KR100853327B1 - Anode active material for rechargeable lithium ion battery and method for preparing thereof and lithium ion battery manufactured using the same - Google Patents

Abstract

The present invention relates to a negative electrode active material for a lithium battery, a method of manufacturing the same, and a lithium secondary battery using the same. The negative electrode active material for a lithium battery of the present invention is characterized in that the surface of the negative electrode active material is coated with a fluorine compound. According to the present invention, by stabilizing the surface of the negative electrode active material to reduce the effect of the decomposition reaction of the organic electrolyte, which is the main cause of irreversible capacity and at the same time to reduce the impact on the acid generated by the oxidation of the electrolyte during charge and discharge, excellent cycle characteristics and There is an advantage that can exhibit high rate characteristics.

Negative electrode active material, fluorine compound, negative electrode, lithium secondary battery, charge and discharge efficiency

Description

Anode active material for rechargeable lithium ion battery and method for preparing pretty and lithium ion battery manufactured using the same}

The present invention relates to a negative electrode active material for a lithium battery, a method of manufacturing the same, and a lithium secondary battery using the same. More particularly, the surface of the negative electrode active material is stabilized to reduce the effects of the organic electrolyte solution decomposition reaction, which is the main cause of irreversible capacity, and at the same time during charge and discharge. The present invention relates to a negative electrode active material for a lithium battery, a method for manufacturing the same, and a lithium secondary battery using the same, which may reduce the influence on an acid generated by oxidizing an electrolyte and thus exhibit excellent cycle characteristics and high rate characteristics during charge and discharge.

Lithium secondary batteries, which are in the spotlight as a power source for portable small electronic devices, show high energy density by showing a discharge voltage that is two times higher than that of a battery using an aqueous alkali solution using an organic electrolyte solution.

As a cathode active material of a lithium secondary battery, an oxide made of lithium and a transition metal having a structure capable of intercalating lithium, such as LiCoO ₂ , LiMn ₂ O ₄ , and LiNi _1-x Co _x O ₂ (0 <x <1) Was mainly used.

As the negative electrode active material, various types of carbon-based materials including lyozyme, natural graphite, and hard carbon capable of lithium insertion / desorption have been applied. The carbon-based negative electrode material has excellent voltage flatness and good life characteristics at low potentials, but due to high reactivity with the organic electrolyte and low diffusion rate of lithium in the material, power characteristics, initial irreversible control, and charge and discharge Improvement of electrode swelling or the like is required.

In this case, in the prior art, in order to improve battery characteristics of graphite (or other carbonaceous material) used in the negative electrode, the shape, particle size and distribution of graphite powder, density, coating of amorphous carbon (pitch), crystallinity control by temperature, etc. Has been using the method.

As a specific example, Korean Patent Laid-Open Publication No. 2005-0020186 discloses a carbon-based compound capable of inserting and detaching lithium ions and Al, Ag, B, Cu, Mg, Si, Ti, Zn, and Zr formed on a surface of the carbon-based compound. It describes a negative electrode active material that can improve the life characteristics and high rate characteristics, including an oxide film or a hydroxide film of one or more elements selected from the group consisting of.

However, the prior art has a problem that the reactivity with the organic electrolyte, which is the main cause of the irreversible capacity, is high, and the influence on the acid produced by oxidation of the electrolyte during charge and discharge is still large.

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

The technical problem to be achieved by the present invention is to exhibit excellent cycle characteristics and high rate characteristics during charge and discharge by reducing the influence of the organic electrolyte solution decomposition reaction which is the main cause of irreversible capacity and the influence on the acid produced by oxidation of the electrolyte during charge and discharge. Another object of the present invention is to provide a negative electrode active material for a lithium battery and a method of manufacturing the same, and a lithium secondary battery including the same as a negative electrode capable of achieving the technical problem.

The negative electrode active material for a lithium secondary battery for achieving the technical problem to be achieved by the present invention is characterized in that the surface is coated with a fluorine compound, the fluorine compound, the fluorine (F) containing compound and the element precursor containing compound the reaction to produce 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 material consisting of a _{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 It is characterized in that it is a single selected from the group or a mixture of two or more selected arbitrarily thereof.

In addition, the method for producing a negative active material for a lithium secondary battery for achieving the technical problem to be achieved by the present invention, the step of adding and reacting the negative electrode active material to (S1) fluorine-based compound; And (S2) forming a negative electrode active material whose surface is coated with a fluorine compound as a result of the reaction, wherein the fluorine compound of step (S1) contains a fluorine (F) -containing compound and an elemental precursor. generated by the interaction of the 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, and WF ₆ It is characterized in that a single material selected from the group consisting of substances or a mixture of two or more selected from these.
Adding and reacting a negative electrode active material to the fluorine compound; And forming a negative electrode active material whose surface is coated with a fluorine-based compound as a result of the reaction.

In addition, the lithium secondary battery for achieving the technical problem to be achieved by the present invention is characterized in that it comprises a negative electrode to which the negative electrode active material prepared by the above-described manufacturing method is applied.

Hereinafter, preferred embodiments of the present invention will be described in detail. Prior to this, the terms or words used in this specification and claims should not be construed as being limited to the common or dictionary meanings, and the inventors will appropriately introduce the concept of terms in order to best explain their invention. It should be interpreted as meanings and concepts in accordance with the technical spirit of the present invention based on the principle that it can be defined. Therefore, the configurations shown in the embodiments described herein are only one of the most preferred embodiments of the present invention and do not represent all of the technical idea of the present invention, and various equivalents may be substituted for them at the time of the present application. It should be understood that there may be variations and variations.

It is preferable for the negative electrode active material of the present invention to coat the surface with a fluorine compound by adding and reacting a negative electrode active material to the fluorine compound. The fluorine-based compound used to coat the surface of the negative electrode active material is produced by mutually reacting a fluorine (F) -containing compound with an element precursor-containing compound, and more preferably in a complex salt form.

The fluoride compound is 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, the VF _4, ZrF _4, etc. _{NbF 5, SbF 5, TaF 5} , BiF 5, MoF 6, ReF 6, SF 6, or WF ₆ is used Can be.

In addition, 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, W, or the like may be used.

After adding and reacting the negative electrode active material to the fluorine compound formed by mixing the fluorine-containing compound and the element precursor-containing compound as described above (S1), the result of the reaction forms a negative electrode active material coated with the fluorine compound (S2) to form a lithium secondary. A negative electrode active material for a battery can be manufactured. Specifically, the step (S1) may be carried out by impregnating the negative electrode active material in the solution containing the element precursor, stirring and impregnating (S1a), mixing the fluorine-containing solution in the resultant impregnated coprecipitation reaction and stirring (S1b). .

In the step (S1a), the element precursor-containing solution is preferably used to be 0.1 to 10 mol% relative to the negative electrode active material. In the numerical range regarding the concentration of the element precursor-containing solution, it is not preferable that the coating effect does not appear when the concentration is less than the lower limit, so that the effect on the acid is not reduced. Reduced energy density is undesirable.

In addition, 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 0.1 to 60 mol% with respect to the element precursor-containing solution. In the numerical range of the concentration of the fluorine-containing solution, if less than the lower limit, there is an element that does not bond with fluorine in the element precursor to be coated, it is not desirable to coat the desired coating amount and thereby do not obtain the desired characteristics, When the upper limit is exceeded, an excessive amount of fluorine may be added to affect the performance of the negative electrode active material, which is not preferable.

In the step (S1b), the fluorine-containing solution is mixed for 3 to 48 hours at a flow rate of 1 to 100 ml / min at a temperature of 50 to 100 ℃ co-precipitation reaction and stirred to coat the fluorine-based compound on the surface of the negative electrode active material Can be.

In the numerical range of the flow rate of the fluorine compound-containing emulsion, if it is less than the lower limit, there is an advantage that the fluorine compound can be slowly formed on the surface of the negative electrode active material, but the reaction time is long, which is not desirable, and when the upper limit is exceeded. Due to the fast bonding speed of fluorine to bond with the element precursor, it is not evenly formed and coated on the surface of the negative electrode active material, and the particle size of the formed fluorine compound becomes large, thereby preventing the formation of a uniform thickness layer on the surface of the active material. Electrochemical performance can be degraded, which is undesirable.

In the numerical range of the reaction time, when less than the lower limit, the element precursor and fluorine are combined to form a fluorine compound, and there is not enough time for the fluorine compound to be uniformly coated on the surface of the anode active material to form a fluorine compound of a desired form. If the upper limit is exceeded, the surface of the negative electrode active material may be oxidized by a solvent, and the like may be deteriorated, which may affect the performance of the negative electrode active material.

In the present invention, in order to coat the negative electrode active material with a fluorine compound, a desired type of fluorine compound should be obtained. When the temperature of the coprecipitation reaction is within the above range, coprecipitation is performed at a high temperature to obtain a highly dispersed fluorine compound having a complex salt form. In addition, such a highly salted fluorine-based compound in the form of a complex salt is better for coating a negative electrode active material.

The negative electrode active material coated with the fluorine compound obtained as described above is then washed (S3); Drying the washed resultant (S4); And a negative electrode active material coated with the final fluorine-based compound may be prepared through the step (S5) of the dried resultant.

At this time, in the step (S3), the washing may be carried out using distilled water according to a conventional method, in the step (S4), the drying step may vary the temperature range depending on the type of solvent, In the present invention, it is carried out at a temperature of 50 to 150 ℃ using water or alcohol solvents such as methanol and ethanol. In the numerical range regarding the drying temperature, when the solvent is less than the lower limit, the removal of the solvent after the coating process takes a long time, and thus, the overall process time is not preferable. When the upper limit is exceeded, the surface of the negative electrode active material is oxidized. It is not preferable because it may affect the performance of the negative electrode active material. In addition, since the drying is a process of removing the solvent after the coating process, the range is not limited as long as the negative electrode active material can be sufficiently dried.

In addition, in the step (S5), the heat treatment step may control the heat treatment temperature differently according to the type of element precursor used to form the fluorine compound, and specifically selected from the oxidizing atmosphere, reducing atmosphere, and vacuum state It is preferable to carry out for 1 to 20 hours at 150 to 900 ℃ under one condition. In the numerical range with respect to the heat treatment temperature, the lower than the lower limit value is not preferable because it does not form a fluorine compound of the desired form, and when the upper limit is exceeded, the fluorine compound of the desired form may not be formed, or carbonization may proceed. It is not preferable because it may affect the physical properties and performance of the negative electrode active material. In addition, in the numerical range related to the heat treatment time, when the temperature is less than the lower limit, the heat treatment time is short, so that a fluorine compound of a desired form cannot be formed or impurities may remain, which is undesirable. It is not preferable because it may affect the active material properties and performance.

The negative electrode active material used in the present invention is not limited as long as it is a negative electrode active material prepared according to a conventional method manufactured in the art, specifically, a negative electrode active material prepared by coating low crystalline carbon on a core carbon material. Can be.

As the core carbon material, natural graphite, artificial graphite, or a mixture thereof may be used, and spherical natural graphite may be particularly used.

As the low crystalline carbon, pitch, tar, phenol resin, furan resin, or furfuryl alcohol may be used.

That is, the present invention is characterized by coating a low crystalline carbon on the core carbon material to prepare a negative electrode active material, and then coating the surface of the negative electrode active material with a fluorine-based compound as described above.

In addition, the lithium secondary battery of the present invention is characterized in that it is prepared including a negative electrode active material prepared by the above method. The lithium secondary battery of the present invention can be produced as follows.

First, a cathode active material composition is prepared by mixing a cathode active material, a conductive material, a binder, and a solvent. The positive electrode active material composition is directly coated on a metal current collector and dried to prepare a positive electrode plate. It is also possible to produce the positive electrode plate by casting the positive electrode active material composition on a separate support, and then laminating the film obtained by peeling from the support onto a metal current collector.

The positive electrode active material may be any lithium-containing metal oxide, as long as it is commonly used in the art, such as LiCoO ₂ , LiMn _x O _2x , LiNi _1-x Mn _x O _2x (x = 1, 2), Ni _1-xy Co _x Mn _y O ₂ (0≤x≤0.5, 0≤y≤0.5) and the like, and more specifically, LiMn ₂ O ₄ , LiCoO ₂ , LiNiO ₂ , LiFeO ₂ , V ₂ O ₅ And compounds capable of redoxing lithium, such as TiS, or MoS.

Carbon black is used as the conductive material, and vinylidene fluoride / hexafluoropropylene copolymer, polyvinylidene fluoride, polyacrylonitrile, polymethyl methacrylate, polytetrafluoroethylene and mixtures thereof And styrene butadiene rubber-based polymers, and the like, and N-methylpyrrolidone, acetone, water and the like are used as the solvent. At this time, the content of the positive electrode active material, the conductive material, the binder, and the solvent is a level commonly used in lithium batteries.

As the separator, any one commonly used in lithium batteries can be used. In particular, it is preferable that it is low resistance with respect to the ion migration of electrolyte, and is excellent in electrolyte-moisture capability. In more detail, the material selected from glass fiber, polyester, Teflon, polyethylene, polypropylene, polytetrafluoroethylene (PTFE), and combinations thereof may be nonwoven or woven. In more detail, a lithium-ion battery uses a rollable separator made of a material such as polyethylene or polypropylene, and a lithium-ion polymer battery uses a separator having excellent organic electrolyte impregnation capability. It can manufacture according to the following method.

That is, a separator composition is prepared by mixing a polymer resin, a filler, and a solvent, and the separator composition is directly coated and dried on an electrode to form a separator film, or the separator composition is cast and dried on a support. The separator film peeled off from the support can be formed by laminating on the electrode.

The polymer resin is not particularly limited, and any material used for the binder of the electrode plate may be used. For example, vinylidene fluoride / hexafluoropropylene copolymer, polyvinylidene fluoride, polyacrylonitrile, polymethyl methacrylate, mixtures 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, and dioxo Column, 4-methyldioxolane, N, N-dimethylformamide, dimethylacetamide, dimethyl sulfoxide, dioxane, 1,2-dimethoxyethane, sulfolane, dichloroethane, chlorobenzene, nitrobenzene, dimethyl carbonate LiPF ₆ , LiBF ₄ , LiSbF in methyl ethyl carbonate, diethyl carbonate, methyl propyl carbonate, methyl isopropyl carbonate, ethyl propyl carbonate, dipropyl carbonate, dibutyl carbonate, diethylene glycol, dimethyl ether, or a mixed solvent thereof. ₆ , LiAsF ₆ , LiClO ₄ , LiCF ₃ SO ₃ , Li (CF ₃ SO ₂ ) ₂ N, LiC ₄ F9SO ₃ , LiSbF ₆ , LiAlO ₄ , LiAlCl ₄ , LiN (C _x F _{2x + 1} SO ₂ ) (C _y F _{2y + 1} SO ₂ ) (wherein x and y are natural waters), one of an electrolyte composed of lithium salts such as LiCl, LiI, or a mixture of two or more thereof can be dissolved and used.

The separator is disposed between the positive electrode plate and the negative electrode plate as described above to form a battery structure. The battery structure may be wound or folded to be placed in a cylindrical battery case or a square battery case, and then an organic electrolyte may be injected to manufacture a lithium ion battery.

In addition, the battery structure may be stacked in a bi-cell structure, and then impregnated in the organic electrolyte, and the resultant is placed in a pouch and sealed to manufacture a lithium ion polymer battery.

Hereinafter, the present invention will be described in more detail with reference to preferred embodiments.

Example 1

A spherical natural graphite carbon material and pitch were prepared.

The pitch dissolved in tetrahydrofuran in the spherical natural graphite was mixed in a constant weight ratio, mixed by wet stirring at normal pressure for 2 hours or more, and then dried to prepare a mixture. The mixture was calcined first and second at 1,100 ° C. and 1,500 ° C. for 1 hour, and classified to remove fine powder to prepare a negative electrode active material.

Then, after dissolving in 2,000 ml beaker of 2 mol% of Al (NO ₃ ) ₃ .9H ₂ O (relative to the weight of the negative electrode active material) 2,000 ml of distilled water, the negative electrode active material prepared above was supported, stirred and 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 to coprecipitation, and further stirred for 12 hours. At this time, the average temperature of the reactor was maintained at about 80 ℃.

The negative electrode active material coated with the fluorine compound obtained through the reaction was washed with distilled water, dried in a warm air bath at 110 ° C. for 12 hours, and heat-treated at 400 ° C. under an inert atmosphere to prepare an AlF ₃ -doped negative active material.

100 g of the AlF ₃ coated negative active material was put into a 500 ml reactor, and a small amount of N-methylpyrrolidone (NMP) and a binder (PVDF) were added and kneaded using a mixer. Compression drying on foil was used as electrode. At this time, electrode density was 1.5 g / cm <3> and electrode thickness was 70 micrometers.

In addition, to evaluate the charging and discharging efficiency, a coin cell was prepared and evaluated.

Example 2

Example 1 was carried out in the same manner as in Example 1, except that Al-isopropoxide and ethanol anhydride were used in place of Al (NO ₃ ) ₃ .9H ₂ O and distilled water.

Example 3

Example 1 was carried out in the same manner as in Example 1, except that Zr (SO ₄ ) ₂ .xH ₂ O was used in place of Al (NO ₃ ) ₃ .9H ₂ O.

Example 4

Example 1 was carried out in the same manner as in Example 1, except that Zr-ethoxide and ethanol anhydride were used in place of Al (NO ₃ ) ₃ .9H ₂ O and distilled water.

Comparative Example 1

A spherical natural graphite carbon material and pitch were prepared.

The pitch dissolved in tetrahydrofuran in the spherical natural graphite was mixed in a constant weight ratio, and the mixture was calcined for 1 hour and 1 hour at 1,100 ° C. and 1,500 ° C., respectively, and classified to remove fine powder to prepare a negative electrode active material.

100 g of the negative electrode active material (a mixture of graphite carbon material and pitch) thus prepared was put into a 500 ml reactor, and a small amount of N-methylpyrrolidone (NMP) and a binder (PVDF) were added thereto. After kneading, it was pressed and dried on a copper foil to use as an electrode. At this time, electrode density was 1.5 g / cm <3> and electrode thickness was 70 micrometers.

In addition, CoinCell was prepared and evaluated to evaluate the charging and discharging efficiency.

Using the negative electrode active materials prepared in Examples 1 to 4 and Comparative Example 1, the charge and discharge tests were evaluated by the battery characteristics as described below, and the results are shown in Table 1 below.

First, the potential is regulated in the range of 0 to 1.5 V to charge until the charging current is 0.5 mA / cm 2 until it becomes 0.01 V, the voltage is maintained at 0.01 V and charging is continued until the charging current becomes 0.02 mA / cm 2. It was. The discharge current was discharged up to 1.5 V at 0.5 mA / cm 2.

In Table 1 below, the charge and discharge efficiency shows the ratio of the discharged capacitance to the charged capacitance.

division Example 1 Example 2 Example 3 Example 4 Comparative Example 1 1st Cycle Discharge Capacity (mAh / g) 351.87 351.1 350.4 350.2 353.8 50 Cycle capacity retention rate (%) 96.8 97.1 96.5 97.6 86.3

Through Table 1, the negative electrode active material of Examples 1 to 4 whose surface is coated with a fluorine-based compound according to the present invention exhibits excellent cycle characteristics during charging and discharging as compared with the negative electrode active material of Comparative Example 1, which is not coated with a surface, and shows high rate characteristics. It was confirmed that the electrochemical properties are improved by this excellent.

Although only described in detail with respect to the described embodiments of the present invention, it will be apparent to those skilled in the art that various modifications and variations are possible within the technical spirit of the present invention, it is natural that such variations and modifications belong to the appended claims. .

The negative electrode active material coated with the fluorine-based compound according to the present invention stabilizes the surface to reduce the effect of the organic electrolyte decomposition reaction, which is the main cause of irreversible capacity, and at the same time reduces the influence on the acid produced by oxidation of the electrolyte during charge and discharge. There is an effect that can exhibit excellent cycle characteristics and high rate characteristics during discharge.

Claims (16)

Characterized in that the surface of the negative electrode active material for a lithium secondary battery is coated with a fluorine-based compound, The fluorine-based compound, a fluorine (F) containing compounds and elemental precursor containing a cross-reacting compound to produce 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 , A negative electrode active material for a lithium secondary battery, characterized in that a single material selected from the group consisting of BiF ₅ , MoF ₆ , ReF ₆ , SF ₆ , and WF ₆ or a mixture of two or more selected from these. The method of claim 1, The fluorine-based compound is a negative electrode active material for a lithium secondary battery, characterized in that the substance in the form of a complex salt. The method of claim 1, Elemental precursors used to produce the fluorine-based compound are 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 is a single element selected from the group or an arbitrary mixture of two or more selected among them A negative electrode active material for a lithium secondary battery, characterized in that. In the manufacturing method of the negative electrode active material for lithium secondary batteries, (S1) adding and reacting a negative electrode active material to the fluorine compound; And (S2) as a result of the reaction, the surface of the negative electrode active material coated with a fluorine-based compound; proceeds including, The fluorine-based compound of step (S1) is CsF, KF, LiF, NaF, RbF, TiF, AgF, AgF ₂ , BaF ₂ , CaF ₂ , produced by mutually reacting a fluorine (F) -containing compound with an element precursor-containing compound. 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 , and WF ₆ A single material selected from the group consisting of materials or a mixture of two or more selected arbitrarily selected from them, characterized in that the method for producing a negative active material for a lithium secondary battery. The method of claim 4, wherein The fluorine-based compound is a method of producing a negative electrode active material for a lithium secondary battery, characterized in that the complex salt material is used. The method of claim 4, wherein Elemental precursors used to produce the fluorine-based compound are 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, A single element selected from the group consisting of Sn, Ti (IV), V, Zr, Nb, Sb (V), Ta, Bi (V), Mo, Re, S, and W, or a mixture of two or more elements selected arbitrarily Method for producing a negative electrode active material for a lithium secondary battery, characterized in that it is used. The method of claim 4, wherein The step (S1) may include: impregnating and stirring the negative active material in the solution containing the element precursor (S1a); And (S1b) a method of manufacturing a negative electrode active material for a lithium secondary battery, comprising the step of: co-reacting and stirring a mixed fluorine-containing solution in the resultant impregnated product. The method of claim 7, wherein In the step (S1a), the element precursor-containing solution is a lithium secondary battery negative electrode active material manufacturing method characterized in that it is used to be 0.1 to 10 mol% compared to the negative electrode active material. The method of claim 7, wherein In the step (S1b), the fluorine-containing solution is used to prepare a negative active material for a lithium secondary battery, characterized in that it is used to 0.1 to 60 mol% with respect to the element precursor containing solution. The method of claim 7, 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 ℃ lithium secondary battery negative electrode active material manufacturing method. The method of claim 4, wherein After the step (S2), (S3) washing the negative active material coated with the fluorine-based compound; (S4) drying the washed resultant; And (S5) heat-treating the washed and dried result; negative electrode active material manufacturing method for a lithium secondary battery, characterized in that further comprising the progress. The method of claim 11, Drying of the step (S4), the negative electrode active material manufacturing method for a lithium secondary battery, characterized in that proceeds at a temperature of 50 to 150 ℃. The method of claim 11, The heat treatment of the step (S5), the negative electrode active material manufacturing method for a lithium secondary battery, characterized in that for 1 to 20 hours at 150 to 900 ℃ under any one condition selected from the oxidizing atmosphere, reducing atmosphere and vacuum state. A lithium secondary battery comprising a negative electrode to which a negative electrode active material prepared by the method according to any one of claims 4 to 13 is applied. delete delete