KR100371404B1 - Non-aqueous electrolyte battery - Google Patents

Abstract

The present invention relates to a negative electrode using a carbon material capable of occluding and releasing lithium as a negative electrode active material and a nonaqueous electrolyte secondary battery using a lithium-containing transition metal composite oxide as a positive electrode active material.

Magnesium oxide in which sodium (Na) is deposited on the surface as an additive to the anode of the present invention

(MgO), calcium oxide (CaO), aluminum oxide (Al ₂ O ₃ ), barium oxide (BaO) or mixtures thereof

Lithium secondary batteries prepared by addition were subjected to high temperature charge / discharge cycles and storage at 40 ° C. or higher.

It is excellent in high temperature charge and discharge life by suppressing side reactions.

Description

Non-Aqueous Electrolyte Secondary Battery {NON-AQUEOUS ELECTROLYTE BATTERY}

[Industrial use]

The present invention relates to a nonaqueous electrolyte secondary battery.

In particular, the present invention relates to a negative electrode using a carbon material capable of occluding and releasing lithium as a negative electrode active material and a nonaqueous electrolyte secondary battery using a lithium-containing transition metal composite oxide as a positive electrode active material.

[Prior art]

The market for portable electronic devices such as mobile phones, camcorders, and notebooks expands and diversifies

The demand for rechargeable secondary batteries that can be recharged also expands and diversifies.

It is becoming. The miniaturization, light weight, high performance, and multifunction of these electronic devices are secondary batteries.

Requires an increase in the energy storage density. In particular, secondary batteries are being developed into nickel-cadmium, nickel-hydrogen, and lithium ion batteries to increase energy storage density, making them possible to manufacture smaller and lighter batteries, thereby accelerating the weight and size of portable electronic devices. That is, it is no exaggeration to say that the development of portable electronic device technology and secondary battery technology is leading the information and communication era of the 21st century.

Among the commercialized rechargeable batteries so far, it is higher than nickel, nickel-hydrogen and lead acid batteries.

BACKGROUND ART A nonaqueous electrolyte secondary battery having an energy storage density is widely used as a rechargeable secondary battery of a portable electronic device. However, lithium secondary batteries do not yet meet the requirements of all portable electronic devices.

In particular, due to the development of semiconductor technology, notebook computers are widely used, and nonaqueous electrolyte lithium secondary batteries are used as power sources of notebook computers. However, unlike other electronic devices, they do not satisfy the high temperature characteristics required by notebook computers that generate a lot of heat. have. In the case of the nonaqueous electrolyte secondary battery, it exhibits poor high temperature life characteristics such as active reaction between the electrolyte and the negative electrode during the high temperature recharge cycle, oxidation of the electrolyte at the positive electrode during charging, decrease in capacity due to dissolution of the positive electrode active material, and increase in electrode resistance.

In general, the poor high temperature characteristics of the nonaqueous electrolyte lithium secondary battery are due to the instability of the electrolyte at a high temperature. This unstable electrolyte can cause many

Reactions occur and, through these side reactions, react with the active materials of the positive and negative electrodes again to form decomposition by-products that degrade the performance of the battery. In particular, the positive electrode active material

When the transition elements of the constituent elements of the positive electrode active material are dissolved by the reaction between the electrolytes, not only the decrease of the usable positive electrode active material but also the dissolved transition element cations are precipitated in the negative electrode to suppress the reaction of the negative electrode, thereby reducing the charge and discharge life. Therefore, if the reaction between the electrolyte decomposition by-product and the positive electrode or the negative electrode can be suppressed, the high temperature life of the battery is improved.

Conventionally, as a method of improving high temperature characteristics, a new electrolyte is developed, or a method of mixing additives such as magnesium oxide and barium oxide on the positive electrode is used. However, in order to develop a new electrolyte, it is necessary to satisfy not only high temperature characteristics but also cycle characteristics and low temperature characteristics, which has consumed enormous cost and time. U.S. Patent No. 5,846,673 also reports a method for improving the initial high temperature properties by adding a liquid additive material to the electrolyte, but it has not been reported that this method also improves long-term cycle and storage properties. Moreover, it was not verified whether the liquid phase addition material caused side reaction with the negative electrode active material.

In addition, U.S. Patent No. 5,168,019 reports a method of improving the high temperature life by adding a solid material such as aluminum oxide (Al ₂ O ₃ ) rather than a liquid phase to the electrolyte, but its effect is insignificant.

In addition, there is a method of stabilizing the positive electrode active material during charging by adding magnesium oxide to the positive electrode, but this method has a great effect on the raw material and surface properties of magnesium oxide and also does not have a great effect.

In order to improve the high temperature life and storage characteristics of the lithium secondary battery, it is essential to suppress the reaction between the electrolyte decomposition by-products and the positive electrode to suppress the decrease in capacity due to the dissolution of the positive electrode active material and the increase in electrode resistance. Closely related. The high temperature characteristics of the battery are greatly improved if the components of the positive electrode are provided with a property of suppressing the reaction between the electrolyte decomposition by-product and the positive electrode. And since it is added only to the positive electrode, no side reaction occurs at the negative electrode. Thus, the method of imparting these properties to the positive electrode is a very comprehensive solution that is compatible with any type of electrolyte.

The present invention has been made to solve the problems of the prior art, and an object of the present invention is to provide a negative electrode and a positive electrode active material for a non-aqueous electrolyte secondary battery that suppresses side reactions occurring during high temperature charge and discharge cycles and storage.

Another object of the present invention is prepared using the above-described negative electrode and positive electrode active material

It is to provide a nonaqueous electrolyte secondary battery having improved high temperature charge and discharge life.

[Means for solving the problem]

The present invention to achieve the above object,

In a nonaqueous electrolyte secondary battery,

i) a lithium metal composite oxide as an active material; And

ii) metal oxides with sodium metal deposited on their surfaces as additives

Anode electrode comprising a; And

b) absorbing and dissolving lithium as an active material

Cathode electrode comprising possible carbon material

It provides a nonaqueous electrolyte secondary battery comprising a.

In addition, the present invention is added to the positive electrode of a nonaqueous electrolyte secondary battery comprising a positive electrode comprising a lithium-containing transition metal oxide as a positive electrode active material and a negative electrode comprising a carbon material capable of occluding and releasing lithium as a negative electrode active material In the manufacturing method of the additive,

a) 200 ~ 300 ℃ under vacuum in the metal oxide having an average particle size of 1 ㎛ or less

Heat-treating to a temperature of to produce an activated metal oxide;

b) a vacuum degree of 10 ^-1 to 10 ^-4 torr on the surface of the activated metal oxide of step a),

Vacuum deposition of metallic sodium on the surface of the temperature of 350 ~ 600 ℃ to the surface

Preparing a metal oxide on which metal sodium is deposited; And

c) a metal oxide having metal sodium deposited on the surface of step b) above 500 ° C.

After heat treatment at temperature for 2 hours or more, sodium is deposited on the surface

Preparing a metal oxide imparted with electron donating properties

It provides a method for producing an additive added to the positive electrode of a nonaqueous electrolyte secondary battery comprising a.

In addition, the present invention is an amount containing a lithium-containing transition metal oxide as a positive electrode active material

In the method of manufacturing the positive electrode of a non-aqueous electrolyte secondary battery comprising a negative electrode comprising a carbon material capable of releasing lithium as a positive electrode and a negative electrode active material,

a) a lithium-containing transition metal oxide as an active material, and a conductive current collector powder

Acetylene black and Polyvinylidenedifluoride (PVDF) as a binder

90: 5 to 8: mixing in a weight ratio of 5 to 8 to prepare a mixed solution;

b) a metal oxide having metal sodium deposited on the surface of the mixed solution of step a);

1 to 3 parts by weight based on 100 parts by weight of the active material of step a) is added and mixed.

To prepare a mixture;

c) a mixture of N-methylpyrrolidine (NMP) as an organic solvent in the mixture of step b)

30 to 50 parts by weight based on 100 parts by weight is added and kneaded to prepare a slurry.

Making;

d) by applying the slurry of step c) to both sides of the aluminum current collector

Drying; And

e) pressing and rolling the current collector to which the slurry of step d) is applied and dried

Manufacturing steps

It also provides a method for producing a positive electrode of a nonaqueous electrolyte secondary battery comprising a.

The metal oxide is selected from the group consisting of magnesium oxide, calcium oxide, aluminum oxide, barium oxide.

The lithium-containing transition metal composite oxide is a compound represented by the formula

desirable.

[Formula 1]

Li _x M _1-y N _y O _z

Where

M is cobalt, nickel or manganese,

N is aluminum, indium, tin, gallium, germanium, silicon or transition metal

At least one selected from the group consisting of,

x represents a value of 0.05 <x <1.10,

y represents a value of 0 <y <0.5,

z represents a value of 1.8 <z <2.2.

The electrolyte of the nonaqueous electrolyte secondary battery is a lithium salt dissolved in a non-aqueous organic solvent

Solution is preferred.

The lithium salt is lithium pentaaxide chloride (LiClO ₅ ), lithium hexafluorophosphate (LiPF ₆ ), lithium tetrachloride aluminum (LiAlCl ₄ ), lithium hexafluoroacenic (LiAsF ₆ ), lithium hexafluoroborate (LiBF ₆ ) It is selected from the group consisting of.

The non-aqueous organic solvent is propylene carbonate (PC), ethylene carbonate (Ethylene Carbonate; EC), butyl carbonate (Butyl Carbonate; BC), vinylene carbonate (Vinylene Carbonate; VC), gamma-butyl lactone (γ-butyl) ractone, Dimethyl Carbonate (DMC), Diethyl Carbonate (DEC), Dimethoxy Ethane (DME), Diethoxy Ethane (DEE) .

The carbon material is preferably graphite.

Hereinafter, the present invention will be described in detail.

In the present invention, sodium is deposited on the surface of a positive electrode of a nonaqueous electrolyte lithium secondary battery.

Transition of positive electrode active material by decomposing by-product electrolyte decomposition byproduct into fixed or stable material by adding a certain amount of at least one metal oxide selected from the group consisting of magnesium oxide, calcium oxide, aluminum oxide and barium oxide having strong electron donor properties By suppressing the dissolution of metal elements, the high temperature life of the lithium secondary battery is improved.

In the positive electrode of the battery of the present invention, the transition metal composite oxide containing lithium represented by Chemical Formula 1 is used as a positive electrode active material, a metal oxide in which sodium is vacuum deposited on the surface, an additive, a fluorinated resin compound, a binder, and a conductive current collector powder. It is an electrode which apply | coated the mixture manufactured by mixing phosphorus carbon to the aluminum current collector board | substrate.

The negative electrode of the battery of the present invention is an electrode coated with a copper current collector substrate by mixing a binder of a fluorine resin compound with a carbon-based material capable of occluding and releasing lithium as a negative electrode active material.

The battery of the present invention is characterized in that magnesium oxide, calcium oxide, aluminum oxide, barium oxide, and mixtures thereof, in which sodium is vacuum deposited on the positive electrode of the nonaqueous electrolyte lithium battery and endowed with strong electron donor properties, are added.

Hereinafter, the present invention will be described in detail through examples and comparative examples. However, the embodiment

It is intended to illustrate the invention, not to limit the invention.

EXAMPLE

Example 1

(Production of Additives)

Metal sodium was deposited on the surface of magnesium oxide having an average particle size of 1.0 μm or less under a vacuum degree of 10 ⁻¹ to 10 ⁻⁴ torr and a temperature of 350 to 600 ° C. It was then heat treated again for 2 hours without sodium at a temperature of 500 ℃.

(Manufacture of Anode Active Material)

Lithium hydroxide (LiOH) and cobalt hydroxide (Co (OH)) were mixed at a molar ratio 1: 1, and heat-treated at 750 ° C. for 20 hours to prepare lithium cobalt oxide (LiCoO ₂ ) having an average particle diameter of 10 μm.

(Manufacture of Anode)

A lithium cobalt oxide active material having a LiCoO ₂ composition prepared as above, a conductive current collector powder, acetylene black, and a fluorinated resin compound (Polyvinylidene difluoride) as a binder in a weight ratio of 90: 5: 5, and a weight ratio of 3 to the positive electrode active material Magnesium oxide with sodium deposited on the surface was further mixed in%. The mixture was kneaded in an organic solvent NMP (N-methylpyrrlidene) at a weight ratio of 100 to 40 to prepare a slurry. This slurry was applied to one side of the aluminum current collector and dried, and then the other side was applied as above and then dried. Then, rolling was performed to prepare an electrode having a thickness of 185 µm, a length of 460 mm, and a width of 54 mm. The aluminum tab to be connected to the outer conductor at one end was fused with a spot welder.

(Manufacture of Cathode)

A crystalline carbon powder (graphite) and a fluorine resin compound (PVDF) are mixed at a weight ratio of 90:10, and 100 parts by weight of the mixture is kneaded with 70 parts by weight of an organic solvent N-methyl pyrrolidene (NMP) to prepare a slurry, and a copper current collector It was applied to one side of the substrate and dried, and then applied on the other side, followed by drying. Then, rolling was performed to prepare an electrode having a thickness of 180 μm, a length of 510 mm, and a width of 56 mm. The copper tab to be connected to the outer conductor at one end was welded with a spot welder.

(Lamination of Anode, Cathode and Separator)

The prepared cathode, cathode, and separator were laminated in a coil shape having an outer diameter of 17.1 mm using a winding device. At this time, the separator was wound in a coil shape between the anode and the cathode, and the aluminum tab fused to the anode was positioned upwardly toward the center of the jelly-roll, and the copper tab fused to the cathode was positioned outward.

(Charging jelly-roll)

The prepared jelly-roll was charged into a battery outer container having an outer diameter of 17.8 mm, the negative electrode nickel tab positioned toward the bottom of the container was fused with a spot welder on the bottom of the outer battery container, and a groove was formed in the upper part of the outer container of the battery to cover the battery lid. I made the part to be located.

(Electrolyte injection)

Electrolyte solution in which lithium hexafluorophosphate (LiPF ₆ ) is dissolved at a concentration of 1 M in a mixed solvent of ethylene carbonate (EC) and diethyl carbonate (DEC) in a volume ratio of 1: 1 is free-fall type in a dry atmosphere having a dew point of -30 ° C. It was dropped into a battery outer container and injected.

(Sealing assembly of battery)

In the center of the battery lid, which is embedded with an aluminum core in the middle and insulated with a round polypropylene, the aluminum tab of the positive electrode is fused and the battery lid is pressed and pressed in the groove made in the jelly-roll charging process. The remaining upper part of the outer container was bent inward to seal it.

(Battery evaluation)

Rechargeable cycle life was evaluated at 55 ° C. for the battery prepared above to evaluate the capacity after 100 cycles and the capacity after 300 cycles for the initial capacity. The charge and discharge conditions were as follows. The prepared nonaqueous electrolyte was discharged in a constant current method under a condition of 1.0 A of charging current, 4.1 V of constant voltage, 2.5 h of charging time, and constant current of 1.0 A of discharge current, and 3.0 V of termination voltage. The battery was charged and discharged. The results are shown in Table 1.

Example 2

A non-aqueous electrolyte secondary battery was prepared in the same manner as in Example 1 except that the cathode was manufactured by using sodium oxide instead of sodium oxide deposited magnesium oxide as an additive for the anode, and the characteristics thereof were measured. It is shown in Table 1.

Example 3

A non-aqueous electrolyte secondary battery was prepared in the same manner as in Example 1 except that the anode was manufactured by using sodium oxide deposited aluminum oxide instead of sodium oxide deposited magnesium as the additive of the cathode, and the characteristics thereof were measured. It described in 1.

Example 4

A non-aqueous electrolyte secondary battery was prepared in the same manner as in Example 1 except that the cathode was manufactured by using barium oxide on which sodium was deposited instead of magnesium oxide on which sodium was deposited as an additive. It described in 1.

Comparative Example 1

A nonaqueous electrolyte secondary battery was prepared in the same manner as in Example 1, except that the positive electrode was prepared without adding an additive, and the properties thereof were measured and the results are shown in Table 1.

battery additive Active material Initial capacity After 100 cycles After 300 cycles Remaining capacity Retention rate Remaining capacity Retention rate Example 1 MgO LiCoO ₂ 1,323 mAh 1,132 mAh 85.6% 1,011 mAh 76.4% Example 2 CaO LiCoO ₂ 1,352 mAh 1,123 mAh 83.1% 1,001 mAh 74.0% Example 3 Al ₂ O ₃ LiCoO ₂ 1,362 mAh 1,092 mAh 80.2% 985 mAh 72.3% Example 4 BaO LiCoO ₂ 1,385 mAh 1,151 mAh 83.1% 1,006 mAh 72.6% Comparative Example 1 - LiCoO ₂ 1,423 mAh 753 mAh 52.9% 456 mAh 32.0%

Table 1 is a comparison of the cycle life of the battery using a conventional positive electrode and the battery added the additive of the present invention to the cobalt-based positive electrode, showing the ratio of the initial capacity of the battery after 100 cycles and 300 cycles of recharge, It can be seen that the batteries of Examples 1 to 4 in which the additives are contained in the battery have good charge and discharge life of 55 ° C. compared to the batteries of Comparative Example 1 in which the additives are not included in the positive electrode.

Example 5

(Production of Additives)

It was prepared in the same manner as in Example 1.

(Manufacture of Anode Active Material)

LiOH, Ni (OH) ₂ , Co (OH) ₂ and Al (OH) ₃ were mixed at a molar ratio of 1.1: 0.8: 0.17: 0.03, and then heat-treated at 750 ° C. for 20 hours to obtain Li _1.0 Ni _0.8 Co _0.17 having an average particle diameter of 10 μm. Al _0.03 0 ₂ was prepared.

(Production of battery)

A nonaqueous electrolyte secondary battery was prepared in the same manner as in Example 1 except for using the cathode active material prepared by the above method.

Rechargeable cycle life was evaluated at 55 ° C. for the prepared battery to evaluate the capacity after 100 cycles and capacity after 300 cycles for the initial capacity. Charge and discharge conditions were the same as in Example 1 above. However, the charging constant voltage was 4.2 V. The results are shown in Table 2.

Example 6

A non-aqueous electrolyte secondary battery was prepared in the same manner as in Example 5 except that sodium anode was used instead of sodium oxide-deposited magnesium oxide as an additive for the cathode, and the characteristics thereof were measured. It is shown in Table 2.

Example 7

A non-aqueous electrolyte secondary battery was prepared in the same manner as in Example 5 except that sodium was deposited instead of magnesium oxide on which sodium was deposited as an additive of the cathode, and the properties thereof were measured. It is shown in Table 2.

Example 8

A non-aqueous electrolyte secondary battery was prepared in the same manner as in Example 5 except that the cathode was manufactured by using barium oxide on which sodium was deposited instead of magnesium oxide on which sodium was deposited as an additive. It is shown in Table 2.

Comparative Example 2

A nonaqueous electrolyte secondary battery was produced in the same manner as in Example 5 except for preparing the positive electrode without adding an additive, and the properties thereof are shown in Table 2.

battery additive Active material Initial capacity After 100 cycles After 300 cycles Remaining capacity Retention rate Remaining capacity Retention rate Example 5 MgO Li _1.0 Ni _0.8 Co _0.17 Al _0.03 O ₂ 1,486 mAh 1,248 mAh 84.0% 1,156 mAh 77.8% Example 6 CaO Li _1.0 Ni _0.8 Co _0.17 Al _0.03 O ₂ 1,423 mAh 1,253 mAh 88.1% 1,123 mAh 78.9% Example 7 Al ₂ O ₃ Li _1.0 Ni _0.8 Co _0.17 Al _0.03 O ₂ 1,501 mAh 1,269 mAh 84.5% 1,056 mAh 70.4% Example 8 BaO Li _1.0 Ni _0.8 Co _0.17 Al _0.03 O ₂ 1,453 mAh 1,241 mAh 85.4% 1,087 mAh 74.8% Comparative Example 2 - Li _1.0 Ni _0.8 Co _0.17 Al _0.03 O ₂ 1,512 mAh 968 mAh 64.0% 654 mAh 43.3%

Table 2 is a comparison of the cycle life of the battery using a conventional positive electrode and the battery of the additive of the present invention to the nickel-based positive electrode 55 ℃ shows the ratio of the initial capacity of the battery after 100 cycles and 300 cycles, It can be seen that the battery of Examples 5 to 8 in which the additive is included in the battery of Comparative Example 2, in which the positive electrode is not included in the positive electrode, has an excellent charge and discharge life of 55 ° C.

Example 9

(Production of Additives)

It was prepared in the same manner as in Example 1.

(Anode Active Material)

MnO ₂ and Li ₂ CO ₃ were mixed so that an atomic ratio of lithium and manganese was 1: 2, and then heat-treated at 800 ° C. for 20 hours in air to prepare LiMn ₂ O ₄ having an average particle diameter of 10 μm.

(Production of battery)

A nonaqueous electrolyte secondary battery was prepared in the same manner as in Example 1 except for using the cathode active material prepared by the above method.

Rechargeable cycle life was evaluated at 55 ° C. for the prepared battery to evaluate the capacity after 100 cycles and the capacity after 300 cycles for the initial capacity. Charge and discharge conditions were the same as in Example 1 above. However, the charging constant voltage was 4.2 V. The results are shown in Table 3.

Example 10

A non-aqueous electrolyte secondary battery was prepared in the same manner as in Example 9 except that the cathode was manufactured by using sodium oxide instead of magnesium oxide on which magnesium was deposited as an additive. It described in 3.

Example 11

A nonaqueous electrolyte secondary battery was prepared in the same manner as in Example 9, except that the cathode was manufactured by using sodium oxide deposited aluminum oxide instead of sodium deposited magnesium oxide as an additive. Described in 3.

Example 12

A non-aqueous electrolyte secondary battery was prepared in the same manner as in Example 9 except that the cathode was manufactured using sodium deposited barium oxide instead of sodium deposited magnesium oxide as an additive. It described in 3.

Comparative Example 3

A nonaqueous electrolyte secondary battery was produced in the same manner as in Example 9, except that the positive electrode was prepared without adding an additive, and the properties thereof were measured and described in Table 3.

battery additive Active material Initial capacity After 100 cycles After 300 cycles Remaining capacity Retention rate Remaining capacity Retention rate Example 9 MgO LiMn ₂ O ₄ 1,253 mAh 1,052 mAh 84.0% 879 mAh 70.2% Example 10 CaO LiMn ₂ O ₄ 1,262 mAh 1,063 mAh 84.2% 975 mAh 77.3% Example 11 Al ₂ O ₃ LiMn ₂ O ₄ 1,296 mAh 1,082 mAh 83.5% 863 mAh 66.6% Example 12 BaO LiMn ₂ O ₄ 1,295 mAh 1,071 mAh 82.7% 956 mAh 73.8% Comparative Example 3 - LiMn ₂ O ₄ 1,323 mAh 531 mAh 40.1% 341 mAh 25.8%

Table 3 is a comparison of the cycle life of the battery using a conventional positive electrode and the battery added the additive of the present invention to the manganese-based positive electrode, showing the ratio of the initial capacity of the battery after 100 cycles and 300 cycles of recharge It can be seen that the batteries of Examples 9 to 12 containing the additives were significantly superior in the charge and discharge life of 55 ° C. compared to the batteries of Comparative Example 3 in which the additives were not included in the positive electrode.

As a result of the above, by depositing sodium on the surface, by adding a metal oxide that gives electron donor properties to the positive electrode, by inhibiting the reaction between the electrolyte decomposition by-products and the positive electrode active material that may occur during high-temperature recharge and dissolution of the transition metal element in the positive electrode active material By preventing the increase in the electrode resistance, the high temperature life of the battery was improved.

In a nonaqueous electrolyte secondary battery using a negative electrode having a carbon material capable of occluding and releasing lithium as a negative electrode active material and a lithium-containing transition metal composite oxide as a positive electrode active material, magnesium oxide in which sodium is deposited on the surface as an additive to the positive electrode The lithium secondary battery prepared by adding calcium oxide, aluminum oxide, barium oxide, or a mixture thereof has excellent high temperature charge and discharge life by suppressing side charges generated during high temperature charge and discharge cycles of 40 ° C. or higher and storage.

Claims (15)

In a nonaqueous electrolyte secondary battery, a) i) a lithium metal composite oxide as an active material: and ii) an additive comprising a metal oxide on which a sodium metal is deposited on the surface Anode electrode: and b) capable of absorbing and dissolving lithium as an active material Cathode electrode comprising a carbon material Non-aqueous electrolyte secondary battery comprising a. The method of claim 1, A nonaqueous electrolyte secondary battery wherein the metal oxide of a) ii) is selected from the group consisting of magnesium oxide, calcium oxide, aluminum oxide and barium oxide. The method of claim 1, A non-aqueous electrolyte secondary battery in which the lithium-containing transition metal composite oxide of a) i) is a compound represented by the following Formula 1: [Formula 1] Li _x M _1-y N _y O _z Where M is cobalt, nickel or manganese, N is aluminum, indium, tin, gallium, germanium, silicon or transition metal At least one selected from the group consisting of, x represents a value of 0.05 <x <1.10, y represents a value of 0 <y <0.5, z represents a value of 1.8 <z <2.2. The method of claim 1, The electrolyte of the nonaqueous electrolyte secondary battery is a nonaqueous electrolyte secondary battery is a solution of lithium salt dissolved in a non-aqueous organic solvent. The method of claim 4, wherein The lithium salt is lithium pentaaxide chloride (LiClO ₅ ), lithium hexafluorophosphate (LiPF ₆ ), lithium tetrachloride aluminum (LiAlCl ₄ ), lithium hexafluoroacenic (LiAsF ₆ ), lithium hexafluoroborate (LiBF ₆ ) A nonaqueous electrolyte secondary battery selected from the group consisting of. The method of claim 4, wherein Non-aqueous electrolyte secondary, wherein the non-aqueous organic solvent is selected from the group consisting of propylene carbonate, ethylene carbonate, butyl carbonate, vinylene carbonate, gamma-butyllactone, dimethyl carbonate, diethyl carbonate, dimethoxy ethane and diethoxy ethane battery. The method of claim 1, A nonaqueous electrolyte secondary battery in which the carbon material of b) is graphite. A method for producing an additive added to a positive electrode of a nonaqueous electrolyte secondary battery comprising a positive electrode comprising a lithium-containing transition metal oxide as a positive electrode active material and a negative electrode comprising a carbon material capable of occluding and releasing lithium as a negative electrode active material. In a) 200 ~ 300 ℃ under vacuum in the metal oxide having an average particle size of 1 ㎛ or less Heat-treating to a temperature of to produce an activated metal oxide; b) a vacuum degree of 10 ^-1 to 10 ^-4 torr on the surface of the activated metal oxide of step a), Vacuum deposition of metallic sodium on the surface of the temperature of 350 ~ 600 ℃ to the surface Preparing a metal oxide on which metal sodium is deposited; And c) a metal oxide having metal sodium deposited on the surface of step b) above 500 ° C. By heat treatment at the temperature of over 2 hours, sodium is deposited on the surface Preparing a metal oxide imparted with electron donating properties Method for producing an additive added to the positive electrode of a nonaqueous electrolyte secondary battery comprising a. The method of claim 8, The method of claim 1, wherein the metal oxide of step a) is added to the positive electrode of a nonaqueous electrolyte secondary battery selected from the group consisting of magnesium oxide, calcium oxide, aluminum oxide and barium oxide. The method of claim 8, Method for producing an additive added to the positive electrode of the non-aqueous electrolyte secondary battery of the lithium-containing transition metal composite oxide is a compound represented by the following formula (1): [Formula 1] Li _x M _1-y N _y O _z Where M is cobalt, nickel or manganese, N is aluminum, indium, tin, gallium, germanium, silicon or transition metal At least one selected from the group consisting of, x represents a value of 0.05 <x <1.10, y represents a value of 0 <y <0.5, z represents a value of 1.8 <z <2.2. The method of claim 8, A method for producing an additive, wherein the carbon material is added to the positive electrode of a nonaqueous electrolyte secondary battery of graphite. In the method of manufacturing the positive electrode of a nonaqueous electrolyte secondary battery comprising a positive electrode containing a lithium-containing transition metal oxide as a positive electrode active material and a negative electrode containing a carbon material capable of releasing lithium as a negative electrode active material, a) a lithium-containing transition metal oxide as an active material, and a conductive current collector powder Acetylene black and Polyvinylidenedifluoride (PVDF) as 85 to 90 5 to 8: mixing in a weight ratio of 5 to 8 to prepare a mixed solution; b) a metal oxide having metal sodium deposited on the surface of the mixed solution of step a); 1 to 3 parts by weight based on 100 parts by weight of the active material of step a) are mixed Preparing a mixture; c) a mixture of N-methylpyrrolidine (NMP) as an organic solvent in the mixture of step b) 30 to 50 parts by weight based on 100 parts by weight is added and kneaded to prepare a slurry. Making; d) by applying the slurry of step c) to both sides of the aluminum current collector Drying; And e) pressing and rolling the current collector to which the slurry of step d) is applied and dried Manufacturing steps A positive electrode manufacturing method of a nonaqueous electrolyte secondary battery comprising a. The method of claim 12, Non-aqueous electrolyte secondary battery, wherein the metal oxide is selected from the group consisting of magnesium oxide, calcium oxide, aluminum oxide, barium oxide. The method of claim 12, A non-aqueous electrolyte secondary battery, wherein the lithium-containing transition metal composite oxide is a compound represented by Formula 1 below: [Formula 1] Li _x M _1-y N _y O _z Where M is cobalt, nickel or manganese, N is aluminum, indium, tin, gallium, germanium, silicon or transition metal At least one selected from the group consisting of, x represents a value of 0.05 <x <1.10, y represents a value of 0 <y <0.5, z represents a value of 1.8 <z <2.2. The method of claim 12, A nonaqueous electrolyte secondary battery in which the carbon material is graphite.