KR101660414B1 - Anode active material, anode comprising anode active material, lithium battery comprising anode, and preparation method thereof - Google Patents

Abstract

A negative electrode comprising the porous transition metal oxide, a negative electrode including the same, a lithium battery employing the same, and a method of manufacturing the same.

MoO2

Description

[0001] The present invention relates to an anode active material, an anode including the anode active material, a lithium battery employing the anode active material, and an anode active material, an anode active material,

A negative electrode including the negative electrode active material, a lithium battery employing the negative electrode, and a method for manufacturing the negative electrode active material.

A representative example of the negative electrode active material for a lithium battery is a carbon-based material such as graphite. Graphite has excellent capacity retention characteristics and dislocation characteristics, and there is no volume change when lithium and alloy are formed, so that the stability of the battery is high.

In addition, a lithium-alloyable metal may be used as the negative electrode active material for the lithium battery.

The metals which can be alloyed with lithium are Si, Sn, Al and the like. The lithium-alloyable metals have a very high electric capacity. However, the lithium-alloyable metals are accompanied by volume expansion during charging and discharging, resulting in isolated active materials in the electrode, and the electrolyte decomposition reaction is increased due to an increase in specific surface area.

There is a growing need for the development of an improved performance anode active material for high capacity batteries.

One aspect is to provide a negative electrode active material containing a transition metal oxide having a novel structure.

Another aspect is to provide a negative electrode comprising the negative active material.

Another aspect is to provide a lithium battery employing the negative electrode.

Another aspect provides a method for producing the negative electrode active material.

According to one aspect, a porous transition metal oxide is included,

Wherein the transition metal oxide is an oxide of at least one transition metal selected from the group consisting of Mo, Ti, V and W.

According to another aspect, there is provided a negative electrode comprising the negative active material.

According to another aspect, there is provided a lithium battery employing the negative electrode.

According to another aspect,

Impregnating the porous compound with a solution containing a salt of a transition metal;

Firing the solution-impregnated porous compound in a reducing atmosphere; And

And etching the resultant of the firing with an etchant.

According to one aspect, the capacitance can be increased by including a porous transition metal oxide.

Hereinafter, a negative electrode active material according to exemplary embodiments, a negative electrode including the negative active material, a lithium battery employing the negative electrode, and a method for manufacturing the negative active material will be described in detail.

The anode active material according to an embodiment includes a porous transition metal oxide, and the transition metal oxide is an oxide of at least one transition metal selected from the group consisting of Mo, Ti, V and W. Since the porous transition metal oxide includes a large number of nano-sized pores, the area of contact with the electrolyte greatly increases, so that the electric capacity per unit mass of the active material is increased. Also, the path of electrons moving from the inside of the active material to the electrolyte is shortened and the moving path of lithium ions is shortened, so that the rate of the electrode reaction can be increased.

The porous transition metal oxide may have a porosity of substantially 80% or less. For example, the porosity of the porous transition metal oxide may be 20 to 70%. The porosity means the volume occupied by the pores in the total volume of the porous transition metal oxide.

The porous transition metal oxide may provide a discharge capacity per unit weight of 1000 mAh / g or more and a discharge capacity per unit volume of 1000 mAh / cc or more.

In the negative electrode active material, the pores of the porous transition metal oxide may have various shapes, and when the pores are spherical, they may have a diameter of about 2 to about 50 nm. For example, the diameter of the pores may be from about 3 to about 30 nm. For example, the diameter of the pores may be from about 3 to about 15 nm. For example, the diameter of the pores may be from about 3 to about 10 nm. The diameter range of the porous transition metal oxide is suitable for improving the discharge capacity of the lithium battery employing the negative electrode active material.

In the negative active material, pores of the porous transition metal oxide may be connected to each other to form a channel. Such channel formation facilitates penetration of the electrolyte into the transition metal oxide and migration of lithium ions.

In the negative electrode active material, the pores of the porous metal oxide may be regularly arranged. By regularly arranging the pores, a uniform electrochemical reaction can be performed, and local loss or deterioration of the negative electrode active material can be avoided.

In the negative electrode active material, the pores of the porous transition metal oxide have a uniform diameter of 3 to 10 nm and are regularly arranged. The skeleton forming the walls between the pores has a uniform skeleton size of 5 to 10 nm, Lt; / RTI > The pore size and the transition metal oxide skeleton size in this range are more suitable for improving the discharge capacity of the lithium battery employing the negative electrode active material. For example, the skeleton, i.e., the wall between the pores, is a portion indicated by black in FIG. 4C. The size of the skeleton is the size of a portion indicated by a black color between spaces in FIG. 4C. The pores correspond to spaces between the skeletons in FIG. 4C. The diameter of the pores is the diameter of the space in Fig. 4C.

In the negative electrode active material, the specific surface area of the pores included in the porous transition metal oxide may be about 50 to about 250 m ² / g. For example, the specific surface area may be from about 80 to about 220 m ² / g. For example, the specific surface area may be from about 100 to about 110 m ² / g.

In the negative electrode active material, the total pore volume, which is the volume occupied by the pores per unit weight of the porous transition metal oxide, may be less than 2 cc / g. For example, the total pore volume may be between 0.1 and 1 cc / g. For example, the total pore volume may be 0.3-0.6 cc / g.

The porous transition metal oxide having the specific surface area and / or the total pore volume in the above range is more suitable for improving the discharge capacity of the lithium battery employing the negative electrode active material.

In the negative electrode active material, the transition metal oxide may be represented by the following chemical formula 1:

≪ Formula 1 >

MxOy

Wherein M is Mo, Ti, W, V, and mixtures thereof, and 1? X? 2, 1? Y? 8, 2? X + y?

In the negative electrode active material, the transition metal oxide may be MoO ₂ , TiO _2, or a mixture thereof.

The negative electrode according to another embodiment includes the negative electrode active material. The negative electrode may be manufactured, for example, by forming the negative electrode active material composition containing the negative electrode active material and the binder in a predetermined shape or by applying the negative electrode active material composition to a current collector such as copper foil.

Specifically, a negative electrode active material composition is prepared and coated directly on the copper foil current collector to obtain a negative electrode plate, or the negative electrode active material film that is cast on a separate support and peeled from the support is laminated on the copper foil collector to obtain a negative electrode plate have. The negative electrode is not limited to the above-described form, but may be in a form other than the above-described form.

A material having a low electric resistance may be used for high capacity of a battery for charging and discharging a large amount of current. Various conductive materials may be added to reduce the resistance of the electrodes, and the conductive materials mainly used are carbon black, graphite fine particles, and the like. Alternatively, the negative electrode active material composition may be printed on a flexible electrode substrate and used for producing a printable battery.

A lithium battery according to another embodiment adopts a negative electrode including the above-described negative electrode active material. The lithium battery can be produced by the following method.

First, a cathode active material composition in which a cathode active material, a conductive material, a binder, and a solvent are mixed is prepared. The positive electrode active material composition is directly coated on the metal current collector and dried to produce a positive electrode plate. Alternatively, the cathode active material composition may be cast on a separate support, and then the film peeled from the support may be laminated on the metal current collector to produce a cathode plate.

As the cathode active material, lithium-containing metal oxides can be used as long as they are commonly used in the art. For example, LiCoO ₂ , LiMn _x O ₂ x (x = 1, 2), LiNi _1-x Mn _x O ₂ (0 <x <1), or LiNi _1-xy Co _x Mn _y O ₂ 0.5, 0? Y? 0.5). For example, it is a compound capable of intercalating / deintercalating lithium such as LiMn ₂ O ₄ , LiCoO ₂ , LiNiO ₂ , LiFeO ₂ , V ₂ O ₅ , TiS or MoS. As the conductive material, carbon black and graphite fine particles can be used. As the binder, vinylidene fluoride / hexafluoropropylene copolymer, polyvinylidene fluoride (PVDF), polyacrylonitrile, polymethyl methacrylate, poly Tetrafluoroethylene, a mixture thereof, or a styrene butadiene rubber-based polymer may be used. As the solvent, N-methylpyrrolidone, acetone, water or the like may be used. The content of the positive electrode active material, the conductive material, the binder and the solvent is a level commonly used in a lithium battery.

The separator can be used as long as it is commonly used in a lithium battery. It is preferable to have a low resistance against the ion movement of the electrolyte and an excellent ability to impregnate the electrolyte. For example, selected from glass fiber, polyester, Teflon, polyethylene, polypropylene, polytetrafluoroethylene (PTFE), or a combination thereof, and may be nonwoven fabric or woven fabric. Specifically, a rewindable separator such as polyethylene, polypropylene, or the like is used for the lithium ion battery, and a separator having excellent organic electrolyte impregnation capability is used for the lithium ion polymer battery. Such a separator can be manufactured by the following method .

The separator composition is prepared by mixing a polymer resin, a filler, and a solvent, and then the separator composition is directly coated on the electrode and dried to form a separator film. Alternatively, after the separator composition is casted and dried on the support, A separator film may be formed by lamination on the electrode.

The polymer resin is not particularly limited, and all the materials used for the binder of the electrode plate can be used. For example, vinylidene fluoride / hexafluoropropylene copolymer, polyvinylidene fluoride, polyacrylonitrile, polymethyl methacrylate, or a mixture thereof may be used.

Next, the electrolyte is prepared.

The electrolyte may be an organic electrolyte. According to another embodiment, the electrolyte may be in a gel or solid state. Examples of the organic electrolyte include organic solvents such as propylene carbonate, ethylene carbonate, fluoroethylene carbonate, diethyl carbonate, methyl ethyl carbonate, methyl propyl carbonate, butylen carbonate, -Butyrolactone, dioxolane, 4-methyldioxolane, N, N-dimethylformamide, dimethylacetamide, dimethylsulfoxide, dioxane, 1,2-dimethoxyethane, sulfolane, dichloroethane, chloro benzene, nitrobenzene, dimethyl carbonate, methyl isopropyl carbonate, ethyl propyl carbonate, dipropyl carbonate, dibutyl carbonate, diethylene glycol, dimethyl ether or _{LiPF 6, LiBF 4, LiSbF 6} , LiAsF 6 in a solvent such as a mixture thereof _{, LiClO 4, LiCF 3 SO 3} , Li (CF 3 SO 2) 2 N, LiC 4 F 9 SO 3, LiAlO 2, LiAlCl 4, LiN (C x F 2x + 1 SO2) (C y F 2y + 1 SO ₂ ) (where x and y are natural numbers ), LiCl, LiI, or a mixture thereof, may be dissolved and used.

As shown in FIG. 6, the lithium battery 1 includes an anode 3, a cathode 2, and a separator 4. The anode 3, the cathode 2 and the separator 4 described above are wound or folded and housed in the battery case 5. Then, an organic electrolytic solution is injected into the battery case 5 and is sealed with a cap assembly 6 to complete the lithium battery 1. The battery case may have a cylindrical shape, a rectangular shape, a thin film shape, or the like. The lithium battery may be a lithium ion battery.

A separator may be disposed between the anode and the cathode to form a battery structure. This battery structure is laminated in a bi-cellular structure, then impregnated with an organic electrolyte solution, and the resulting product is received in a pouch and sealed to complete a lithium ion polymer battery.

In addition, a plurality of battery structures may be stacked to form a battery pack, and such a battery pack may be used as an electric vehicle battery requiring high temperature and high output. Also, the battery structure may be used as a large-area thin-type battery.

The lithium battery may provide a discharge capacity of 1000 mAh / g or more per unit weight of the negative electrode active material. In addition, the lithium battery may provide a discharging capacity of 1000 mAh / cc or more per unit volume of the negative electrode active material.

According to another embodiment of the present invention, there is provided a method for manufacturing an anode active material, comprising: impregnating a porous compound with a solution containing a salt of a transition metal; Firing the solution-impregnated porous compound in a reducing atmosphere; And etching the resultant of the firing with an etchant.

In the method for producing an anode active material, the porous compound may be selected from the group consisting of silica (SiO ₂ ), Al ₂ O ₃ , ZnO, MgO, and mixtures thereof. The porous compound acts as a template for preparing a porous transition metal compound. The porous compound is impregnated with a solution containing a salt of a transition metal to fill the pores, and then the porous compound impregnated with the solution is calcined to obtain a composite of the porous compound and the transition metal compound. Then, the porous compound in the composite is removed with an etching solution to obtain a porous transition metal compound.

In the negative electrode active material preparation method, the salt of the transition metal may be selected from the group consisting of MoCl ₅ , ammonium molybdate, and mixtures thereof. These can be used after being dissolved in a solution in the form of a salt of a transition metal.

In the negative electrode active material manufacturing method, the firing temperature of the firing step may be about 400 to about 600 ° C. The firing temperature in the above range is suitable for the production of an anode active material having nanopores.

During the firing, the reducing atmosphere may be at least one gas atmosphere selected from the group consisting of nitrogen, argon, helium, and hydrogen.

In the negative electrode active material manufacturing method, the etchant may be selected from the group consisting of hydrofluoric acid (HF), NaOH, and HF-NH ₄ F (buffer). The etchant may be an acid or a base.

In the method of manufacturing an anode active material, the step of heat-treating the result of the etching in a reducing atmosphere after the etching step may be further included. Adhesion of the negative electrode active material can be improved by the additional heat treatment. For example, the adhesion between the negative electrode active material and the current collector can be improved.

The heat treatment temperature of the additional heat treatment step may be 100 to 600 ° C. For example, 200 to 500 &lt; 0 &gt; C.

In the additional heat treatment step, the reducing atmosphere may be at least one gas atmosphere selected from the group consisting of nitrogen, argon, helium, and hydrogen.

EXAMPLES The following examples and comparative examples illustrate exemplary embodiments in more detail. It should be noted, however, that the embodiments are for illustrative purposes only and are not intended to limit the scope of the present invention.

(Preparation of negative electrode active material)

Example 1

A solution of ammonium molybdate in 1 g of ethanol was injected into the porous SiO ₂ (KIT-6). The SiO ₂ was injected into the ammonium molybdate to be 100 parts by weight of ammonium molybdate ratio 20 parts by weight of date with respect to the solution in ethanol to SiO _2. Subsequently, the porous SiO ₂ into which the ammonium molybdate was injected was fired at 500 ° C. for 4 hours in a reducing (100% hydrogen gas) atmosphere to obtain a SiO ₂ -MoO ₂ composite. The complex was introduced into a 1 M aqueous solution of hydrofluoric acid and reacted for 2 hours to remove the SiO ₂ template to obtain porous MoO ₂ .

Example 2

The same procedure as in Example 1 was carried out except that the porous MoO ₂ from which the template had been removed was further heat-treated at 100 ° C for 2 hours in a hydrogen atmosphere.

Example 3

The same procedure as in Example 1 was carried out except that the porous MoO ₂ from which the template was removed was further heat-treated at 200 ° C for 2 hours in a hydrogen atmosphere.

Example 4

The same procedure as in Example 1 was carried out except that the porous MoO ₂ from which the template had been removed was further heat-treated at 300 ° C for 2 hours in a hydrogen atmosphere.

Example 5

The same procedure as in Example 1 was carried out except that the porous MoO ₂ from which the template had been removed was further heat-treated at 400 ° C for 2 hours in a hydrogen atmosphere.

Example 6

The same procedure as in Example 1 was carried out except that the porous MoO ₂ from which the template had been removed was further heat-treated at 500 ° C for 2 hours in a hydrogen atmosphere.

Example 7

Titanium chloride (Titanium chloride) in the porous SiO ₂ (KIT-6) was injected dissolved in methanol 1g. A solution of a titanium chloride in a proportion of 20 parts by weight of titanium chloride with respect to the 100 parts by weight of SiO ₂ in methanol was injected into the SiO _2. Subsequently, the porous SiO ₂ injected with the titanium chloride was fired in a reducing atmosphere (100% hydrogen gas) at 500 ° C. for 4 hours to obtain a SiO ₂ -TiO ₂ composite. The complex was introduced into a 1M hydrofluoric acid aqueous solution and reacted for 2 hours to remove the SiO ₂ template to obtain porous TiO ₂ .

Comparative Example 1

The pore-free bulk MoO ₂ was used as is.

(Cathode and lithium battery manufacturing)

Example 8

15 mg of a negative electrode active material powder prepared in Example 1, 15 mg of a carbon conductive agent (Super-P, Timcal Inc.) and 15 mg of polyvinylidene fluoride (PVdF) were dissolved in 15 mL of N-methylpyrrolidone (NMP) And agar mortar to prepare a slurry. The slurry was applied on a copper collector to a thickness of about 50 탆 using a doctor blade, dried at room temperature for 2 hours, and dried again under vacuum at 120 캜 for 2 hours to prepare a negative electrode plate.

The above-mentioned negative electrode plate was used as a separator (Cellgard 3510), lithium metal as a counter electrode, separator (Cellgard 3510), 1.3M LiPF ₆ EC (ethylene carbonate) + DEC (diethyl carbonate) Volume ratio) was used as an electrolyte to prepare a coin cell of CR-2016 standard.

Example 9

Except that the negative electrode active material prepared in Example 2 was used in place of the negative electrode active material prepared in Example 1 above.

Example 10

Except that the negative electrode active material prepared in Example 3 was used instead of the negative electrode active material prepared in Example 1 above.

Example 11

Except that the negative electrode active material prepared in Example 4 was used in place of the negative electrode active material prepared in Example 1,

Example 12

Except that the negative electrode active material prepared in Example 5 was used in place of the negative electrode active material prepared in Example 1,

Example 13

Except that the negative electrode active material prepared in Example 6 was used in place of the negative electrode active material prepared in Example 1,

Example 14

Except that the negative electrode active material prepared in Example 7 was used in place of the negative electrode active material prepared in Example 1,

Comparative Example 2

Except that the negative active material of Comparative Example 1 was used in place of the negative active material prepared in Example 1 above.

Evaluation example 1: X-ray diffraction experiment

X-ray diffraction experiments were performed on the negative electrode active material powder prepared in Example 1, and the results are shown in FIGS. 1 and 2, respectively.

As shown in FIGS. 1 and 2, it was confirmed that porous MoO ₂ having regular nano-sized pores having a diameter of 5 to 7 nm was produced in Example 1. It can be confirmed that the phase of the Mo oxide synthesized from FIG. 1 is MoO ₂ . Also, as shown in FIG. 2, a diffraction pattern due to a regular pore arrangement was observed from a low angle X-ray diffraction result. Therefore, it can be confirmed that porous MoO ₂ having regular nano-sized pores is synthesized. The two MoO _2's shown in FIG. 1 were used as a reference for the X-ray diffraction pattern of MoO ₂ used in the present invention as a known MoO ₂ .

Evaluation Example 2: Nitrogen adsorption experiment

The negative electrode active material powder prepared in Example 1 was subjected to a nitrogen adsorption / desorption experiment, and the results are shown in FIG.

The specific surface area was calculated using the BET (Brunauer-Emmett-Teller) method using the data of P / P ₀ values from 0.15 to 0.3 in the nitrogen adsorption curve. The total pore volume was calculated from the P / P ₀ value And the volume of the nitrogen liquid converted from the adsorption amount of nitrogen at the point of 0.99.

3, it was confirmed that the MoO ₂ prepared in Example 1 had nano-sized pores. The specific surface area of the pores calculated by the above-mentioned method was 102 m ² / g and the total volume of the pores was 0.51 cc / g Able to know. The specific surface area and the total volume of the pores of the negative electrode active material prepared in Examples 1 to 7 are shown in Table 1 below.

Evaluation Example 3: Electron transmission microscope (TEM) experiment

The negative electrode active material powder prepared in Example 1 was subjected to an electron transmission microscope and the results are shown in FIGS. 4A to 4D.

As shown in FIGS. 4A to 4D, the MoO ₂ prepared in Example 1 includes nano-sized pores which are regularly arranged and connected with each other to form channels. The diameter of the nanopores was 5 to 7 nm.

Regular arrangement of the nanopores and channel formation were also observed in the negative electrode active materials prepared in Examples 1 to 7. The nano pore diameter of the negative electrode active material prepared in Examples 1 to 7 and the size of the skeleton forming the wall between the nano pores are shown in Table 1 below.

<Table 1>

Pore diameter
[nm] The size of the skeleton forming the wall between the pores [nm] Specific surface area
[m ² / g] Pore volume
[cc / g] Example 1 5 ~ 7 5 to 10 102 0.51 Example 2 5 ~ 7 5 to 10 102 0.51 Example 3 5 ~ 7 5 to 10 102 0.51 Example 4 5 ~ 7 5 to 10 102 0.51 Example 5 5 ~ 7 5 to 10 102 0.51 Example 6 5 ~ 7 5 to 10 102 0.51 Example 7 3 to 7 5 ~ 7 220 0.41

Evaluation Example 4: Charge-discharge experiment

The lithium batteries prepared in Examples 8 to 14 and Comparative Example 2 were charged at a current of 40 mA per 1 g of the negative electrode active material until the voltage reached 0.001 V (vs. Li) (Li). Subsequently, charging and discharging were repeated 50 times in the same current and voltage sections. The results of charging and discharging in the second cycle are shown in Fig. 5 and Table 2, respectively. The capacity retention rate is defined by the following equation (1). The capacity retention ratios of Examples 8 to 14 and Comparative Example 2 are shown in Table 2.

&Quot; (1) &quot;

Capacity retention rate [%] = Discharge capacity in the 50th cycle / Discharge capacity in the second cycle

Evaluation Example 5: Evaluation of adhesion

The adhesion of the negative electrode prepared in Examples 8 and 14 and Comparative Example 2 to the current collector was evaluated. The adhesion was evaluated according to the following criteria.

?: 10% or more of the total area of the negative electrode active material layer after the negative electrode is formed is separated from the current collector.

?: 10% or less of the total area of the negative electrode active material layer after the negative electrode formation is separated from the current collector.

?: The negative electrode active material layer after the negative electrode formation is not separated from the current collector.

The adhesion evaluation results for Examples 8 to 14 are shown in Table 2 below.

<Table 2>

Additional heat treatment
Temperature [° C] 1 ^st cycle discharge capacity [mAh / g] Capacity retention rate
[%] Adhesion Example 8 No additional heat treatment 1181.96 83 △ Example 9 100 ℃ 1061.17 86 △ Example 10 200 ℃ 1142.54 95 ○ Example 11 300 ° C 1201.67 99 ◎ Example 12 400 ° C 1125.79 95 ◎ Example 13 500 ℃ 1126.42 96 ◎ Example 14 No additional heat treatment 334 30 ○ Comparative Example 2 No additional heat treatment 410 50 ◎

As shown in Table 2, the discharge capacity of the lithium battery of Comparative Example 2 was 410 mAh / g at 3 V, while the discharge capacity of the lithium battery of Example 8 was 1181 mAh / g. The discharge capacity of the lithium battery of Example 8 was 2.75 times higher than that of the lithium battery of Comparative Example 2. [ That is, the lithium storage capacity increased by 2.75 times.

In the case of Examples 9 to 13 after the SiO ₂ template was etched and subjected to the additional hydrogen reduction heat treatment step, a higher discharge capacity was exhibited as compared with Comparative Example 2,

As shown in Table 2, in Examples 10 to 13, which are lithium batteries using an additional heat-treated active material, the adhesion was improved after electrode formation. This is believed to be attributable to the removal of impurities such as oxygen and hydroxyl present in the pore walls present in the anode active material, thereby enhancing the slurry adhesion properties during electrode formation, It is the cause of improvement of characteristics in terms of maintenance rate. Therefore, additional heat treatment processes can provide improved performance and improved manufacturing efficiency in battery manufacturing.

1 and 2 are X-ray diffraction experimental results of the negative electrode active material according to Example 1. Fig.

3 is a graph showing the results of nitrogen adsorption experiments on the negative electrode active material according to Example 1. FIG.

4A to 4D are transmission electron microscope images of the negative electrode active material according to the first embodiment.

5 is a graph showing the results of charge and discharge tests of the lithium battery according to Example 8 and Comparative Example 2. Fig.

6 is a schematic view of a lithium battery according to one embodiment.

Claims (23)

And a porous transition metal oxide having a gyroid structure, Wherein the transition metal oxide is an oxide of at least one transition metal selected from the group consisting of Mo, Ti, and V. The negative electrode active material according to claim 1, wherein the porous transition metal oxide has a pore diameter of 2 to 50 nm. The negative electrode active material according to claim 1, wherein the porous transition metal oxide has a pore diameter of 3 to 15 nm. The negative electrode active material according to claim 1, wherein the pores of the porous transition metal oxide are connected to each other to form a channel. The negative electrode active material according to claim 1, wherein pores of the porous metal oxide are regularly arranged. The negative electrode active material according to claim 1, wherein the porous transition metal oxide has a pore diameter of 3 to 10 nm and a skeleton forming a wall between the pores has a size of 5 to 10 nm. The negative electrode active material according to claim 1, wherein the porous transition metal oxide has a specific surface area of 50 to 250 m ² / g. The negative electrode active material according to claim 1, wherein the porous transition metal oxide has a specific surface area of 80 to 220 m ² / g. The negative electrode active material according to claim 1, wherein the transition metal oxide is represented by the following formula (1) &Lt; Formula 1 > MxOy Wherein M is Mo, V, Ti and mixtures thereof, and 1? X? 2, 1? Y? 8, 2? X + y? The negative electrode active material according to claim 1, wherein the transition metal oxide is MoO ₂ . The negative electrode active material according to claim 1, wherein the transition metal oxide is TiO ₂ . An anode comprising the anode active material according to any one of claims 1 to 11. A lithium battery employing the negative electrode of claim 12. 14. The lithium battery according to claim 13, wherein the discharge capacity per unit weight of the negative electrode active material is 1000 mAh / g or more. 12. A method for manufacturing an anode active material according to any one of claims 1 to 11, Impregnating the porous compound with a solution containing a salt of a transition metal; Firing the solution-impregnated porous compound in a reducing atmosphere; And And etching the resultant of the firing with an etchant to obtain a porous transition metal oxide. Of claim 15 wherein the porous compound is silica (SiO _2), how Al ₂ O _3, ZnO, MgO, and the negative electrode active material is selected from the group consisting of a mixture thereof for manufacture. The method of claim 15, wherein the salt of the transition metal is selected from the group consisting of MoCl ₅ , ammonium molybdate, titanium chloride, and mixtures thereof. 16. The method of claim 15, wherein the firing temperature of the firing step is 400 to 600 占 폚. The method of claim 15, wherein the negative electrode active material manufacturing method in which the etchant is hydrofluoric acid (HF), selected from the group consisting of NaOH and NH ₄ F-HF. 16. The method of claim 15, wherein the reducing atmosphere is at least one gas atmosphere selected from the group consisting of nitrogen, argon, helium, and hydrogen. 16. The method of claim 15, further comprising heat treating the result of the etching in a reducing atmosphere after the etching step. 22. The method of claim 21, wherein the heat treatment temperature in the heat treatment step is 100 to 600 占 폚. 22. The method of claim 21, wherein the reducing atmosphere is at least one gas atmosphere selected from the group consisting of nitrogen, argon, helium, and hydrogen.

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