electrode made of the positive electrode active material. The positive electrode may be prepared as a positive electrode by applying a positive electrode mixture prepared by mixing a positive electrode active material, a conductive material and a binder to a current collector.

As the conductive material, any battery can be used as long as it is an electronic conductive material without causing chemical change, and examples thereof include natural graphite, artificial graphite, carbon black, acetylene black, ketjen black, carbon fiber, copper, nickel, Metal powders, such as aluminum and silver, metal fiber, etc. can be used, and 1 type (s) or 1 or more types can be mixed and used for electrically conductive materials, such as a polyphenylene derivative (as described in Unexamined-Japanese-Patent No. 59-20971, etc.). .

As the binder, polyvinyl alcohol, carboxymethyl cellulose, hydroxypropylene cellulose, diacetylene cellulose, polyvinyl chloride, polyvinylpyrrolidone, polytetrafluoroethylene, polyvinylidene fluoride, polyethylene or polypropylene may be used. It may be, but is not limited thereto.

As the separator, an olefin porous film such as polyethylene or polypropylene can be used.

In the lithium secondary battery of the present invention, the electrolyte includes an organic solvent and a lithium salt as an electrolyte.

The electrolyte serves as a medium through which ions involved in the electrochemical reaction of the battery can move. As the electrolyte solution, an organic solvent such as carbonate, ester, ether or ketone can be used. Dimethyl carbonate, diethyl carbonate, dipropyl carbonate, methylpropyl carbonate, ethylpropyl carbonate, methylethyl carbonate, ethylene carbonate, propylene carbonate, butylene carbonate, etc. may be used as the carbonate, and the ester may be γ-butyro. Lactone, decanolide, valerolactone, mevalonolactone, caprolactone, n-methyl acetate, n-ethyl acetate, n-propyl acetate, and the like may be used. Dibutyl ether may be used, but is not limited thereto. In addition, the organic solvent may be used alone or as a mixture of one or more, as an electrolyte, the mixing ratio in the case of using one or more mixed can be appropriately adjusted according to the desired battery performance.

In addition, the electrolyte may further include an aromatic hydrocarbon-based organic solvent. Examples of the aromatic hydrocarbon organic solvent include benzene, fluorobenzene, toluene, fluorotoluene, trifluorotoluene, xylene and the like.

Lithium salts include LiPF ₆ , LiBF ₄ , LiSbF ₆ , LiAsF ₆ , LiCF ₃ SO ₃ , LiN (CF ₃ SO ₂ ) ₃ , Li (CF ₃ SO ₂ ) ₂ N, LiC ₄ F ₉ SO ₃ , LiClO ₄ , LiAlO ₄ , LiAlCl ₄ , LiN (C _x F _{2x + 1} SO ₂ ) (where x and y are natural numbers), LiCl and LiI selected from the group consisting of You can use more than one. They dissolve in the organic solvent and act as a source of lithium ions in the cell to enable operation of the basic lithium secondary battery and to promote the movement of lithium ions between the positive and negative electrodes. The concentration of lithium salt in the electrolyte is preferably about 0.1 to 2.0 M. Hereinafter, examples and comparative examples of the present invention are described. Such following examples are only one preferred embodiment of the present invention, and the present invention is not limited to the following examples.

Example 1

Mix solid phase of Li ₂ CO ₃ , V ₂ O ₃ , and MoO ₃ to make the ratio of Li: V: Mo to 1.08: 0.9: 0.02, heat-treat at nitrogen atmosphere for 10 hours, and then cool to room temperature Was prepared.

150g of natural graphite was finely ground and then mixed with 150g of the prepared metal oxide in a planetary mixer to prepare a negative electrode active material.

(Example 2)

A negative electrode active material was prepared in the same manner as in Example 1, except that Li ₂ CO ₃ , V ₂ O ₃ , and WO ₃ were mixed in solid phase so that the ratio of Li: V: W was 1.12: 0.85: 0.05.

(Example 3)

Li ₂ CO ₃ , V ₂ O ₃ , and MoO ₃ are mixed in a solid phase so that the ratio of Li: V: Mo is 1.08: 0.9: 0.02, and heat-treated at 1,000 ° C. for 10 hours in a nitrogen atmosphere, followed by cooling to room temperature. Oxides were prepared.

After finely pulverizing 210g of natural graphite, and then mixed with 90g of the metal oxide prepared in a planetary mixer (planetary mixer) to prepare a negative electrode active material.

(Comparative Example 1)

100 g of natural graphite was finely ground and then mixed with 100 g of SnO in a planetary mixer to prepare a negative electrode active material.

(Comparative Example 2)

Li ₂ CO ₃ , V ₂ O ₃ , and MoO ₃ are mixed in a solid phase so that the ratio of Li: V: Mo is 3: 0.85: 0.05, heat-treated at 1,000 ° C. for 10 hours, and then cooled to room temperature to obtain metal oxides. Was prepared.

100 g of natural graphite was finely ground and then mixed with 100 g of the prepared metal oxide in a planetary mixer to prepare a negative electrode active material.

(Comparative Example 3)

The solid phase of Li ₂ CO ₃ , V ₂ O ₃ , and MoO ₃ is mixed so that the ratio of Li: V: Mo is 2: 0.9: 0.01, heat-treated at 1,000 ° C. for 10 hours, and then cooled to room temperature. A metal oxide was prepared and used as it is as a negative electrode active material.

X-ray diffraction patterns of the negative electrode active materials prepared in Examples 1 and 3 and Comparative Examples 1 and 3 of the present invention are shown in FIGS. 2 to 5, respectively.

[Manufacture of test cell for charge / discharge test]

A negative electrode slurry was prepared by mixing negative electrode active materials and polyvinylidene fluoride of Examples 1 to 3 and Comparative Examples 1 to 2 in N-methylpyrrolidone at a ratio of 90:10, respectively. In the negative electrode active material of Comparative Example 3, a negative electrode slurry was prepared by mixing a conductive agent (super-P) and polyvinylidene fluoride in N-methylpyrrolidone at a ratio of 80:10:10, respectively. The negative electrode slurry was coated on a copper foil (Cu-foil) to form a thin electrode plate (40 to 50 μm, including base thickness), dried at 135 ° C. for at least 3 hours, and then pressed to roll the negative electrode plate. The X-ray diffraction patterns of the negative electrode plates including the negative electrode active materials prepared in Examples 1, 3 and Comparative Example 3 are shown in FIG. 6.

With the cathode as the working electrode and the metal lithium foil as the counter electrode, a separator made of a porous polypropylene film is inserted between the working electrode and the counter electrode, and propylene carbonate (PC), diethyl carbonate (DEC) and ethylene carbonate ( A half-cell of coin type 2016 using dissolving LiPF6 to a concentration of 1 (mol / L) in a mixed solvent (PC: DEC: EC = 1: 1: 1) of EC). It was configured.

The electrical characteristics of the battery were evaluated between 0.2C ↔ 0.2C (single charge and discharge) between 0.01 and 2.0 V, 0.2C ↔ 0.2C (single charge and discharge) between 0.01 and 1.0 V, and 1C between 0.01 and 1.0 V. ↔ 1C (50 times charge and discharge) was carried out under the conditions, the measurement results are shown in Table 1 below.

TABLE 1

Plate Density [g / cc] Initial capacity [mAh / cc] Initial Efficiency [%] 50th capacity [mAh / cc] life span(%) Example 1 2.25 725 86 680 93.8 Example 2 2.21 718 85 659 91.8 Example 3 2.18 722 86 638 88.4 Comparative Example 1 2.23 583 72 283 48.5 Comparative Example 2 2.15 550 65 315 57.3 Comparative Example 3 2.45 503 80 293 58.3

7 is a graph showing the charge and discharge characteristics of the half cell prepared by Example 1 and Comparative Example 3 of the present invention.

 The technical scope of the present invention is not limited to the above embodiments, and various changes can be made without departing from the spirit of the present invention.

As described in detail above, the anode active material for a lithium secondary battery of the present invention is a mixture of a metal oxide and graphite having an excellent energy density per unit volume, and overcomes the low capacity and efficiency of the metal oxide and maintains high density. It is possible to manufacture a high capacity lithium secondary battery, and to improve the lifespan characteristics and high rate charge / discharge characteristics excellently.

1 is a perspective view illustrating an example of a lithium secondary battery.

2 is a graph showing an X-ray diffraction pattern of Example 1 of the present invention.

3 is a graph showing an X-ray diffraction pattern of Example 3 of the present invention.

4 is a graph showing an X-ray diffraction pattern of Comparative Example 1. FIG.

5 is a graph showing an X-ray diffraction pattern of Comparative Example 3.

6 is a graph showing X-ray diffraction patterns of the negative electrode active materials of Examples 1, 3 and Comparative Example 3 of the present invention.

7 is a graph showing charge and discharge characteristics of Example 1 and Comparative Example 3 of the present invention.

<Description of the symbols for the main parts of the drawings>

1: lithium secondary battery 2: negative electrode

3: anode 4: separator

5: battery container 6: sealing member

Claims (18)

A negative electrode active material for a lithium secondary battery including the metal oxide of the formula (1) and graphite. [Formula 1] Li _x M _y V _z O _{2 + d} Wherein 0.1 ≦ x ≦ 2.5, 0 ≦ y ≦ 0.5, 0.5 ≦ z ≦ 1.5, 0 ≦ d ≦ 0.5, and M is at least selected from the group consisting of Al, Cr, Mo, Ti, W, and Zr Is an element.) The negative active material of claim 1, wherein M is Mo or W. 4. The negative active material of claim 1, wherein the graphite is included in an amount of 1 to 99 wt% based on the negative active material. The area (M (003)) of the X-ray diffraction peak of the (003) plane of the metal oxide and the area (G (002)) of the X-ray diffraction peak of the (002) plane of the graphite. The negative electrode active material for lithium secondary batteries whose M (003) / G (002) value which is ratio of 0.01-100. The negative active material of claim 4, wherein the M (003) / G (002) value is 1 to 50. 6. a) solid-state mixing the vanadium raw material, the lithium raw material and the metal raw material, and heat treating the mixture at a temperature of 500 to 1400 ° C. under a reducing atmosphere to produce an oxide of Chemical Formula 1 below; And [Formula 1] Li _x M _y V _z O _{2 + d} Wherein 0.1 ≦ x ≦ 2.5, 0 ≦ y ≦ 0.5, 0.5 ≦ z ≦ 1.5, 0 ≦ d ≦ 0.5, and M is at least selected from the group consisting of Al, Cr, Mo, Ti, W, and Zr Is an element.) b) mixing the oxide and graphite Method for producing a negative electrode active material for a lithium secondary battery comprising a. The method of claim 6, wherein M is Mo or W. 8. According to claim 6, The vanadium raw material is a group consisting of vanadium metal, VO, V ₂ O ₃ , V ₂ O ₄ , V ₂ O ₅ , V ₄ O ₇ , VOSO ₄ nH ₂ O and NH ₄ VO ₃ Method for producing a negative active material for a lithium secondary battery that is selected from. The method of claim 6, wherein the lithium raw material is selected from the group consisting of lithium carbonate, lithium hydroxide, lithium nitrate, and lithium acetate. The negative electrode active material of claim 6, wherein the metal raw material is selected from the group consisting of an oxide and a hydroxide including a metal selected from the group consisting of Al, Cr, Mo, Ti, W, and Zr. Way. The method of claim 6, wherein the reducing atmosphere is nitrogen atmosphere, argon atmosphere, N ₂ / H ₂ mixed gas atmosphere, CO / CO ₂ mixed gas atmosphere, or helium atmosphere. The method of claim 6, wherein the graphite is mixed in an amount of 1 to 99% by weight based on the entire negative electrode active material. 7. The area (M (003)) of the X-ray diffraction peak of the (003) plane of the metal oxide and the area (G (002)) of the X-ray diffraction peak of the (002) plane of the graphite. A method for producing a negative electrode active material for a lithium secondary battery, wherein the ratio M (003) / G (002) is 0.01 to 100. The method of claim 13, wherein the M (003) / G (002) value is 1 to 50. A positive electrode comprising a positive electrode active material capable of intercalating and deintercalating lithium ions; A negative electrode comprising the negative electrode active material of any one of claims 1 to 5; And Electrolyte Lithium secondary battery comprising a. The lithium secondary battery of claim 15, wherein the cathode active material is selected from the group consisting of Chemical Formulas 2 to 12. 17. [Formula 2] Li _x Mn _1-y M _y A ₂ [Formula 3] Li _x Mn _1-y M _y O _2-z X _z [Formula 4] Li _x Mn ₂ O _4-z X _z [Formula 5] Li _x Co _1-y M _y A ₂ [Formula 6] Li _x Co _1-y M _y O _2-z X _z [Formula 7] Li _x Ni _1-y M _y A ₂ [Formula 8] Li _x Ni _1-y M _y O _2-z X _z [Formula 9] Li _x Ni _1-y Co _y O _2-z X _z [Formula 10] Li _x Ni _1-yz Co _y M _z A _a [Formula 11] Li _x Ni _1-yz Co _y M _z O _2-a X _a [Formula 12] Li _x Ni _1-yz Mn _y M _z A _a [Formula 13] Li _x Ni _1-yz Mn _y M _z O _2-a X _a (Wherein 0.90 ≦ x ≦ 1.1, 0 ≦ y ≦ 0.5, 0 ≦ z ≦ 0.5, 0 ≦ a ≦ 2, M is Al, Ni, Co, Mn, Cr, Fe, Mg, Sr, V and At least one element selected from the group consisting of rare earth elements, A is an element selected from the group consisting of O, F, S and P, and X is F, S or P.) The lithium secondary battery of claim 15, wherein the electrolyte comprises one or more organic solvents. The method of claim 15, wherein the electrolyte is LiPF ₆ , LiBF ₄ , LiSbF ₆ , LiAsF ₆ , LiCF ₃ SO ₃ , LiN (CF ₃ SO ₂ ) ₃ , Li (CF ₃ SO ₂ ) ₂ N, LiC ₄ F ₉ SO At least one lithium salt selected from the group consisting of ₃ , LiClO ₄ , LiAlO ₄ , LiAlCl ₄ , LiN (C _x F _{2x + 1} SO ₂ ), where x and y are natural water, LiCl and LiI Phosphorus Lithium Secondary Battery.