JP2010519682A - Anode active material for lithium battery, method for producing the same, and lithium secondary battery using the same - Google Patents

Abstract

The present invention relates to an anode active material for a lithium battery, a method for producing the same, and a lithium secondary battery using the same. The anode active material for a lithium battery of the present invention is characterized in that the surface of the anode active material is coated with a fluorine-based compound.
According to the present invention, it is possible to stabilize the surface of the anode active material and reduce the influence of the organic electrolyte decomposition reaction which is the main cause of the irreversible capacity. In addition, the present invention can reduce the influence due to the acid generated by oxidation of the electrolyte during charge / discharge, and can exhibit excellent cycle characteristics and high rate characteristics during charge / discharge.
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Description

  The present invention relates to an anode active material for a lithium battery, a method for producing the same, and a lithium secondary battery using the anode active material. More specifically, the present invention stabilizes the surface of the anode active material and is a major cause of irreversible capacity. Reduces the influence of organic electrolyte decomposition reaction, and at the same time reduces the influence of acid generated by oxidation of the electrolyte during charge / discharge, and exhibits excellent cycle characteristics and high rate characteristics during charge / discharge The present invention relates to an anode active material for a lithium battery, a manufacturing method thereof, and a lithium secondary battery using the same.

  Recently, lithium secondary batteries, which have been in the spotlight as a power source for portable small electronic devices, have high energy by showing a discharge voltage more than twice as high as that of batteries using existing alkaline aqueous solutions using organic electrolytes. It is a battery showing density.

The cathode active material of a lithium secondary _{battery, LiCoO 2, LiMn 2 O 4} , LiNi 1-x Co x O 2 (0 <x <1) , such as, capable lithium intercalation (intercalation) Oxides composed of lithium having a structure and a transition metal were mainly used.

  As the anode active material, various forms of carbon-based materials including artificial graphite capable of inserting / extracting lithium, natural graphite, and hard carbon have been applied. The carbon-based anode material has excellent voltage flatness at a low potential and has good life characteristics. However, improvements in power characteristics, initial irreversible control, electrode swelling during charging / discharging, and the like are required due to high reactivity with organic electrolytes and low diffusion rate of lithium in the material.

  Therefore, in the prior art, in order to improve the battery characteristics of graphite (or other carbon-based material) used in the anode, the shape, particle size and distribution, density, and amorphous carbon (pitch) of graphite powder are used. A method of adjusting the coating, the crystallinity depending on the temperature, and the like has been used.

  As a specific example, in Korean Patent Publication No. 2005-0020186, a carbon compound capable of inserting and removing lithium ions and Al, Ag, B, Cu, Mg formed on the surface of the carbon compound are described. An anode active material capable of improving lifetime characteristics and high-rate characteristics including an oxide film or hydroxide film of one or more elements selected from the group consisting of Si, Ti, Zn, and Zr It is described.

  However, the conventional technique has a high reactivity with the organic electrolyte that is the main cause of the irreversible capacity, and the influence by the acid generated by the oxidation of the electrolyte during charge / discharge is still large. There was a point.

  Therefore, efforts to solve the above-mentioned problems of the prior art have been sustained in related industries, and the present invention has been devised under such technical background.

Korean Published Patent No. 2005-0020186

  The technical problem to be solved by the present invention is to reduce the influence of the decomposition reaction of the organic electrolyte, which is the main cause of the irreversible capacity, and the influence of the acid generated by the oxidation of the electrolyte during charge / discharge. An anode active material for a lithium battery capable of achieving such a technical problem, a method for producing the same, and a lithium secondary battery comprising the same as an anode There is an object of the present invention to provide.

  An anode active material for a lithium secondary battery for achieving the technical problem to be solved by the present invention is characterized in that the surface of the anode active material for a lithium secondary battery is coated with a fluorine compound.

  Further, a method for producing an anode active material for a lithium secondary battery for achieving the technical problem to be solved by the present invention includes a step of adding and reacting an anode active material to a fluorine-based compound; Forming an anode active material whose surface is coated with a fluorine-based compound.

  In addition, a lithium secondary battery for achieving the technical problem to be solved by the present invention includes an anode to which an anode active material prepared according to the above manufacturing method is applied.

  Hereinafter, preferred embodiments of the present invention will be described in detail. Prior to this, terms and words used in the specification and claims should not be construed to be limited to ordinary or lexicographic meanings, and the inventor will best explain his invention. Therefore, in accordance with the principle that the concept of a term can be appropriately defined, it should be interpreted as a meaning and a concept consistent with the technical idea of the present invention. Accordingly, the configurations shown in the embodiments described in the present specification are only the most preferred embodiments of the present invention, and do not represent all the technical ideas of the present invention. It should be understood that there can be various equivalents and variations that can be substituted.

  The anode active material of the present invention is preferably coated on the surface with a fluorine compound by adding and reacting the anode active material to a fluorine compound. The fluorine-based compound used for coating the surface of the anode active material is produced by reacting fluorine (F) with a precursor. More preferably, the fluorine-based compound is in the form of a complex salt.

Examples of the fluorine-based _{compound, CsF, KF, LiF, NaF} , RbF, TiF, AgF, AgF 2, BaF 2, CaF 2, CuF 2, CdF 2, FeF 2, HgF 2, Hg 2 F 2, MnF 2, _{MgF 2, NiF 2, PbF 2} , SnF 2, SrF 2, XeF 2, ZnF 2, AlF 3, BF 3, BiF 3, CeF 3, CrF 3, DyF 3, EuF 3, GaF 3, GdF 3, FeF 3 _{, HoF 3, InF 3, LaF} 3, LuF 3, MnF 3, NdF 3, VOF 3, PrF 3, SbF 3, ScF 3, SmF 3, TbF 3, TiF 3, TmF 3, YF 3, YbF 3, TlF ₃ , CeF ₄ , GeF ₄ , HfF ₄ , SiF ₄ , SnF ₄ , TiF ₄ , VF ₄ , ZrF ₄ , NbF ₅ , SbF ₅ , TaF ₅ , BiF ₅ , MoF ₆ , ReF ₆ , SF ₆ , WF _{6 and the} like can be used.

  The precursors include Cs, K, Li, Na, Rb, Ti, Ag (I), Ag (II), Ba, Ca, Cu, Cd, Fe, Hg (II), Hg (I), Mn (II), Mg, Ni, Pb, Sn, Sr, Xe, Zn, Al, B, Bi (III), Ce (III), Cr, Dy, Du, Ga, Fe, Ho, In, La, Lu , Mn (III), Nd, VO, Pr, Sb (III), Sc, Sm, Tb, Ti (III), Tm, Y, Yb, Tl, Ce (IV), Ge, Hf, Si, Sn, Ti (IV), V, Zr, Nb, Sb (V), Ta, Bi (V), Mo, Re, S, W, etc. can be used.

The anode active material for a lithium secondary battery can be manufactured as follows.
First, an anode active material is added to and reacted with the fluorine-based compound formed by mixing the fluorine-containing compound and the element precursor-containing compound as described above (S1). Next, as a result of the reaction, an anode active material whose surface is coated with a fluorine compound is formed (S2). Specifically, in the step (S1), the anode active material is supported on the element precursor-containing solution, impregnated by stirring (S1a), and then the fluorine-containing solution is mixed with the impregnated result. A precipitation reaction may be performed and stirring may be performed (S1b).

  In the step (S1a), the element precursor-containing solution is preferably used in an amount of 0.1 to 10 mol% with respect to the anode active material. In the numerical range relating to the concentration of the element precursor-containing solution, if it is less than the lower limit value, the coating effect does not appear, and the influence by the acid cannot be reduced, which is not desirable. Further, when the upper limit is exceeded, the capacity and energy density are reduced by its own weight, which is not desirable.

  In the step (S1b), the amount of the fluorine-containing solution is determined according to the element precursor-containing solution. Specifically, it is preferably used in an amount of 0.1 to 60 mol% with respect to the element precursor-containing solution. In the numerical range relating to the concentration of the fluorine-containing solution, if it is less than the lower limit value, there is an element that cannot be bonded to fluorine in the element precursor to be coated, and thus the desired coating amount cannot be coated, and thus the desired characteristics. Is not desirable because it cannot be obtained. On the other hand, if the upper limit is exceeded, an excessive amount of fluorine is added, which may affect the performance of the anode active material, which is not desirable.

  In the step (S1b), the fluorine-containing solution is mixed at a temperature of 50 to 100 ° C. at a flow rate of 1 to 100 ml / min for 3 to 48 hours to be coprecipitated and then stirred to form a surface on the anode active material. A fluorine compound can be coated.

  Regarding the numerical range of the flow rate of the fluorine compound-containing solution, when it is less than the lower limit, there is an advantage that the fluorine compound can be gradually formed on the surface of the anode active material, but the reaction time is long. So undesirable. On the other hand, when the upper limit is exceeded, it is not desirable because the surface of the anode active material cannot be uniformly coated due to the fast binding rate of fluorine that binds to the element precursor. In addition, the particle size of the fluorine-based compound to be formed is increased, and a layer having a uniform thickness cannot be formed on the surface of the active material, which is undesirable because electrochemical performance may be deteriorated.

  With respect to the numerical range of the reaction time, when it is less than the lower limit value, the element precursor and fluorine are combined to form a fluorine compound, and this fluorine compound is uniformly coated on the surface of the anode active material. In this case, it is not desirable because a sufficient amount of time is not sufficient to form a fluorine compound in a desired form. When the upper limit is exceeded, the surface of the anode active material may be altered, such as being oxidized by a solvent, which is undesirable because it may affect the performance of the anode active material.

  In the present invention, the desired form of the fluorine compound should be obtained in order to coat the anode active material with the fluorine compound. When the temperature of the coprecipitation reaction is within the above range, coprecipitation is performed at a high temperature, whereby a highly disperse fluorine compound in the form of a complex salt can be obtained. Such a highly disperse fluorine compound in the form of a complex salt is more preferable in the coating of the anode active material.

The anode active material coated with the fluorine-based compound obtained as described above is
The subsequent washing step (S3);
A step of drying the washed result (S4); and a step of heat-treating the dried result (S5),
Finally it can be manufactured.

At this time, in the step (S3), the washing can be performed using distilled water according to a conventional method.
In the (S4) drying step, the temperature range can be varied depending on the type of solvent. In the present invention, the reaction is carried out at a temperature of 50 to 150 ° C. using water or an alcohol solvent such as methanol or ethanol. In the numerical range related to the drying temperature, if it is less than the lower limit, it takes a long time to remove the solvent after the coating process, which is undesirable because the overall process time becomes long. There is a possibility that the surface of the active material is altered, such as being oxidized. In addition, if it is altered, it may affect the performance of the anode active material, which is not desirable. In addition, the drying is a step of removing the solvent after the coating step, and therefore the drying time is not limited as long as the anode active material can be sufficiently dried.

  In the step (S5), in the heat treatment step, the heat treatment temperature may be varied depending on the type of the element precursor used for forming the fluorine compound. Specifically, it is preferably performed at 150 to 900 ° C. for 1 to 20 hours under any one condition selected from an oxidizing atmosphere, a reducing atmosphere, and a vacuum state. In the numerical range related to the heat treatment temperature, if it is less than the lower limit value, it is not desirable because a fluorine compound in a desired form cannot be formed. On the other hand, when the above upper limit is exceeded, it is not desirable because a fluorine compound in a desired form cannot be formed or carbonization proceeds to affect the physical properties and performance of the anode active material. Further, in the numerical range related to the heat treatment time, when the heat treatment time is less than the lower limit, the heat treatment time is short, so that a fluorine compound in a desired form cannot be formed or impurities may remain, which is not desirable. Further, when the upper limit is exceeded, the physical properties and performance of the anode active material may be affected, which is not desirable.

  The anode active material used in the present invention is not limited as long as it is an anode active material manufactured according to a conventional method manufactured in the art. Specifically, an anode active material produced by coating a core carbon material with low crystalline carbon can be used.

  As the core carbon material, natural graphite, artificial graphite, or a mixture thereof can be used. In particular, it is preferable to use spherical natural graphite as the core carbon material.

As the low crystalline carbon, pitch, tar, phenol resin, furan resin, furfuryl alcohol, and the like can be used.
That is, the present invention is characterized in that a core carbon material is coated with low crystalline carbon to prepare an anode active material, and then the surface of the anode active material is coated with a fluorine compound as described above.

In addition, the lithium secondary battery of the present invention is manufactured by including the anode active material manufactured by the above method. The lithium secondary battery of the present invention can be manufactured as follows.
First, a cathode active material, a conductive material, a binder, and a solvent are mixed to prepare a cathode active material composition. The cathode active material composition is directly coated on a metal current collector and dried to prepare a cathode plate. In addition, the cathode active material composition can be cast on a separate support, and then a film obtained by peeling from the support can be laminated on a metal current collector to produce a cathode plate. .

As the cathode active material, any lithium-containing metal oxides that are usually used in the art can be used. For example, as the cathode active _{material, LiCoO 2, LiMn x O 2x} , LiNi 1-x Mn x O 2x (x = 1,2), Ni 1-x-y Co x Mn y O 2 (0 ≦ x ≦ 0.5, 0 ≦ y ≦ 0.5), etc. can be used. More specifically, a compound capable of oxidation and reduction of lithium, such as LiMn ₂ O ₄ , LiCoO ₂ , LiNiO ₂ , LiFeO ₂ , V ₂ O ₅ , TiS, and MoS, can be used.

  Carbon black is used as the conductive material, and vinylidene fluoride / hexafluoropropylene copolymer, polyvinylidene fluoride, polyacrylonitrile, polymethyl methacrylate, polytetrafluoroethylene and a mixture thereof, and styrene-butadiene rubber-based polymer are used as the binder. be able to. As the solvent, N-methylpyrrolidone, acetone, water or the like can be used. At this time, the cathode active material, the conductive material, the binder, and the solvent are used at a content level normally used in a lithium battery.

  As the separator, any separator that is usually used in lithium batteries can be used. In particular, it is desirable to have a low resistance to ion migration of the electrolyte and an excellent electrolyte solution moisture-containing ability. Specifically, the separator is a material selected from glass fiber, polyester, Teflon (registered trademark), polyethylene, polypropylene, polytetrafluoroethylene (PTFE), and a mixture thereof, and may be a nonwoven fabric or a woven fabric. . More specifically, in the case of a lithium ion battery, a rollable separator made of a material such as polyethylene or polypropylene is used, and in the case of a lithium ion polymer battery, the organic electrolyte solution has excellent impregnation ability. Use a separator. Such a separator can be manufactured according to the following method.

  That is, a polymer resin, a filler, and a solvent are mixed to prepare a separator composition. The separator composition is coated directly on the electrode and dried to form a separator film, or after casting and drying on a support, the separator film peeled off from the support is laminated on the electrode. be able to.

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

Examples of the electrolyte include propylene carbonate, ethylene carbonate, diethyl carbonate, ethyl methyl carbonate, methyl propyl carbonate, butylene carbonate, benzonitrile, acetonitrile, tetrahydrofuran, 2-methyltetrahydrofuran, γ-butyrolactone, dioxolane, 4-methyldioxolane, N, N-dimethylformamide, dimethylacetamide, dimethyl sulfoxide, dioxa, 1,2-dimethoxyethane, sulfolane, dichloroethane, chlorobenzene, nitrobenzene, dimethyl carbonate, methyl ethyl carbonate, diethyl carbonate, methyl propyl carbonate, methyl isopropyl carbonate, ethyl propyl carbonate, Dipropyl carbonate, dibutyl carbonate 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 , diethylene glycol, dimethyl ether, or a mixed solvent thereof. LiSbF ₆ , LiAlO ₄ , LiAlCl ₄ , LiN (C _x F _{2x + 1} SO ₂ ) (C _y F _{2y + 1} SO ₂ ) (where x and y are natural numbers), among electrolytes made of lithium salts such as LiCl and LiI 1 type or these can melt | dissolve and use 2 or more types of mixtures.

  A battery structure is formed by disposing a separator between the cathode plate and the anode plate as described above. After winding or folding such a battery structure into a cylindrical battery case or a rectangular battery case, an organic electrolyte can be injected to manufacture a lithium ion battery.

  Moreover, after laminating | stacking the said battery structure by a bicell structure, this can be made to impregnate with an organic electrolyte solution, and the obtained result can be sealed in a pouch, and a lithium ion polymer battery can be manufactured.

Hereinafter, the present invention will be described more specifically through preferred embodiments in order to help understanding of the present invention.
Example 1
Spherical natural graphite carbon material and pitch were prepared.

  The spherical natural graphite was mixed with a pitch dissolved in tetrahydrofuran at a constant weight ratio. This was wet-stirred for 2 hours or more at normal pressure, mixed and then dried to produce a mixture. This mixture was subjected to primary and secondary firing for 1 hour at 1,100 ° C. and 1,500 ° C. for 1 hour, respectively, and classified to remove fine powders to produce an anode active material.

Next, after dissolving 2 mol% of _{Al (NO 3) 3 · 9H} 2 O in a beaker of 2,000 ml (based on weight of the anode active material) of distilled water 2,000 ml, the anode was the production The active material was supported and stirred until it was completely impregnated. While maintaining the temperature of the beaker at about 80 ° C., 500 ml of a 6 mol% NH ₄ F mixed solution was mixed at a flow rate of 1 ml / min for coprecipitation reaction. The reaction was further stirred for 12 hours. At this time, the average temperature of the reaction vessel was maintained at about 80 ° C.

The anode active material coated with the fluorine compound obtained through the above reaction was washed with distilled water and dried in a hot air constant temperature bath at 110 ° C. for 12 hours. Next, the dried anode active material was heat-treated at 400 ° C. under an inert atmosphere to produce an anode active material coated with AlF ₃ .

100 g of the prepared anode active material coated with AlF ₃ was placed in a 500 ml reactor, and a small amount of N-methylpyrrolidone (NMP) and a binder (PVDF) were added and kneaded using a mixer. Subsequently, the mixture was pressure-dried on copper foil and used as an electrode. At this time, the electrode density was 1.5 g / cm ³ and the electrode thickness was 70 μm.

Moreover, in order to evaluate charging / discharging efficiency, the coin cell (Coin Cell) was manufactured and evaluated.
Example 2
In Example 1, except that Al-isopropoxide and absolute ethanol were used instead of Al (NO ₃ ) ₃ · 9H ₂ O and distilled water, the same method as in Example 1 was used. did.

Example 3
In Example 1, except for using Zr (SO ₄ ) ₂ .xH ₂ O instead of Al (NO ₃ ) ₃ .9H ₂ O, the same method as in Example 1 was used. .

Example 4
Example 1 was prepared in the same manner as in Example 1 except that Zr-ethoxide and absolute ethanol were used in place of Al (NO ₃ ) ₃ · 9H ₂ O and distilled water.

Comparative Example 1
Spherical natural graphite carbon material and pitch were prepared.
The spherical natural graphite was mixed with a pitch dissolved in tetrahydrofuran at a constant weight ratio. This mixture was subjected to primary and secondary firing for 1 hour at 1,100 ° C. and 1,500 ° C. for 1 hour, respectively, and classified to remove fine powders to produce an anode active material.

100 g of the anode active material (a mixture of graphitic carbon material and pitch) thus produced is put into a 500 ml reactor, and a small amount of N-methylpyrrolidone (NMP) and a binder (PVDF) are added to the mixer. And kneaded. Next, it was pressure-dried on a copper foil and used as an electrode. At this time, the electrode density was 1.5 g / cm ³ and the electrode thickness was 70 μm.

Moreover, in order to evaluate charging / discharging efficiency, the coin cell was manufactured and evaluated.
Using the anode active materials prepared in Examples 1 to 4 and Comparative Example 1, the charge / discharge test was evaluated by battery characteristics by the following method. The results are shown in Table 1 below.

First, the battery was charged to 0.01 V at a charging current of 0.5 mA / cm ³ while regulating the potential in the range of 0 to 1.5 V. While maintaining the voltage of 0.01 V, the charging was continued until the charging current reached 0.02 mA / cm ³ . The discharge current was 0.5 mA / cm ³ and discharge was performed up to 1.5 V.

  In the following Table 1, the charge / discharge efficiency indicates the ratio of the discharged electric capacity to the charged electric capacity.

前記表１からわかるように、本発明によって表面がフッ素系化合物でコートされた実施例１ないし４のアノード活物質は、表面がコートされていない比較例１のアノード活物質と比較して充・放電時に優れたサイクル特性を現わし、高率特性に優れているので電気化学的特性が向上されることを確認することができた。

As can be seen from Table 1, the anode active materials of Examples 1 to 4 whose surfaces were coated with a fluorine-based compound according to the present invention were charged as compared with the anode active materials of Comparative Example 1 whose surfaces were not coated. Excellent cycle characteristics were exhibited during discharge, and it was confirmed that the electrochemical characteristics were improved because of excellent high rate characteristics.

  Although the present invention has been described in detail only for the specific examples described above, it is obvious to those skilled in the art that various modifications and corrections are possible within the scope of the technical idea of the present invention. It goes without saying that the modifications belong to the appended claims.

  The anode active material whose surface is coated with a fluorine-based compound according to the present invention can stabilize the surface and reduce the influence of the organic electrolyte decomposition reaction, which is the main cause of irreversible capacity. In addition, the anode active material of the present invention can exhibit excellent cycle characteristics and high rate characteristics during charge / discharge by reducing the influence of an acid generated by oxidation of the electrolyte during charge / discharge.

Claims (16)

An anode active material for a lithium secondary battery, wherein a surface of the anode active material for a lithium secondary battery is coated with a fluorine compound. The fluorine-based compounds are CsF, KF, LiF, NaF, RbF, TiF, AgF, AgF ₂ , BaF ₂ , CaF ₂ , CuF ₂ , CdF, which are produced by reacting fluorine (F) with a precursor. ₂ , FeF ₂ , HgF ₂ , Hg ₂ F ₂ , MnF ₂ , MgF ₂ , NiF ₂ , PbF ₂ , SnF ₂ , SrF ₂ , XeF ₂ , ZnF ₂ , AlF ₃ , BF ₃ , BiF ₃ , CeF ₃ , CrF _{3, DyF 3, EuF 3,} GaF 3, GdF 3, FeF 3, HoF 3, InF 3, LaF 3, LuF 3, MnF 3, NdF 3, VOF 3, PrF 3, SbF 3, ScF 3, SmF 3, TbF ₃ , TiF ₃ , TmF ₃ , YF ₃ , YbF ₃ , TlF ₃ , CeF ₄ , GeF ₄ , HfF ₄ , SiF ₄ , SnF ₄ , TiF ₄ , VF ₄ , ZrF ₄ , NbF ₅ , SbF ₅ , TaF ₅ , BiF ₅ , MoF ₆ , ReF ₆ , SF _6, and WF _6, or a mixture thereof The anode active material for a lithium secondary battery according to claim 1. The anode active material for a lithium secondary battery according to claim 1, wherein the fluorine compound is a complex salt material. The element precursor is Cs, K, Li, Na, Rb, Ti, Ag (I), Ag (II), Ba, Ca, Cu, Cd, Fe, Hg (II), Hg (I), Mn ( II), Mg, Ni, Pb, Sn, Sr, Xe, Zn, Al, B, Bi (III), Ce (III), Cr, Dy, Du, Ga, Fe, Ho, In, La, Lu, Mn (III), Nd, VO, Pr, Sb (III), Sc, Sm, Tb, Ti (III), Tm, Y, Yb, Tl, Ce (IV), Ge, Hf, Si, Sn, Ti (IV ), V, Zr, Nb, Sb (V), Ta, Bi (V), Mo, Re, S and W, or a single element arbitrarily selected from these. The anode active material for a lithium secondary battery according to claim 2, wherein the anode active material is an element mixture of the following. In the method for producing an anode active material for a lithium secondary battery,
(S1) adding and reacting an anode active material to the fluorine-based compound; and (S2) forming an anode active material whose surface is coated with the fluorine-based compound as a result of the reaction;
A method for producing an anode active material for a lithium secondary battery, comprising: In the step (S1),
As the fluorine-based compound, a fluorine (F) is reacted with the precursor is _{generated, CsF, KF, LiF, NaF} , RbF, TiF, AgF, AgF 2, BaF 2, CaF 2, CuF 2, CdF 2, _{FeF 2, HgF 2, Hg 2} F 2, MnF 2, MgF 2, NiF 2, PbF 2, SnF 2, SrF 2, XeF 2, ZnF 2, AlF 3, BF 3, BiF 3, CeF 3, CrF 3, _{DyF 3, EuF 3, GaF 3} , GdF 3, FeF 3, HoF 3, InF 3, LaF 3, LuF 3, MnF 3, NdF 3, VOF 3, PrF 3, SbF 3, ScF 3, SmF 3, TbF 3 _{, TiF 3, TmF 3, YF} 3, YbF 3, TlF 3, CeF 4, GeF 4, HfF 4, SiF 4, SnF 4, iF _{4, VF 4,} a _{ZrF 4, NbF 5, SbF 5} , TaF 5, BiF 5, MoF 6, the use of the _ReF 6, SF _6, and one or a mixture thereof selected from the group of substances consisting of WF ₆ The method for producing an anode active material for a lithium secondary battery according to claim 5. The method for producing an anode active material for a lithium secondary battery according to claim 6, wherein the fluorine-based compound is a complex salt material. The precursor is Cs, K, Li, Na, Rb, Ti, Ag (I), Ag (II), Ba, Ca, Cu, Cd, Fe, Hg (II), Hg (I), Mn (II ), Mg, Ni, Pb, Sn, Sr, Xe, Zn, Al, B, Bi (III), Ce (III), Cr, Dy, Du, Ga, Fe, Ho, In, La, Lu, Mn ( III), Nd, VO, Pr, Sb (III), Sc, Sm, Tb, Ti (III), Tm, Y, Yb, Tl, Ce (IV), Ge, Hf, Si, Sn, Ti (IV) , V, Zr, Nb, Sb (V), Ta, Bi (V), Mo, Re, S, and W, or a mixed element thereof. 6. A method for producing an anode active material for a lithium secondary battery according to 6. The step (S1) includes:
(S1a) a step of supporting an anode active material in an element precursor-containing solution, stirring and impregnating; and (S1b) a step of mixing the impregnated product with a fluorine-containing solution to perform a coprecipitation reaction and stirring;
The manufacturing method of the anode active material for lithium secondary batteries of Claim 5 characterized by the above-mentioned. The lithium secondary battery according to claim 9, wherein in the step (S1a), the element precursor-containing solution is used in an amount of 0.1 to 10 mol% with respect to the anode active material. A method for producing an anode active material. The lithium secondary battery according to claim 9, wherein in the step (S1b), the fluorine-containing solution is used in an amount of 0.1 to 60 mol% with respect to the element precursor-containing solution. A method for producing an anode active material. The lithium secondary solution according to claim 9, wherein, in the step (S1b), the fluorine-containing solution is mixed and stirred for 3 to 48 hours at a flow rate of 1 to 100 ml / min at a temperature of 50 to 100 ° C. A method for producing an anode active material for a secondary battery. After the step (S2), (S3) a step of washing the anode active material coated with the fluorine compound;
6. The lithium secondary battery according to claim 5, further comprising: (S4) drying the washed result; and (S5) heat treating the washed result. A method for producing an anode active material. The method according to claim 13, wherein the drying in the step (S4) is performed at a temperature of 50 to 150 ° C. The heat treatment of the step (S5) is performed at 150 to 900 ° C. for 1 to 20 hours under any one condition selected from an oxidizing atmosphere, a reducing atmosphere, and a vacuum state. Item 14. A method for producing an anode active material for a lithium secondary battery according to Item 13. A lithium secondary battery comprising an anode to which an anode active material manufactured according to the method according to any one of claims 5 to 15 is applied.