KR101236436B1 - High power anode material for lithium secondary battery and preparation method thereof - Google Patents

Abstract

The present invention mixes precursor particles of lithium carbonate (Li ₂ CO ₃ ), vanadium oxide (V ₂ O ₃ ), tungsten oxide (WO ₂ ) and molybdenum oxide (MoO ₂ ), which is 90 mol% nitrogen gas and 10 mol% The present invention relates to a high output negative electrode material for a lithium secondary battery synthesized by a method of pyrolysis by a solid-state reaction in a mixed gas phase composed of hydrogen gas, and to a volume of the initial irreversible capacity and the continuous charge / discharge reaction. Since the change is small, the present invention provides a negative electrode material for a lithium secondary battery having high output, high capacity, high rate charge / discharge characteristics, and improved cycle performance.

Description

High power anode material for lithium secondary battery and preparation method

The present invention relates to a negative electrode material for a lithium secondary battery, a negative electrode and a method for manufacturing the same, and more particularly, to a samsung system high output negative electrode material for a lithium secondary battery and a method for manufacturing the same.

Conventional lithium secondary battery oxide-based negative electrode material using a precursor such as lithium carbonate (Li ₂ CO ₃ ) and vanadium oxide (V ₂ O ₃ ) as a precursor was prepared by a method of pyrolysis under a pure nitrogen atmosphere.

The conventional technology related to such a lithium / vanadium oxide negative electrode material for a lithium secondary battery is a method of mixing and firing precursors such as Li ₂ CO ₃ and V ₂ O ₅ and organic acids such as (COOH) ₂ (Patent Application No. 10- 2007-0120974, Samsung SDI Co., Ltd., LiNiVO ₄ , LiMnVO ₄ and the like cathode material manufacturing method using crystalline vanadium (Patent Application No. 10-2004-0056699, Korea Electrotechnology Research Institute), Li _{0 .1-2.5} M _{0 -0.5} V _{0 .5-1.5} O _{2 -2.5,} and M is Al, Cr, Mo, Ti, Zr and the negative electrode material consisting of W (Patent No. 10-056537, Ltd. Samsung SD children), Li _a Mg _b VO _c (0.05 <= a <= 3, 0.12 <= b <= 2, 2 <= 2c-a-2b <= 5) anode material (Japanese Patent Laid-Open No. 2002-216753, Sumitomo), lithium salt, Hydrothermal method of manufacturing lithium vanadium oxide negative electrode material by sol-gel method using vanadium salt (patent application No. 10-2007-0037983 ~ 0037988, Samsung SDI Co., Ltd.), lithium salt, vanadium salt, additive salt Active material bulb by mixing with solvent Method for producing a method and by this reduction calcined for producing a cathode material (Patent Application No. 10-2007-0073377, Ltd. Samsung SD children), Li _a Mg _b VO _c (0.05 <= a <= 3 , 0.12 <= b <= 2, 2 <= ca-2b <= 5) in the form of anode material, or Ce _{0 .7} Zr _{0 .3} O lithium vanadium oxide comprising _{at 0.9} Oxide-based anode material manufacturing method (US Patent Application No. 2008/0241688), Li ₂ CO ₃ , V ₂ O ₅ Precursor and ((COOH) ₂₎ in a method of mixing a lithium vanadium oxide cathode material of the organic acid precursor (U.S. Patent Application No. _{2008/0182171), Li 1 .1 Ti 0} .1 V 0 .9 O 2 Li SiO _{2 on the} surface of vanadium oxide anode material Manufacturing method by surface treatment method of coating inorganic oxide such as US Patent Application No. 2008/0118840, Method of manufacturing negative electrode material by mixing with lithium vanadium oxide and additives such as ZrO ₂ , Y ₂ O ₃ (patent application No. 10-2007-0120978, Samsung SDI Co., Ltd., a manufacturing method (Patent No. 10-08056123, Samsung SDI Co., Ltd.) by a surface treatment method of coating a carbon-based material on lithium vanadium oxide, and the like are known. have.

However, conventional negative electrode materials manufactured through these methods are generally Li ₃ VO ₄ during the manufacturing process There is a problem in that generation of impurities, such as many, is difficult to control the oxidation number of vanadium.

Therefore, since the initial charge / discharge capacity and efficiency are low, and the cycle performance tends to be reduced, research to improve this is in progress.

The present invention is to solve the problems of the conventional negative electrode material for lithium secondary batteries as described above, the initial low charge / discharge efficiency and output characteristics and cycle performance that is the biggest problem in the commercialization of lithium / vanadium oxide-based negative electrode material It is an object of the present invention to provide a high-output negative electrode material for a lithium secondary battery and a method for manufacturing the same, which improve the efficiency and lower the amount of impurities.

The present invention also provides a lithium carbonate (Li ₂ CO ₃ ), vanadium oxide (V ₂ O ₃ ) and high density and environmentally friendly tungsten oxide (WO ₂ ), molybdenum oxide (MoO ₂ ) in manufacturing a negative electrode material for a lithium secondary battery It is an object of the present invention to provide a high-output negative electrode material for a lithium secondary battery comprising a method of mixing the metal oxide particles and thermally decomposing the same by an inert gas such as argon, nitrogen, and hydrogen gas by a solid phase method. .

The present invention also uses lithium ternary negative electrode material with improved electrode mixture density compared to conventional carbon-based negative electrode material, transition metal negative electrode material, lithium / vanadium oxide-based negative electrode material, and has high power, high capacity, and long life. It is an object to provide a battery.

Above object of the present _{invention, Li 1 .1 V 0 .9-2x (} M1) x (M2) is achieved by providing a high-output lithium secondary battery negative electrode material having the mixture ratio of _{x O 2 (x = 0.01 ~} 0.09) .

In the production of a lithium secondary battery negative electrode material according to the present invention, lithium carbonate (Li ₂ CO _3), vanadium oxide (V ₂ O _3), metal 1 (M1), metal 2 (M2) Li _{1 .1} mixing in a ratio of _{V 0 .9-2x (M1) x (} M2) x O 2 (x = 0.01 ~ 0.09); Milling at 200-300 rpm for 1 hour so that the average particle diameter of the mixed precursor is 100 nm-20 μm; Charging the milled precursor to a tubular furnace and heat-treating at a temperature of 400-1300 ° C. for 5-20 hours in a gas mixture of inert gas and hydrogen gas; And cooling and pulverizing the heat-treated precursor, and then sieving through a sieve of 200 to 270 mesh. Provided is a method of manufacturing a high output negative electrode material for a lithium secondary battery, comprising a configuration.

In the above method of manufacturing a high-output negative electrode material for a lithium secondary battery, the heat treatment step proceeds first at a temperature of 450 ~ 550 ℃ 6 hours, and proceeds while raising the temperature at a rate of 5 ℃ / min to 1100 ℃ second.

In the method of manufacturing a high-output negative electrode material for a lithium secondary battery, injecting a mixed gas of 90 mol% inert gas and 10 mol% hydrogen gas into the tubular furnace before the heat treatment step for 1 hour or more to create an inert atmosphere. It may include.

Preparation of the negative electrode for a lithium secondary battery using the negative electrode material prepared by the present invention, the negative electrode material according to the invention 80 to 90% by weight, the binder 5 to 10% by weight, the conductive material 5 to 10% by weight of mixing; Preparing a slurry having a viscosity of 1000 to 3000 cP by adding 1 to 2 times the NMP organic solvent to the mixture; Stirring the prepared slurry for 30 minutes at 1000 ~ 3000rpm in a mixer; And applying the stirred slurry to a copper thin film having a thickness of 5 to 15 μm using a doctor blade method at a thickness of 30 to 200 μm and drying it at a temperature of 70 to 90 ° C .; It is made by a method comprising a.

The negative electrode material for a lithium secondary battery according to the present invention has the characteristics of high output, high capacity, and long life compared to the existing negative electrode material due to improved electrode mixture density, and particularly, the initial charge / discharge efficiency and output characteristics are high, and the cycle performance is improved. There is.

In addition, the method of manufacturing a negative electrode material for a lithium secondary battery according to the present invention has a small amount of impurities compared to the conventional method, and because it is made of a simple, environmentally friendly manufacturing process, it is effective to produce a large amount of anode material for excellent performance at a low cost. have.

Figure 1 is a graph showing the X-ray diffraction (XRD) analysis results of the lithium-based negative electrode material prepared by Examples 1 to 3 and the lithium / vanadium oxide anode material according to a comparative example.
FIG. 2 is a photograph showing SEM (Scanning electron microscopy) analysis results of a lithium-based negative electrode material prepared in Example 3 of the present invention and a lithium / vanadium oxide negative electrode material according to a comparative example.
3A, 3B, and 3C are graphs showing potential / current circulating characteristic curves of a battery composed of a ternary negative electrode and a lithium / vanadium oxide negative electrode manufactured by Examples 1 to 3 of the present invention.
FIG. 4 is a graph showing a low-rate charge / discharge voltage characteristic curve of a battery composed of a lithium-based negative electrode prepared in Examples 1 to 4 and a lithium / vanadium oxide negative electrode and a lithium / oxide negative electrode according to a comparative example.
5 is a graph showing a high-rate charge / discharge voltage characteristic curve of a battery composed of a ternary negative electrode prepared in Examples 1 to 3 of the present invention and a lithium / vanadium oxide negative electrode according to a comparative example.
6 is a diagram showing the cycle characteristics of a battery using a composite anode using a ternary oxide based graphite material prepared in Example 5 of the present invention.

A negative electrode material according to the present invention is _{Li 1 .1 V 0 .9-2x (M1} ) x (M2) is represented by the following formula, where the value of x in the _x O ₂ is 0.01 ~ 0.09, M1 and M2 is Mg, Ca , Two different metals selected from aluminum, titanium, copper, chromium, manganese, tin, indium, zinc, gallium, germanium, zirconium, molybdenum, antimony and tungsten.

The present invention lithium carbonate (Li ₂ CO ₃ ), vanadium oxide (V ₂ O ₃ ), Tungsten oxide (WO ₂ ), Molybdenum Oxide (MoO ₂ ) Precursors Mixing the particle ratio different stoichiometry and this by using an inert gas and a gas mixture consisting of hydrogen gas of argon, nitrogen or the like by heat treatment at a high temperature _{Li 1 .1 V 0 .9-2 x W} x Mo x O 2 (x = It provides a negative electrode material for a lithium secondary battery made of a compound of 0.01 ~ 0.09).

These particles such as lithium carbonate, vanadium oxide, tungsten oxide and molybdenum oxide are mixed in a stoichiometric ratio and then mixed in an atmosphere of a mixed gas composed of inert gas such as argon and nitrogen and hydrogen gas (argon and nitrogen are each independently hydrogen). And a method of manufacturing a negative electrode material for a lithium secondary battery manufactured by heat treatment at a high temperature and a method of manufacturing a negative electrode for a lithium secondary battery using the negative electrode material will be described in detail as follows.

First, precursor particles of lithium carbonate (Li ₂ CO ₃ ), vanadium oxide (V ₂ O ₃ ), and two metal oxides were _{prepared using} the formula of Li _1.1 V _0.9-2x (M1) _x (M2) _x O ₂ , wherein Value is 0.01 ~ 0.09, and M1 and M2 are each selected from magnesium, calcium, aluminum, titanium, copper, chromium, manganese, tin, indium, zinc, gallium, germanium, zirconium, molybdenum, antimony and tungsten) Mix in a stoichiometric ratio, mill the ball to an average particle diameter of 100nm ~ 20μm using a zirconia ball for 1 hour at 250rpm in a ball mill, transfer the milled mixed precursor to an alumina crucible It is charged in a tubular furnace and heat-treated at high temperature in a mixed gas atmosphere composed of inert gas such as argon and nitrogen and hydrogen gas.

At this time, the tubular furnace is inert atmosphere by injecting a mixed gas consisting of 90 mol% inert gas such as argon, nitrogen and 10 mol% hydrogen gas for 1 hour before heat treatment.

This is to prevent the oxidation of the precursor and the generation of impurities during the heat treatment by forming an inert atmosphere in advance to remove residual oxygen remaining in the tubular furnace.

Temperature and time of the heat treatment process is 400 ~ 1,300 ℃, 5 ~ 20 hours, which is a temperature and time conditions for preventing the generation of impurities generated by excessively changing the oxidation number of vanadium.

The heat treatment is preferably a two-stage heat treatment method in which the heat treatment is first performed at about 500 ° C. for about 6 hours, and then the temperature is gradually raised to 1,100 ° C. at a rate of 5 ° C./min.

Next, after cooling the heat-treated precursor mixture is pulverized with a mortar and sifted through a sieve of 200 ~ 270 mesh (mesh) to prepare a negative electrode material for a lithium secondary battery uniform size.

In addition, the binder and the conductive material are mixed and stirred in the negative electrode material for the lithium secondary battery. At this time, the proportion of the negative electrode material is 80 to 90% by weight, the ratio of the binder is 5 to 10% by weight, the ratio of the conductive material is 5 to 10% by weight, and the most ideal mixing ratio is 90% by weight of the negative electrode material, the binder 5 weight% and 5 weight% of electrically conductive materials.

As the binder and the conductive material, all materials conventionally used in secondary batteries can be used. The binder includes 5% by weight of polyvinylidene fluoride (PVdF) in N-methyl-pyridone (NMP), an organic solvent. It is preferable to use the polymer solution, and carbon black (denka black) as the conductive material.

In this case, to prepare a slurry having a suitable viscosity, that is, a viscosity of 1,000 to 3,000 centi-poise, a pure NMP organic solvent is added in an amount of 1 to 2 times the weight of the mixture.

In addition, in order to homogeneously mix the prepared slurry using a homogenizer (homogenizer) at a high speed of stirring for 30 minutes at a rotation speed of 1,000 ~ 3000rpm, 10μm thick copper thin film (copper) used as a current collector of the negative electrode Using a doctor blade method on a foil) to a predetermined thickness, for example, 30 ~ 200μm thickness and dried at a temperature of 70 ~ 90 ^° C to prepare a negative electrode for a lithium secondary battery.

Hereinafter, preferred examples and comparative examples are provided to help understanding of the present invention, but the following examples are merely to illustrate the present invention, and the scope of the present invention is not limited to the following examples.

In the examples below, M1 selected tungsten (W) and M2 selected molybdenum (Mo).

Mechanical milling was performed by mixing lithium carbonate (Li ₂ CO ₃ ), vanadium oxide (V ₂ O ₃ ), tungsten oxide (WO ₂ ), and molybdenum oxide (MoO ₂ ) in a mixing ratio of Li _1.1 V _0.85 W _0.025 Mo _0.025 O ₂ . The mixture was placed in a crucible, placed in a tubular furnace, and first cooled by natural heat treatment at a temperature of about 500 ° C. for 6 hours in a mixed gas atmosphere composed of 90 mol% nitrogen gas and 10 mol% hydrogen gas. It was cooled by secondary heat treatment for 8 hours at a temperature of about 1,100 ℃ in the atmosphere.

At this time, in order to prevent oxidation of the mixture, oxygen is removed by injecting a gas mixed with 90 mol% of nitrogen gas and hydrogen gas for at least 1 hour before heat treatment to the tubular furnace.

Thereafter, the heat-treated mixture was ground in a mortar and sieved through a 200 mesh sieve to prepare a negative electrode material having a uniform particle size.

The thus produced ternary cathode material _{Li 1 .1 V 0 .85 W 0} .025 Mo 0 .025 O 2 To 4.5 g, 0.25 g of carbon black as a conductive material and 5 g of a 5% PVdF solution as a binder were mixed and 5 g of NMP was further added to prepare a slurry having a viscosity of 2000 cP, which was easy to apply to a copper thin film, and the slurry was mixed at a high speed of 2000 rpm in a mixer. Stirred for 30 minutes.

Subsequently, a thickness of 80 μm was applied to the copper thin film having a thickness of 10 μm using the doctor blade method, and dried at about 80 ° C. for 24 hours to prepare a negative electrode for a lithium secondary battery.

The lithium secondary battery negative electrode thus prepared was punched to a predetermined size and laminated alternately with a lithium metal electrode. A polypropylene (PP) separator was inserted between the two electrodes, and the volume ratio of ethyl carbonate and diethyl carbonate was 3: 7. 1 M LiPF ₆ was added to the organic solvent (EC / DEC solution) The dissolved electrolyte solution was injected, and the battery using the CR2032 coin cell was assembled.

Of Example 1, and the stoichiometric use of chemical precursors under the same conditions to prepare a ratio _{Li 1 .1 V 0 .8 W 0} .05 _{0 .05} O ₂ cathode material of Mo with the same heat treatment conditions with different.

A uniform cathode material _{Li 1 .1 V 0 .8 W 0} .05 Mo 0 .05 O 2 by mixing 4.5g, re-conductive carbon black 0.25g, 5% binder PVdF solution, and further adding the NMP 5g 5g copper film The electrode was prepared in the same manner as in Example 1, and the battery was assembled.

That is, was carried out in the same manner as in Example 1 except that the negative electrode material having the mixing ratio of the _{Li 1 .1 V 0 .8 W 0} .05 Mo 0 .05 O 2.

Of Example 1, and the stoichiometric use of chemical precursors under the same conditions to prepare a ratio Li _{1 .1 0} V cathode material of _{.75 W 0 .075 Mo 0 .075 O} 2 in the same heat treatment conditions with different.

A uniform cathode material _{Li 1 .1 V 0 .75 W 0} .075 Mo 0 .075 O 2 by mixing 4.5g, re-conductive carbon black 0.25g, 5% binder PVdF solution, and further adding the NMP 5g 5g copper film The electrode was prepared in the same manner as in Example 1, and the battery was assembled.

That is, was carried out in the same manner as in Example 1 except that the negative electrode material having the mixing ratio of the _{Li 1 .1 V 0 .75 W 0} .075 Mo 0 .075 O 2.

Of Example 1, and the stoichiometric use of chemical precursors under the same conditions to prepare a ratio _{Li 1 .1 V 0 .7 W 0} .1 _{0 .1} O ₂ cathode material of Mo with the same heat treatment conditions with different.

A uniform cathode material _{Li 1 .1 V 0 .7 W 0} .1 Mo 0 .1 O 2 by mixing 4.5g, re-conductive carbon black 0.25g, 5% binder PVdF solution, and further adding the NMP 5g 5g copper film The electrode was prepared in the same manner as in Example 1, and the battery was assembled.

That is, except that the negative electrode material having the mixing ratio of the _{Li 1 .1 V 0 .7 W 0} .1 Mo 0 .1 O 2 was performed in the same manner as in Example 1.

The composite negative electrode was prepared by mixing graphite in a samsung based negative electrode material prepared in Examples 1 to 3 in a weight ratio of 1: 4.

4.5 g of the composite negative electrode material, 0.25 g of carbon black as a conductive material, and 5 g of a 5% PVdF solution as a binder were mixed, and 5 g of NMP was further added to the copper thin film. The electrode was manufactured in the same manner as in Example 1, and the battery was assembled.

[Comparative Example]

Lithium carbonate (Li ₂ CO _3), vanadium oxide (V ₂ O ₃₎ mixing the precursor with the mixing ratio of the Li _{1 .1} V _{0 .9} O ₂ subjected to mechanical milling, and the same method as in Example 1 Li _{1 .1} a V _{0 .9} O ₂ was prepared.

Manufactured Li _{1 .1} V _{0 .9} O ₂ An electrode was manufactured under the same conditions as in Example 1 with respect to the negative electrode material, and a battery was assembled.

The charge / discharge voltage characteristics and the cycle performance of the battery were evaluated using the negative electrode material, the negative electrode, and the battery prepared in Examples 1 to 5 and Comparative Examples, and the results are shown in FIGS. 1 to 6.

1 is a view showing a pattern of XRD (X-ray diffraction) analysis results of a lithium-based negative electrode material prepared in Examples 1 to 3 of the present invention and a lithium / vanadium oxide negative electrode material according to a comparative example, and FIG. SEM (Scanning electron microscopy) analysis results of the lithium-based negative electrode material prepared in Example 3 of the present invention and the lithium / vanadium oxide negative electrode material according to the comparative example is a photograph, Figures 3A, 3B and 3C Figure 4 is a graph showing the potential / current circulating characteristic curve of a battery composed of a ternary negative electrode prepared by Examples 1 to 3 and a lithium metal electrode, and FIG. 4 is a ternary negative electrode prepared by Examples 1 to 4 of the present invention and a comparison The figure shows a low-rate charge / discharge voltage characteristic curve of a battery composed of a lithium / vanadium oxide negative electrode and a lithium metal electrode according to an example, and FIG. 5 is a ternary negative electrode prepared in Examples 1 to 3 of the present invention and a comparative example. Caused by lithium / Figure 6 shows a high-rate charge / discharge voltage characteristic curve of a battery composed of a vanadium oxide cathode and a lithium metal electrode, and FIG. 6 shows a composite anode and a lithium metal using a ternary oxide based graphite material prepared in Example 5 of the present invention. The figure shows the cycle characteristics of a battery composed of electrodes.

As shown in FIG. 1, due to the doping of tungsten and molybdenum in the negative electrode material according to Examples 1 to 3 of the present invention, the axis of the main peak of the negative electrode material showed a difference compared with that of the negative electrode material of the comparative example, and in particular, some doping It can be seen that the respective peaks corresponding to the non-tungsten and molybdenum are observed.

As shown in FIG. 2, the Samsung negative electrode material according to Example 3 of the present invention exhibits a more spherical shape than the comparative example, and the diameter of the negative electrode material of Example 3 is about 1 to 3 μm. An increase in the electrode mixture density and an improvement in the charge / discharge rate can be expected in manufacturing the electrode rather than the negative electrode material of the comparative example.

As shown in FIGS. 3A, 3B, and 3C, the battery composed of the negative electrode material and the lithium metal electrode according to Examples 1 to 3 of the present invention showed an irreversible reaction near the potential of 0.3 to 0.5 V in the first cycle. This irreversible reaction did not appear from the second cycle, and as the third, fourth, and fifth cycles progressed, it can be seen that the charge / discharge reaction was more reversible.

In particular, in the case of Example 3 it can be seen that the charge / discharge capacity is larger than the other embodiments it can be seen that the negative electrode material of Example 3 is a preferred mixing ratio.

As shown in FIG. 4, the battery composed of the negative electrode material and the lithium metal electrode according to Examples 1 to 3 of the present invention had an initial cycle efficiency of about 70% as a result of measuring charge / discharge voltage characteristics at a low rate of 0.1C. It can be seen that it has a specific capacity higher than 250 mAh / g higher than the battery of the comparative example.

In this case, the battery according to Example 4 of the present invention shows a different type of charge / discharge voltage characteristic curve without a flat potential as compared with Examples 1 to 3 and Comparative Examples, so that the battery is doped with the negative electrode material according to the present invention. And it can be seen that the maximum molar ratio of the metal material such as Mo should be adjusted to within 0.1.

As shown in Figure 5, the battery according to Examples 1 to 3 of the present invention, the charge / discharge voltage characteristics at high rates of 1C and 5C measured the overall specific capacity higher than the battery of the comparative example In particular, in the case of Example 3 has a specific capacity of 150mAh / g or more even at a high rate charge / discharge rate of 5C it can be seen that the best performance.

As shown in FIG. 6, the battery according to Example 5 of the present invention exhibits cycle characteristics conducted at a potential range of 0.01 to 2 V at a speed of 0.1 C, and mixed natural graphite with the ternary negative electrode material of Example 3 One composite anode material showed the highest specific capacity with an average charge / discharge capacity of 330mAh / g, and from the second cycle, the cycle efficiency of all the composite anodes showed excellent performance of 99% or more.

After addition to the above embodiment experimenting with different magnesium as _{Li 1 .1 V 0 .9-2x (M1} ) x (M2) x O 2 (x = 0.01 ~ 0.09) for the negative electrode material is suitable, and a metal component having It has been found that calcium, aluminum, titanium, copper, chromium, manganese, tin, indium, zinc, gallium, germanium, zirconium, molybdenum, antimony and tungsten can be used.

While the present invention has been described with reference to specific embodiments, the scope of the present invention is not necessarily limited thereto, and modifications and variations may be made without departing from the scope of the technical idea of the present invention.

Claims (20)

Li _1.1 V _0.9-2x (W) _x (Mo) _x O ₂ (x = 0.01 ~ 0.09) A high output negative electrode material for a lithium secondary battery having a mixing ratio. delete The method of claim 1,
A high output negative electrode material for a lithium secondary battery, characterized in that the average particle diameter is 100nm ~ 20μm. The method of claim 1,
High-output negative electrode material for a lithium secondary battery, characterized in that it further comprises graphite. Lithium secondary battery comprising a negative electrode of the negative electrode material of claim 1. Lithium secondary battery comprising a negative electrode of the negative electrode material of claim 4. Lithium carbonate (Li ₂ CO ₃ ), vanadium oxide (V ₂ O ₃ ), metal component 1 (M1), metal component 2 (M2) Li _1.1 V _0.9-2x (M1) _x (M2) _x O ₂ (x = 0.01 ~ 0.09) ratio (above the metal component 1 (M1), metal component 2 (M2) is magnesium, calcium, aluminum, titanium, copper, chromium, manganese, tin, indium, zinc, gallium, germanium, zirconium, molybdenum , Antimony, tungsten, and two different metal components selected from [2];
Milling at 200-300 rpm for 1 hour so that the average particle diameter of the mixed precursor is 100 nm-20 μm;
Charging the milled precursor to a tubular furnace and heat-treating at a temperature of 400-1300 ° C. for 5-20 hours in a gas mixture of inert gas and hydrogen gas; And
Cooling and pulverizing the heat-treated precursor and then sieving through a sieve of 200 to 270 mesh; Method for producing a high output negative electrode material for a lithium secondary battery, characterized in that comprises a. delete The method of claim 7, wherein
The metal component 1 (M1), metal component 2 (M2) is a high output negative electrode material manufacturing method for a lithium secondary battery, characterized in that W and MO, respectively. The method according to claim 7 or 9,
The heat treatment step is first proceeds for 6 hours at a temperature of 450 ~ 550 ℃, and secondly to a high output negative electrode material manufacturing method for a lithium secondary battery, characterized in that proceeding while increasing the temperature at a rate of 5 ℃ / min to 1100 ℃. The method according to claim 7 or 9,
Prior to the heat treatment step, a high-output negative electrode material for a lithium secondary battery, further comprising the step of injecting a mixed gas consisting of 90 mol% inert gas and 10 mol% hydrogen gas into the tubular furnace for 1 hour or more in advance to form an inert atmosphere. Manufacturing method. The method according to claim 7 or 9,
Method for producing a high output negative electrode material for a lithium secondary battery, characterized in that for mixing the graphite in the milling step. The method of claim 11,
The inert gas is a high output negative electrode material manufacturing method for a lithium secondary battery, characterized in that one selected from nitrogen and argon. In the production of a negative electrode for a lithium secondary battery using the negative electrode material produced by the method of claim 7 or 9,
Mixing 80 to 90% by weight of the negative electrode material, 5 to 10% by weight of the binder, and 5 to 10% by weight of the conductive material;
Preparing a slurry having a viscosity of 1000 to 3000 cP by adding 1 to 2 times the NMP organic solvent to the mixture;
Stirring the prepared slurry for 30 minutes at 1000 ~ 3000rpm in a mixer; And
Applying the stirred slurry to a copper thin film having a thickness of 5 to 15 μm using a doctor blade method at a thickness of 30 to 200 μm and drying it at a temperature of 70 to 90 ° C .; High output negative electrode manufacturing method for a lithium secondary battery, characterized in that comprises a. 15. The method of claim 14,
The mixing ratio of the mixture is 90% by weight of the negative electrode material, 5% by weight of the binder, 5% by weight of the conductive material, a high output negative electrode manufacturing method for a lithium secondary battery. 15. The method of claim 14,
The binder is a high-output negative electrode manufacturing method for a lithium secondary battery, characterized in that the solution containing 5% by weight of polyvinylidene fluoride (PVdF) in the N-methyl-pyridone (NMP) organic solvent. 15. The method of claim 14,
The conductive material is a high output negative electrode manufacturing method for a lithium secondary battery, characterized in that the carbon black. 17. The method of claim 16,
The conductive material is a high output negative electrode manufacturing method for a lithium secondary battery, characterized in that the carbon black. 16. The method of claim 15,
The binder is a high-output negative electrode manufacturing method for a lithium secondary battery, characterized in that the solution containing 5% by weight of polyvinylidene fluoride (PVdF) in the N-methyl-pyridone (NMP) organic solvent. 16. The method of claim 15,
The conductive material is a high output negative electrode manufacturing method for a lithium secondary battery, characterized in that the carbon black.

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