KR100646546B1 - Negative active material for lithium secondary battery and method of preparing same - Google Patents

Abstract

The present invention relates to a negative electrode active material for a lithium secondary battery and a method for manufacturing the same, wherein a composite metal compound formed of a metal alloyed with lithium and a metal not alloyed with lithium is attached to a surface of graphite particles, and thus has excellent charge and discharge efficiency and life characteristics. It relates to a negative electrode active material for a secondary battery and a method of manufacturing the same.

Cathode active material, metal alloy, carbon, lithium secondary battery

Description

Negative active material for lithium secondary battery and manufacturing method thereof {NEGATIVE ACTIVE MATERIAL FOR LITHIUM SECONDARY BATTERY AND METHOD OF PREPARING SAME}

1 is a schematic diagram schematically showing a process for producing a negative electrode active material for a lithium secondary battery of the present invention.

<Description of Symbols for Major Parts of Drawings>

10-complex metal compound 12-alloyed metal compound

14-unalloyed metal compound 20-graphite particles

30-carbon coating

The present invention relates to a negative electrode active material for a lithium secondary battery and a method for manufacturing the same, and more particularly, a composite metal compound formed of a metal alloyed with lithium and a metal not alloyed with lithium is attached to a surface of graphite particles, thereby charging and discharging efficiency and lifespan. It relates to a negative electrode active material for a lithium secondary battery with excellent characteristics and a method of manufacturing the same.

In general, as the light weight and high functionality of a portable wireless device such as a video camera, a portable telephone, a portable computer, and the like progress, a lot of researches have been conducted on secondary batteries used as driving power. Such secondary batteries include, for example, nickel cadmium batteries, nickel hydrogen batteries, nickel zinc batteries, and lithium secondary batteries. Among them, lithium secondary batteries are rechargeable, compact, and large-capacity, and are widely used in advanced electronic devices because of their high operating voltage and high energy density per unit weight.

Conventionally, it has been proposed to use lithium metal having a very high energy density as a negative electrode active material of a lithium secondary battery, but dendrite is formed on the negative electrode during charging, and the electrode penetrates through the separator during subsequent charge / discharge. There is a danger of reaching the anode and causing an internal short circuit. In addition, the precipitated dendrite rapidly increases the reactivity according to the increase in the specific surface area of the lithium electrode, and forms a polymer film lacking electron conductivity by reacting with the electrolyte at the electrode surface. For this reason, the battery resistance rapidly increases or there are particles isolated from the network of electron conduction, which acts as a factor that inhibits charging and discharging.

Because of these problems, a method of using a graphite material that can absorb / release lithium ions instead of lithium metal as a negative electrode active material has been proposed. In general, since the graphite negative electrode active material does not precipitate metal lithium, internal short circuit caused by dendrites does not occur and thus additional disadvantages do not occur. However, graphite has a theoretical lithium storage capacity of 372 mAh / g, which is a very small capacity corresponding to 10% of the lithium metal theoretical capacity.

Therefore, in order to increase the capacity, an attempt has recently been made to use metal and nonmetallic materials that form a compound with lithium as a negative electrode active material. For example, in the case of tin (Sn), lithium can be occluded as much as possible to form a compound of Li ₂₂ Sn ₅ , and within this range, no precipitation of metallic lithium occurs, so the problem of internal short circuit due to dendrite formation is It does not occur. Therefore, in the case of forming such a compound, the theoretical capacity in terms of electrochemical capacity is about 993 mAh / so that only the electrochemical reversibility can be ensured, which can achieve a much higher discharge capacity than graphite. In addition, in addition to the tin, a negative electrode active material using various materials such as Ni and Si that can be alloyed with Li has been proposed.

However, in the case of metal active materials including tin, the theoretical and discharge capacities are very high, but the electrochemical reversibility and thus the charge / discharge efficiency, and the rate of deterioration of the electrochemical cycling charge and discharge capacities are very high. Particularly, in the case of the metal active material, due to the formation of a lithium-metal intermetallic compound generated during charging and discharging, cracks are generated in the metal powder due to the rapid increase and contraction of the lattice volume of the metal, which leads to the miniaturization of particles. There is a problem that triggers the growth of the solid electrolyte layer (solid electrolyte interface layer) by generating a.

The present invention for solving the above problems is attached to a composite metal compound formed of a metal alloyed with lithium and a metal that is not alloyed with lithium on the surface of the graphite particles, the negative electrode active material for lithium secondary battery excellent in charge and discharge efficiency and life characteristics; Its purpose is to provide a method for its preparation.

In order to solve the above problems, the negative electrode active material of the present invention is a graphite particle capable of absorbing and releasing lithium, and a metal or metal compound attached to at least a part of the surface of the graphite particle and not alloyed with lithium. And a composite metal compound including a non-alloyed metal compound to be formed and a metal or metal compound alloyed with the lithium and dispersed and present in the non-alloyed metal compound.

In addition, the graphite particles to which the composite metal compound is attached in the present invention is preferably a carbon coating layer is formed on the surface.

In addition, the method for producing a negative electrode active material according to the present invention is a process of forming a composite metal compound powder of a predetermined size by mixing the alloying metal compound and the non-alloyed metal compound, and by mixing the composite metal compound and graphite particles wet or dry And forming a negative electrode active material precursor to which the composite metal compound is attached to graphite particles, and firing the negative electrode active material precursor at a predetermined temperature to form a negative electrode active material powder.

In addition, the process of forming the negative electrode active material precursor in the present invention preferably further comprises adding a polymer material for forming a carbon coating layer on at least a portion of the graphite particles to which the composite metal compound is attached.

Hereinafter, a method for preparing a negative electrode active material and a negative electrode active material according to an embodiment of the present invention will be described in detail.

The present invention is formed by dispersing a metal or a metal compound (hereinafter referred to as a "non-alloyed metal compound") which is not alloyed with lithium as a matrix and a metal or metal compound (hereinafter referred to as "alloyed metal compound") alloyed with lithium. The present invention relates to a negative electrode active material for a lithium secondary battery using a composite metal or a composite metal compound (hereinafter referred to as a "composite metal compound").

As described above, the alloying compound has excellent charge and discharge capacity, but as the electrochemical reaction proceeds, a lithium metal compound is formed, and a sudden increase and shrinkage of the crystallographic lattice volume of the metal causes cracking in the alloying compound powder. There was a problem such as to occur, it was difficult to use in the negative electrode active material. Therefore, in order to solve this problem, in the present invention, a negative electrode active material was prepared by using a non-alloyed metal compound as a matrix and including a predetermined amount of a composite metal compound in which the alloyed metal compound was dispersed in the matrix.

Figure 1 shows a schematic diagram of a process for producing a negative electrode active material comprising a composite metal compound according to an embodiment of the present invention. In addition, Figure 1 shows a structure for the negative electrode active material particles according to an embodiment of the present invention.

In the negative electrode active material according to the embodiment of the present invention, referring to FIG. 1, the fine composite metal compound 10 adheres to the surface of the graphite particles 20 and the graphite particles 20 and the composite metal compound 10 are separated. Carbon is coated on at least a portion of the outer surface to form a carbon coating layer 30. In addition, the composite metal compound 10 is a metal or metal compound that alloys with lithium capable of absorbing and releasing lithium, that is, a metal or metal compound that is not alloyed with lithium, i.e., a non-alloyed metal compound. It is dispersed and formed in (14), and like the graphite particles 20, since the reversible charge and discharge reaction with respect to lithium can be improved to improve the energy density of the entire negative electrode active material.

The graphite particles 20 may be any compound capable of reversibly absorbing and releasing lithium as a compound capable of reversible intercalation or deintercalation of lithium ions. For example, one or two or more kinds of carbon materials including natural graphite, artificial graphite, and amorphous carbon are mixed and formed. The graphite particles are formed in the size of 5 to 50 ㎛ range. If the size of the graphite particles is 5㎛ or less there is a problem that the initial efficiency is lowered due to the characteristics of the electrode, if larger than 50㎛ there is a problem in controlling the coating thickness when coating the negative electrode active material.

The composite metal compound 10 is formed by dispersing the non-alloyed metal compound 14 as a matrix and dispersing the alloyed metal compound 12.

The non-alloyed metal compound 14 may be formed by using one or two or more kinds of metals or metal compounds that do not alloy with lithium. Metals not alloyed with lithium include Cu, Fe, Zr, and Nb, and metal compounds include SiNi, SiO _2, CuO ₂ , CuCl, Fe ₂ O ₃ , ZrO ₂ , and Nb ₂ O ₃ . However, the present invention is not limited to the metal or metal compound not alloyed with lithium, and in addition to this, all metals or metal compounds not alloyed with lithium may be used. In addition, a material that does not alloy with lithium may be used even if it is not a metal or a metal compound.

On the other hand, when the non-alloyed metal compound is not a conductor such as an oxide, Cu, Ag, Ni, and Al are separately added as a conductive agent.

The alloying metal compound 12 may be formed by using one or two or more kinds of metals or metal compounds alloyed with lithium. Metals alloyed with lithium include Cr, Sn, Si, Ti, Al, Mn, Ni, Zn, Co, In, Cd, Bi, Pb, V, etc., and metal compounds such as SnO ₂ , Al ₂ O ₃ , Al (OH) ₃ , CrO ₂ , MnO ₂ , Mn ₂ O ₃ , NiO ₂ , ZnO, CoO, InO ₃ , CdO, Bi ₂ O ₃ , PbO, TiS ₂ , V ₂ O ₅ , and the like. As described above, the metal to be alloyed with the lithium is not limited, and any metal or metal compound not alloyed with lithium may be used.

The composite metal compound 10 has an average particle size of 0.05 μm to 1.0 μm, preferably 0.1 μm to 0.5 μm. When the particle size of the composite metal compound is smaller than 0.05 μm, the coagulation phenomenon between particles increases, which makes it difficult to use the powder. When the particle size of the composite metal compound is larger than 1.0 μm, the composite metal compound 10 is sufficient for the graphite particles 20. There is a problem that is difficult to attach.

The alloying metal compound 12 is formed to include 20 to 80% of the total weight of the composite metal or composite metal compound. Therefore, the non-alloyed metal compound 14 will contain 20 to 80% of the total weight of the composite metal compound. When the weight of the alloying metal compound 12 is included less than 20%, the increase in energy density of the negative electrode active material is small. In addition, when the weight of the metal alloy compound 12 exceeds 80%, the amount of non-alloyed metal compound is relatively increased, so it is insufficient to buffer the expansion and contraction of the metal alloy compound during charging and discharging. This has a problem of deterioration.

The alloyed metal compound 12 may be partially alloyed with the non-alloyed metal compound 14 to be present in the non-alloyed metal compound 14, and may be independently dispersed and formed without being alloyed with the non-alloyed metal compound 14. Can be. This is affected by the kind of the alloying metal compound 12 and the non-alloying metal compound 14 forming the composite metal compound 10.

For example, when the composite metal compound 10 is formed by using both the metal alloy compound 12 and the non-alloyed metal compound 14 as a metal, the metal alloy compound 12 and the non-alloyed metal compound 14 are formed. This may be partly formed of an alloy. In addition, when the alloyed metal compound 12 or the non-alloyed metal compound 14 is formed of a metal compound and is not alloyed with each other, the alloyed metal compound is dispersed and present in the non-alloyed metal compound.

It is preferable to use particles smaller than the composite metal compound 10 in order to disperse the metal alloy compound 12 in the non-alloyed metal compound 14. Therefore, it is preferable that the alloying metal compound 12 uses micronized powder having a size of 0.02 to 0.08 μm. When the particle size of the alloying metal compound is smaller than 0.02 μm, powdering is difficult, and when the particle size is larger than 0.08 μm, it is difficult to be dispersed and present in the non-alloyed metal compound.

The composite metal compound 10 is formed to contain 3 to 70% of the total weight of the negative electrode active material, preferably 5 to 50%. When the content of the composite metal compound exceeds 70%, the charge and discharge efficiency and cycle characteristics of the negative electrode active material is lowered, which is undesirable. In addition, when the content of the composite metal or composite metal compound is less than 3%, the energy density of the negative electrode active material is lowered, which is undesirable.

The carbon coating layer 30 is formed by coating the carbon to a thickness of less than micrometer, the surface of the graphite particles 20 and at the same time the composite metal compound 10 is attached to the surface of the graphite particles 20 Be sure to In addition, the carbon coating layer 30 does not proceed graphitization, so there is no fear that the electrolyte may be decomposed even when the electrolyte is in contact, and the charge and discharge efficiency of the anode material may be increased. The carbon coating layer 30 may be formed by firing polymer materials such as pitches and thermosetting resins. In this case, examples of the pitches used may include coal tar pitches from soft pitches to light pitches in which carbonization has advanced in the liquid phase. As the thermosetting resin, a phenol resin, a furan resin vinyl resin or a tar resin, a polyvinyl alcohol resin or the like is used. In addition, the carbon coating layer 30 may be directly formed on the surface of the graphite particles 20 through a deposition process such as a chemical vapor deposition (CVD) process. In this case, the carbon coating layer 30 may be formed on the surface of the graphite particles 20 without undergoing a separate process.

In the lithium ion secondary battery formed using the negative electrode active material, the negative electrode plate to which the negative electrode active material is applied, the positive electrode plate to which the positive electrode active material is applied, and the jelly roll formed by winding a separator placed between the positive electrode plate and the negative electrode plate are deposited. It is formed including the electrolyte. The electrolyte may be used in the liquid phase, a solid electrolyte may be used.

The material used as the cathode active material includes a compound capable of occluding and releasing lithium such as LiMn 2 O 4, LiCoO 2, LiNIO 2, LiFeO 2, and the like.

In addition, an olefin-based porous film such as polyethylene, polypropylene, or the like may be used as the separator.

Moreover, as said electrolyte solution, propylene carbonate, ethylene carbonate, butylene carbonate, benzonitrile, acetonitrile, tetra hydrofuran, 2-methyl tetrahydrofuran, (gamma) -butyrolactone, dioxolane, 4-methyldioxolane, N , N-dimethylformamide, dimethylacetamide, dimethyl sulfoxide, dioxane, 1,2-dimethoxyethane, sulfolane, dichloroethane, chlorobenzene, nitrobenzene, dimethyl carbonate, methyl ethyl carbonate, diethyl carbonate, methyl To an aprotic solvent such as propyl carbonate, methyl isopropyl carbonate, ethyl propyl carbonate, dipropyl carbonate, diisopropyl carbonate, dibutyl carbonate, diethylene glycol, or dimethyl ether, or a mixed solvent in which two or more kinds thereof are mixed. LiPF ₆ , LiBF ₄ , LiSbF ₆ , LiAsF ₆ , LiClO ₄ , LiCF ₃ SO ₃ , Li (CF ₃ SO ₂ ) ₂ N, LiC ₄ F ₉ SO ₃ , LiSbF ₆ , LiAl One or two or more electrolytes consisting of lithium salts such as O ₄ , LiAlCl ₄ , LiN (CxF ₂ x + 1SO ₂ ) (CyF ₂ y + 1SO ₂ ) (where x and y are natural water), LiCl, and LiI It can mix and melt | dissolve.

Next, a method of preparing a negative electrode active material including the composite metal compound 10 will be described.

First, the alloyed metal compound corresponding to 20 to 80% of the total weight of the composite metal compound is mixed with the non-alloyed metal compound to form a mixture. In this case, the alloying metal compound is preferably used in a powder state of a predetermined size, the non-alloyed metal compound may be used in a powder or lump state. The mixture of the alloyed metal compound and the non-alloyed metal compound may be an arc melting process, an atomization process, a roll-quenching process, a melt-spinning process, or a vacuum. Processes such as a vacuum induction melting process are used to form powder alloys in which the alloyed metal compound is dispersed in the non-alloyed metal compound. Since the general process is a method generally used to prepare a powder alloy, a detailed description thereof will be omitted.

The composite metal compound 10 prepared through the alloy powder manufacturing process has an average particle size of 0.05 μm to 1.0 μm, preferably 0.1 μm to 0.5 μm. The composite metal is refined through a separate refinement process such as a jet milling method when the particles are formed larger than 1.0㎛.

The prepared composite metal compound particles 10 and graphite particles 20 are mixed to form a negative electrode active material precursor. At this time, the composite metal compound 10 is mixed to be 3 to 70% of the total weight of the negative electrode active material. The negative electrode active material precursor is formed by mixing graphite particles and the composite metal compound in a dry or wet manner. Alcohol is used when the composite metal compound particles and graphite particles are wet mixed, and ethanol, methanol, or isopropyl alcohol may be used as the alcohol.

When the carbon coating layer 30 is formed on the surface of the negative electrode active material particles, a polymer material is mixed with a mixture of the composite metal compound 10 and the graphite particles 20. That is, the polymer material is dissolved in a solvent to prepare a solution and mixed with the mixture of the composite metal compound and the graphite particles. The polymer material is coated on the surface of the mixture of the composite metal compound and the graphite particles to form a polymer material film.

Pitches and thermosetting resins may be used as the polymer material. Examples of the pitch include coal tar pitch from the soft pitch to the light pitch in which carbonization has been advanced in the liquid phase. In addition, the thermosetting resin may be a phenol resin, furan resin vinyl resin or tar-based resin, polyvinyl alcohol-based resin and the like.

In the next step, the mixture of the composite metal and the graphite particles is calcined. Through the firing process, the solvent present in the mixture is evaporated, and the composite metal fine particles adhere to the surface of the graphite particles. At this time, 500-2000 degreeC is preferable and 500-1400 degreeC of baking temperature is more preferable. When the calcination temperature is lower than 500 ° C., components other than carbon remain in the mixture of the composite metal and the graphite particles, and the performance of the final negative electrode active material is degraded. When the temperature exceeds 2000 ° C., the volatilization phenomenon of the metal or metal compound and Agglomeration phenomenon between particles of metal or metal compound occurs, which is not preferable.

In addition, when the carbon coating layer 30 is formed on the surface of the negative electrode active material particles, the polymer solution coated on the surface of the negative electrode active material particles is carbonized to form the carbon coating layer 30. As described above, in the case of forming the carbon coating layer 30 on the surface of the negative electrode active material, the temperature in a predetermined process may be adjusted according to the use of the polymer material used and the characteristics of the polymer material used. For example, since the polymer material is generally carbonized at 1400 ° C. or lower, the firing process is performed at 1400 ° C. or lower. If the firing temperature exceeds 1400 ℃ carbon coating layer may change to graphite. In the case of using a polyvinyl alcohol-based resin as a polymer material, the firing temperature is 800 ° C. or higher to allow the carbonization to proceed sufficiently.

In the negative electrode active material prepared by the above method, fine composite metal compound particles 10 are attached to the surface of the graphite particles, and a carbon coating layer 30 is formed on the surface of the negative electrode active material. More tightly packed. In addition, the electrolyte solution used in the secondary battery is prevented from contacting the graphite particles, thereby preventing the electrolyte solution from being decomposed.

Since the negative electrode active material may be alloyed with lithium and includes an alloying metal compound capable of reversibly occluding and releasing lithium, the energy density of the negative electrode active material layer may be increased. In addition, since the metal alloy compound is dispersed in a matrix formed of the non-alloyed metal compound, the change in lattice volume due to occlusion and release of lithium is minimized, thereby reducing the charge / discharge efficiency and the lifetime.

Hereinafter, preferred examples and comparative examples of the present invention are described. However, the following examples are only preferred examples of the present invention, and the present invention is not limited to the following examples.

(Example 1)

40 wt% of the non-alloyed metal compound ZrO ₂ and 60 wt% of the Sn alloyed metal compound are mixed and dissolved by vacuum induction heating dissolution to form a powder. In this case, Sn, the alloying metal compound, uses a powder formed of an average particle of 0.06 μm, and Sn is present in an oxide state such as metal or SnO _{2 in the} formed composite metal compound. The composite metal compound and graphite particles are made into a slurry using methyl alcohol. In this case, the composite metal compound has an average particle size of 0.5 μm, and graphite particles use a powder having an average particle size of 15 μm. In addition, the content of the composite metal compound based on the total anode active material is 30% by weight. When the carbon coating layer is formed on the surface of the negative electrode active material, a phenol resin is mixed to prepare a negative electrode active material slurry. The negative electrode active material slurry is calcined at 1000 ° C. under a nitrogen gas atmosphere to prepare a negative electrode active material. (When the carbon coating layer is formed by the CVD method, the solvent is first mixed well and then the solvent is removed. Coal tar pitch is coated on the surfaces of the particles to which the graphite particles and the graphite particles are adhered to each other to form a carbon coating layer.) Since ZrO ₂ used as a non-alloyed metal compound is a non-conductor, a composite of fine Cu particles Add 3% of the total weight of the compound.

90 wt% of the negative electrode active material and 10 wt% of the polytetrafluoroethylene binder were mixed in an N-methyl pyrrolidone solvent to prepare a negative electrode active material slurry.

The prepared negative electrode active material slurry was coated on a copper foil having a thickness of 10 μm by a doctor-blade method, dried at 100 ° C. for 24 hours in a vacuum atmosphere to volatilize N-methyl pyrrolidone to form a circular shape having a diameter of 16 mm. A coin-shaped negative electrode plate was prepared by laminating a negative electrode active material layer having a thickness of 80 μm.

(Example 2)

The same process as in Example 1 was repeated except that a composite metal compound was prepared by mixing 30 wt% of the non-alloyed metal compound compound ZrO ₂ and 70 wt% of the Sn alloyed metal compound.

(Comparative Example)

The same procedure as in Example 1 was carried out except that only Sn metal powder having an average particle size of 0.06 μm was used instead of the composite metal compound.

(Evaluation of electrochemical performance including charge and discharge performance)

Coin-type half cells were prepared using a circular metal lithium foil as a counter electrode using the negative electrodes prepared by the methods of Examples 1 and 2 and Comparative Example 1. Electrolyte solution is ethylene carbonate and dimethoxyethane in 1 was used by dissolving LiPF ₆ to a 1 molar concentration (mol / L) in 1 volume ratio mixed solvent.

The prepared half cell was charged and discharged at a charge / discharge current density of 0.2C, with a charge end voltage of 0 V (vs Li / Li +) and a discharge end voltage of 2.0 V (vs Li / Li +). The results are shown in Table 1 below.

Charge capacity (mAh / g, 0.2C) Discharge Capacity (mAh / g, 0.2C) Charge and discharge efficiency life span(%) Example 1 450 420 90 90 Example 2 430 405 89 88 Comparative example 400 410 83 50

As shown in Table 1, it can be seen that the battery using the negative electrode active material of Examples 1 to 2 is superior in charge and discharge capacity, charge and discharge efficiency and life characteristics compared to the comparative example. That is, in the case of a negative electrode active material containing a composite metal compound, even if the alloying compound occludes and releases lithium during charging and discharging, the non-alloyed metal compound supports the alloying metal compound. Therefore, the alloying compound does not rapidly increase or decrease the grid volume. It will not occur. Therefore, in the case of the negative electrode active material containing a composite metal compound, the charge and discharge efficiency and life characteristics are excellent. On the other hand, in the comparative example using a negative electrode active material containing Sn metal alone, the discharge capacity is similar to those of Examples 1 to 2, but it can be seen that the charging and discharging efficiency and life is significantly lower. This is because as the Sn metal charges and discharges, as the metal lattice volume increases and contracts, the metal powder is balanced, which promotes miniaturization of the metal particles, and forms fine gaps between the graphite particles.

In the negative electrode active material for a lithium secondary battery of the present invention, since the metal alloyed with lithium is dispersed in a metal compound that does not alloy with lithium, the non-alloyed metal compound supports the alloyed metal compound even when the alloyed metal compound occludes and releases lithium during charging and discharging. Therefore, the sudden increase or decrease of the grid volume does not occur, and thus the charge and discharge capacity, the charge and discharge efficiency, and the life characteristics are excellent.                     

In addition, according to the present invention, since the carbon coating layer is formed on the surface of the negative electrode active material particles, the carbon film and the electrolyte do not react in the charging and discharging process, so that decomposition of the electrolyte is suppressed and high charging and discharging efficiency can be maintained.

Claims (22)

Graphite particles capable of absorbing and releasing lithium; And It is adhered to at least a part of the surface of the graphite particles, is formed of a non-alloyed metal compound formed of a metal or a metal compound that does not alloy with lithium and is dispersed in the non-alloyed metal compound formed of a metal or a metal compound alloyed with the lithium. Comprising a composite metal compound containing a metal alloy compound, The graphite particles to which the composite metal compound is attached are a cathode active material for a lithium secondary battery, characterized in that the carbon coating layer is formed on the surface. delete The method of claim 1, The graphite particles are natural graphite or artificial graphite or amorphous carbon, the negative electrode active material for lithium secondary battery. The method of claim 1, The graphite particles are lithium secondary battery negative electrode active material, characterized in that the particles having a size of 5 to 50 ㎛. The method of claim 1, The non-alloyed metal compound is a cathode active material for a lithium secondary battery, characterized in that it is formed containing one or two or more metals of Cu, Fe, Zr, Nb. The method of claim 1, The non-alloyed metal compound is formed of SiNi, SiO _2, CuO ₂ , CuCl, Fe ₂ O ₃ , ZrO ₂ , Nb ₂ O ₃ One or two or more metal compounds formed of a negative electrode for a lithium secondary battery characterized in that formed Active material. The method of claim 6, The non-alloyed metal compound is a negative active material for a lithium secondary battery, characterized in that the additional conductive agent is further formed. The method of claim 7, wherein The conductive agent is a negative electrode active material for a lithium secondary battery, characterized in that formed by containing one or two or more of Cu, Ag, Ni, Al. The method of claim 1, The alloying metal compound is lithium, characterized in that it is formed containing one or two or more metals of Cr, Sn, Si, Ti, Al, Mn, Ni, Zn, Co, In, Cd, Bi, Pb, V Anode active material for secondary battery. The method of claim 1, The alloying metal compound is SnO ₂ , Al ₂ O ₃ , Al (OH) ₃ , CrO ₂ , MnO ₂ , Mn ₂ O ₃ , NiO ₂ , ZnO, CoO, InO ₃ , CdO, Bi ₂ O ₃ , PbO, TiS ₂ , V ₂ O ₅ One or two or more metal compounds comprising a negative electrode active material, characterized in that formed. The method of claim 1, The alloying metal compound is a lithium secondary battery negative electrode active material, characterized in that the particles having a size of 0.02㎛ to 0.08㎛. The method of claim 1, The alloying metal compound is a negative electrode active material for a lithium secondary battery, characterized in that formed by containing 20 to 80% of the total weight of the composite metal compound. The method of claim 1, The composite metal compound is a lithium secondary battery negative electrode active material, characterized in that the particles having a size of 0.05㎛ to 1.0㎛. The method of claim 1, The composite metal compound is a lithium secondary battery negative electrode active material, characterized in that the particles having a size of 0.1㎛ to 0.5㎛. The method of claim 1, The composite metal compound is a negative electrode active material for a lithium secondary battery, characterized in that formed by containing 3 to 70% of the total weight of the negative electrode active material. The method of claim 1, The composite metal compound is a negative electrode active material for a lithium secondary battery, characterized in that formed by containing 5 to 50% of the total weight of the negative electrode active material. The method of claim 1, The carbon coating layer is a lithium secondary battery negative electrode active material, characterized in that formed using one or two or more of the phenol resin, furan resin, vinyl resin, tar resin, polyvinyl alcohol-based resin. Mixing the alloying metal compound and the non-alloying metal compound to form a composite metal compound powder having a predetermined size; Mixing the composite metal compound and the graphite particles in a wet or dry manner to form a negative electrode active material precursor having the composite metal compound attached to the graphite particles; And Firing the negative electrode active material precursor at a predetermined temperature to form a negative electrode active material powder; The process of forming the negative electrode active material precursor And adding a polymer material to form a carbon coating layer on the surface of the graphite particles having the composite metal compound attached thereto. delete The method of claim 18, The metal alloy compound is a method for producing a negative electrode active material for a lithium secondary battery, characterized in that particles having a size of 0.02㎛ to 0.08㎛. The method of claim 18, The composite metal compound is a method for producing a negative electrode active material for a lithium secondary battery, characterized in that particles having a size of 0.05㎛ to 1.0㎛ are used. The method of claim 18, The firing temperature is a method for producing a negative electrode active material for a lithium secondary battery, characterized in that 500 to 2000 ℃.

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