KR101384197B1 - Positive active material for rechargeable, method of preparing same, and rechargeable lithium battery comprising same - Google Patents

Abstract

A cathode active material for a lithium secondary battery, a method of manufacturing the same, and a lithium secondary battery including the same, wherein the cathode active material is represented by the following Formula 1, and has a particle size of 1 to 3 μm in which primary particles having an average size of 10 to 20 nm are assembled. It includes a spherical secondary particles having an average size, the carbon coating layer is formed on the surface of the secondary particles.

[Chemical Formula 1]

Li _a Mn _1-x M _x PO _4-y Z _y

(Wherein M, Z, a, x and y are as defined in the specification).

Cathode active material, Olivine, LiMnPO4, Carbon layer, Lithium secondary battery

Description

FIELD OF THE INVENTION [0001] The present invention relates to a positive active material for a lithium secondary battery, a method for producing the same, and a lithium secondary battery including the same. BACKGROUND OF THE INVENTION [0002]

The present invention relates to a cathode active material for a lithium secondary battery, a method for producing the same, and a lithium secondary battery comprising the same. More particularly, the present invention relates to a cathode active material for a lithium secondary battery exhibiting improved electrochemical characteristics, a method for producing the same, and a lithium secondary battery comprising the same. .

[0002] Lithium secondary batteries, which have been popular as power sources for portable electronic devices in recent years, exhibit a high energy density by using an organic electrolytic solution and exhibiting discharge voltages two times higher than those of conventional batteries using an aqueous alkaline solution.

LiCoO ₂ , LiMn ₂ O ₄ , LiNi _1-x Co _x O ₂ (0 <X <1) and the like were mainly used as positive electrode active materials of a lithium secondary battery. However, such a positive electrode active material is expensive, there is a problem such as safety, and research on a new positive electrode active material is in progress.

Among them, research on olivine type positive electrode active materials such as LiFePO ₄ or LiMnPO ₄ has been actively conducted. In particular, LiFePO ₄ has been developed as an energy source for hybrid vehicles and electric vehicles due to its excellent thermal safety. However, LiFePO ₄ has a disadvantage of low LiCoO ₂ discharge voltage currently used because the average operating voltage is about 3.5V.

LiMnPO ₄ is expected to exhibit high energy density from the high redox potential of Mn, but its electrical conductivity (<10 ^-10 S / cm) is much lower than LiFePO ₄ (1.8 X 10 ^-9 S / cm). Not much reported As a method for solving the problem of low electrical conductivity of the LiMnPO ₄ , there is a method of smoothing the de-insertion of lithium ions by making the particle size nano and improving the electrical conductivity by uniformly coating the carbon. Among these methods, the carbon coating method has a problem in that the dispersibility of the positive electrode active material decreases as the specific surface area of the positive electrode active material increases, which makes it difficult to apply the current collector in a high density and uniform state. In order to synthesize nano-sized particles, hydrothermal synthesis, solid phase, sol-gel, and precipitation have been studied, but the electrochemical properties of the lithium secondary battery cathode active material are still poorly degraded and have low tap density. There is this.

One embodiment of the present invention is to provide a cathode active material for a lithium secondary battery exhibiting increased tap density and excellent electrochemical properties.

Another embodiment of the present invention is to provide a method for producing the cathode active material.

Another embodiment of the present invention provides a lithium secondary battery comprising the cathode active material.

An embodiment of the present invention is represented by the following formula (1), and comprises a spherical secondary particles having an average size of 1 to 3㎛ assembled primary particles having an average size of 10 to 20nm, the secondary particles It provides a positive electrode active material for a lithium secondary battery that a carbon coating layer is formed on the surface.

[Chemical Formula 1]

Li _a Mn _1-x M _x PO _4-y Z _y

Wherein M is Fe, Co, Ti, Ni, Cu, Zn, Zr, Nb, Mo, or a combination thereof,

Z is F, S or a combination thereof,

0.85 ≦ a ≦ 1,

0 ≤ x ≤ 0.9,

0 ≤ y ≤ 0.5)

Another embodiment of the present invention is to add a lithium raw material, manganese raw material and phosphorus raw material to water to prepare a metal aqueous solution; A chelating agent and a first carbon raw material were added to the aqueous metal solution to prepare a mixed solution; Preparing the primary particles represented by Chemical Formula 1 by first heat treatment while ultrasonically spraying the mixed solution; Secondary particles are heat-treated to prepare secondary particles; Provided are a method for producing a positive electrode active material for a lithium secondary battery, including a step of mixing the secondary particles with the second carbon raw material and subjecting the mixture to a third heat treatment.

Another embodiment of the present invention is to provide a lithium secondary battery including a positive electrode including the positive electrode active material, a negative electrode including the negative electrode active material and a nonaqueous electrolyte.

The positive electrode active material according to the embodiment of the present invention is prepared by ultrasonic spray pyrolysis, and the nanometer-sized primary particles of uniform particles are formed of the assembled micrometer-sized secondary particles, and may exhibit high tap density. Thus, a lithium secondary battery exhibiting excellent electrochemical characteristics can be provided.

Hereinafter, embodiments of the present invention will be described in detail. However, this is presented as an example, by which the present invention is not limited and the present invention is only defined by the scope of the claims to be described later.

The cathode active material according to the embodiment of the present invention includes secondary particles in which primary particles of a lithium compound represented by Chemical Formula 1 are assembled. In this case, the average particle diameter of the primary particles may be 10 to 20nm, the average particle diameter of the secondary particles may be 1 to 3㎛.

At this time, the secondary particles have a spherical shape. As used herein, the term &quot; spherical &quot; includes a shape that may be circular or elliptical and may be referred to as a substantially spherical shape, but is not limited thereto. In addition, a carbon coating layer is formed on the surface of the secondary particles.

[Chemical Formula 1]

Li _a Mn _1-x M _x PO _4-y Z _y

Wherein M is Fe, Co, Ti, Ni, Cu, Zn, Zr, Nb, Mo or a combination thereof, Z is F, S or a combination thereof, 0.85 ≦ a ≦ 1, 0 ≦ x ≦ 0.9 and 0 ≦ y ≦ 0.5. The lithium compound represented by Chemical Formula 1 may have an olivine structure.

In the cathode active material, the average particle diameter of the primary particles is 10 to 20 nm, and when the average particle diameter of the primary particles is less than 10 nm, there is a problem that the primary particles are too small to take a long time to grow, and when the average particle diameter exceeds 20 nm There may be a problem that the particles are too large to obtain the desired electrochemical properties.

In addition, the average particle diameter of the secondary particles may be 1 to 3㎛. If the average particle diameter of the secondary particles is less than 1 μm, there is a problem in that the tap density is lowered. If the average particle diameter is more than 3 μm, the particles become large and a uniform carbon coating layer cannot be formed, so that the carbon coating layer can be uniformly formed as a whole. Therefore, the surface of the secondary particles having no carbon coating layer reacts with the electrolyte to form side reactions, thereby deteriorating the electrochemical properties.

The carbon coating layer is formed of amorphous carbon, and examples thereof include soft carbon (soft carbon), mesophase pitch carbide, calcined coke, and the like.

The carbon coating layer may have a thickness of about 1 nm to about 10 nm. When the thickness of the carbon coating layer is included in this range, the carbon coating layer may be uniformly coated on the surface of the secondary particles, the detachment and insertion of lithium ions can occur properly can exhibit improved electrochemical properties. In the cathode active material according to the embodiment of the present invention, the carbon coating layer formed on the surface of the secondary particles may prevent the secondary particles from being assembled in the secondary particle formation process and may improve conductivity of the lithium compound of Formula 1 Can be.

The effect of the presence of such a carbon coating layer can be obtained when the lithium compound of Formula 1, in particular, a compound having an olivine structure, is composed of primary particles and secondary particles. For example, compounds such as LiMnO ₂ , Li _{1 + x} (Ni _1/2 Mn _1/2 ) O ₂ (where 0 ≦ x ≦ 0.1), particularly compounds having a layered structure, can hardly serve as active materials. This is because oxygen bonding of the layered structure occurs during sintering in an inert atmosphere during the carbon coating layer forming process, so that the coefficient of oxygen is inappropriately changed.

Since the positive electrode active material according to the embodiment of the present invention is a micron sized material, it is possible to increase the tap density than the nano sized material, thereby reducing the battery volume. In addition, the carbon coating layer is formed on the surface can exhibit an improved electrical conductivity.

Another embodiment of the present invention is to provide a method of manufacturing a positive electrode active material according to an embodiment of the present invention.

First, lithium raw material, manganese raw material and phosphorus raw material are added to water to prepare an aqueous metal solution. At this time, the mixing ratio of the lithium raw material, manganese raw material and phosphorus raw material is adjusted so that Li: Mn: P is 0.85: 1: 1 to 1: 1: 1 molar ratio.

In addition, in the preparation of the metal aqueous solution, a compound containing F or S may be further added. In the case where the compound including F or S is further added, an active material in which a part of oxygen sites are replaced with F and S is prepared, and the active material may exhibit improved high C-rate characteristics.

The addition amount of the compound containing F or S can be suitably adjusted according to the molar ratio of the target product. Compounds containing F or S include nickel fluoride, iron fluoride, cobalt fluoride, manganese fluoride, chromium fluoride, zirconium fluoride, niobium fluoride, copper fluoride, vanadium fluoride, titanium fluoride, zinc Fluoride, aluminum fluoride, gallium fluoride, manganese fluoride, boron fluoride, NH ₄ F, LiF, AlF ₃ , S, Li ₂ S, hydrates thereof may be used alone or in combination of one or more thereof. .

In addition, when preparing the aqueous metal solution, M (Fe, Co, Ti, Ni, Cu, Zn, Zr, Nb, Mo or a combination thereof) may be further added. Since M is present in the final product by substituting a part of Mn, the amount of M-containing raw material used is 100: 0 to 10: 90 mol% when the total amount of Mn-containing raw material and M-containing raw material is 100 mol%. It can be used as rain. As the M-containing raw material, M-containing sulfate, M-containing hydroxide, M-containing nitrate, M-containing acetate or a mixture thereof can be used.

The lithium raw material may be lithium carbonate, lithium hydroxide, lithium nitrate, lithium acetate or a mixture thereof, and the manganese raw material may be manganese sulfate, manganese hydroxide, manganese nitrate, manganese acetate or Mixtures of these can be used. In addition, the phosphorus raw material may be used by phosphoric acid, metaphosphoric acid, diphosphoric acid, orthophosphoric acid, orthophosphoric acid, ammonium dihydrogen phosphate (NH ₄ H ₂ PO ₄ ) or a mixture thereof. .

The concentration of the metal aqueous solution is appropriately adjusted so that the concentration of the total metal is 0.5 to 2M concentration. When the concentration of the total metal in the aqueous metal solution is included in the above range, the particles of the desired spherical particles can be formed by inhibiting the formation of particles that are cracked or crushed, and also the particles of the desired spherical shape while suppressing the formation of unwanted precipitates It can form suitably.

Subsequently, a chelating agent and a first carbon raw material are added to the aqueous metal solution to prepare a mixed solution. As the chelating agent, citric acid, ascorbic acid, polyvinyl alcohol, urea or a mixture thereof may be used. Sucrose, glucose, cellulose or a mixture thereof may be used as the first carbon raw material. When the first carbon raw material is added, the carbon source is physically or chemically bonded to the particles within or between the particles present in the aqueous metal solution, so that the carbon source is first decomposed during the subsequent heat treatment, particularly in an air atmosphere. As primary particles are formed, particles can be prevented from agglomerating, thereby suppressing grain growth.

The amount of the chelating agent may be 0.1 to 0.5M, and the amount of the first carbon raw material may be 5 to 50% by weight based on the weight of the manganese raw material. When the amount of the chelating agent is included in the above range, spherical particles can be appropriately formed, and when the amount of the first carbon raw material is included in the above range, grain growth during heat treatment can be suppressed and appropriate By maintaining the viscosity, the liquid crystal can be effectively formed in the ultrasonic spray process.

Subsequently, primary spraying is performed by ultrasonically spraying the mixed solution to prepare primary particles represented by Chemical Formula 1. The ultrasonic spraying is performed using an oscillation of 1.7 to 2.5 MHz, and a liquid crystal is produced according to an ultrasonic spraying process, and when the liquid crystal is heat-treated, primary particles are formed. The heat treatment step is preferably carried out at 300 to 700 ℃. When the temperature of the heat treatment process is included in the above range, spherical particles of appropriate size are appropriately suitable. The first carbon raw material used according to the primary heat treatment process is decomposed and does not remain in the primary particles as the final product.

The heat treatment process may be performed while passing the liquid crystal through a vertical pyrolysis furnace at a desired temperature.

The prepared primary particles have an amorphous phase and may be represented by the following Chemical Formula 1.

[Chemical Formula 1]

Li _a Mn _1-x M _x PO _4-y Z _y

Wherein M is Fe, Co, Ti, Ni, Cu, Zn, Zr, Nb, Mo, or a combination thereof,

Z is F, S or a combination thereof,

0.85 ≦ a ≦ 1,

0 ≤ x ≤ 0.9,

0 ≤ y ≤ 0.5)

The prepared primary particles are subjected to secondary heat treatment. According to this process, primary particles are assembled with each other to form crystalline secondary particles. The heat treatment process may be carried out at 500 to 700 ℃. In addition, the heat treatment process is preferably performed for 3 to 10 hours, the heat treatment process atmosphere may be an air atmosphere, Ar, N ₂ or Ar / H ₂ atmosphere.

The secondary particles formed and the second carbon raw material are mixed, and the mixture is subjected to a third heat treatment under an inert atmosphere. The inert atmosphere may include nitrogen atmosphere, argon atmosphere or Ar / H ₂ (mixing ratio of Ar / H ₂ 90:10 to 95: 5% by volume), and the third heat treatment may be performed at 500 to 700 ° C. can do. In addition, the third heat treatment may be performed for 1 to 5 hours. As the second carbon raw material, carbon black such as sucrose, glucose, polyvinyl alcohol, polypyrrole, pitch, cellulose, acetylene black, super-p, or a mixture thereof may be used. The mixing ratio of the secondary particles and the second carbon raw material may be 90:10 to 80:20 weight ratio. The second carbon raw material can suppress secondary particles from agglomerating and grain growth. When the mixing ratio of the secondary particles and the second carbon raw material is included in the above range, the carbon coating layer may be evenly formed on the surface of the secondary particles, thereby exhibiting excellent electrochemical properties and adversely affecting the lithium diffusion rate. The carbon coating layer can be formed to an appropriate thickness that does not fall.

According to the third heat treatment process, a carbon coating layer is formed on the surface of the secondary particles. The carbon coating layer may have a thickness of 1 to 10 nm. As described above, the tertiary heat treatment process is performed in an inert atmosphere, and in the present invention, the compound of Formula 1 constituting the primary particles is covalently bonded to metals (manganese and M) and PO ₄ , whereby oxygen is diffused. Without a problem, since the PO ₄ may be present as it is, without improving the physical properties, it is possible to obtain an effect of improving conductivity due to the carbon coating layer formation. However, if the compound having no composition of Formula 1, for example, a compound having a layered structure such as a spinel type, is deficient in oxygen during the tertiary heat treatment process, the oxygen coefficient of the compound is not appropriate and loses activity as an active material. Can be.

The method for preparing a cathode active material according to an embodiment of the present invention is spray pyrolysis, and compared to hydrothermal synthesis, sol-gel method, and precipitation method, a micron-sized spherical LiMn _1-x M _x PO _4-y Z _y ( M is Fe, Co, Ti, Ni, Cu, Zn, Zr, Nb, Mo or a combination thereof, Z is F, S or a combination thereof, 0 ≦ x ≦ 0.9, 0 ≦ y ≦ 0.5) The material can be synthesized, and the lithium raw material, manganese raw material and phosphorus raw material can be uniformly mixed at a time, thereby enabling mass synthesis.

The positive electrode active material according to the embodiment of the present invention may be usefully used for the positive electrode of a lithium secondary battery. The lithium secondary battery includes a negative electrode including a negative electrode active material together with a positive electrode, and a nonaqueous electrolyte.

The positive electrode is prepared by mixing a positive electrode active material according to an embodiment of the present invention, a conductive material, a binder and a solvent to prepare a positive electrode active material composition, and then directly coating and drying on the aluminum current collector. Or by casting the positive electrode active material composition on a separate support, then peeling the support from the support, and laminating the resulting film on an aluminum current collector.

The conductive material is carbon black, graphite, metal powder, the binder is vinylidene fluoride / hexafluoropropylene copolymer, polyvinylidene fluoride, polyacrylonitrile, polymethyl methacrylate, polytetrafluoroethylene And mixtures thereof. In addition, N-methylpyrrolidone, acetone, tetrahydrofuran, decane, etc. are used as a solvent. At this time, the content of the cathode active material, the conductive material, the binder and the solvent is used at a level normally used in a lithium secondary battery.

The negative electrode is prepared by mixing the negative electrode active material, the binder and the solvent in the same manner as the positive electrode. The negative electrode active material composition is coated directly on the copper current collector or cast on a separate support, and the negative active material film, Laminated. At this time, the negative electrode active material composition may further contain a conductive material if necessary.

As the negative electrode active material, a material capable of intercalating / deintercalating lithium is used, and for example, lithium metal, lithium alloy, coke, artificial graphite, natural graphite, organic polymer compound combustor, carbon fiber, or the like is used. . The conductive material, the binder and the solvent are used in the same manner as in the case of the above-mentioned anode.

The separator may be polyethylene, polypropylene, polyvinylidene fluoride or a multilayer film of two or more thereof. The separator may be a polyethylene / polypropylene double-layer separator, It is needless to say that a mixed multilayer film such as a polyethylene / polypropylene / polyethylene three-layer separator, a polypropylene / polyethylene / polypropylene three-layer separator and the like can be used.

As the electrolyte to be charged in the lithium secondary battery, a non-aqueous electrolyte or a known solid electrolyte may be used, and a lithium salt is used.

Although the solvent of the said non-aqueous electrolyte is not specifically limited, Chain carbonate methyl acetate, ethyl acetate, such as cyclic carbonate dimethyl carbonate, methyl ethyl carbonate, diethyl carbonate, such as ethylene carbonate, propylene carbonate, butylene carbonate, vinylene carbonate, Esters such as propyl acetate, methyl propionate, ethyl propionate and γ-butyrolactone 1,2-dimethoxyethane, 1,2-diethoxyethane, tetrahydrofuran, 1,2-dioxane, 2-methyltetrahydro Nitriles, such as ether acetonitrile, such as furan, or amides, such as dimethylformamide, etc. can be used. These can be used individually or in combination of two or more. Particularly, a mixed solvent of cyclic carbonate and chain carbonate can be preferably used.

As the electrolyte, a gelated polymer electrolyte in which an electrolyte solution is impregnated with a polymer electrolyte such as polyethylene oxide or polyacrylonitrile, or an inorganic solid electrolyte such as LiI or Li ₃ N can be used.

At this time, the lithium salt is 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 , LiAlO ₄ , LiAlCl ₄ , LiCl , And one selected from the group consisting of LiI is possible.

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

(Example 1)

Lithium nitrate (Li (NO) ₃ .6H ₂ O), manganese nitrate (Mn (NO ₃ ) ₂ .4H ₂ O), phosphoric acid (H ₃ PO ₄ ) were used as starting materials. The starting material was dissolved in distilled water in a ratio of the ratio Li: Mn: P = 1: 1: 1 to prepare a metal aqueous solution having a total metal concentration of 1M. To the aqueous metal solution was added 0.2% citric acid as a chelating agent and 20% by weight of sucrose as a carbon raw material to Mn (NO ₃ ) ₂ .4H ₂ O, followed by stirring to prepare a mixed solution.

The mixed solution was ultrasonically sprayed using a 1.7 MHz oscillator to generate droplets. The first liquid was passed through a mixed solution of the liquid phase in a vertical pyrolysis furnace at 400 ° C. to obtain primary particles of the powdered solid solid oxide LiMnPO ₄ . The prepared LiMnPO ₄ primary particles were amorphous.

Subsequently, the LiMnPO ₄ secondary particles were heat-treated at 500 ° C. for 5 hours in an air atmosphere to prepare LiMnPO ₄ secondary particles having crystallinity.

A scanning electron microscope (SEM) photograph (50,000 magnification) of the prepared LiMnPO ₄ secondary particles is shown in FIG. 1. As shown in Figure 1, it can be seen that it is composed of spherical secondary particles having an average size of 1 to 3㎛. Moreover, the primary particle which comprises the said secondary particle was about 10 nm in average particle diameter.

Subsequently, 20 wt% of the second carbon raw material sucrose was added to 80 wt% of the LiMnPO ₄ material of the spherical secondary particles having an average size of 1 to 3 μm and mixed well by a ball mill. The obtained mixture was placed in an alumina container and sintered (third heat treatment) for 5 hours under Ar / H ₂ (mixing ratio of Ar and H ₂ = 95: 5 volume ratio) in an inert atmosphere at 550 ° C. temperature.

The obtained product comprises a secondary particle having an average size of 1 to 3 μm, spherical particles of 10 nm primary particles, represented by LiMnPO ₄ , and having a carbon layer formed on the surface of the secondary particles. It was a positive electrode active material having. At this time, the thickness of the carbon layer was 10 nm.

* Measurement of physical properties of active materials

SEM of the cathode active material prepared by the above method was measured to analyze the microstructure of the cathode active material (FIG. 2, 50,000 magnification). As shown in FIG. 2, it can be seen that the prepared cathode active material has carbon on its surface.

In addition, X-ray diffraction intensity using CuKα of the cathode active material prepared by the above method was measured, and the results are shown in FIG. 3. As shown in FIG. 3, it can be seen that the prepared cathode active material exhibits crystallinity.

In addition, nitrogen adsorption and desorption analysis (BET) of the positive electrode active material prepared by the above method was carried out, and the results are shown in FIG. 4. From the results shown in FIG. 4, it can be seen that the specific surface area of the positive electrode active material is 66.17 m ² / g, and the pore volume is 2.085 × 10 ⁻¹ cc ⁻¹ (at relative pressure P / P ₀ = 0.99364). .

* Battery manufacturing

85 wt% of the positive electrode active material prepared in Example 1, 7.5 wt% of Super-P (carbon black), 7.5 wt% of KS-6 (carbon black), and 10 wt% of polyvinylidene fluoride were N-methylpyrrolidone The positive electrode active material slurry composition was prepared by uniformly mixing in a solvent.

The positive electrode active material slurry composition was applied to an aluminum foil current collector, pressed in a roll-press, and dried at 110 ° C. to prepare a positive electrode for a lithium secondary battery.

A positive electrode prepared by the above method, a lithium foil as a counter electrode, a porous polyethylene membrane (Celgard ELC, Celgard 2300, thickness: 25 μm) as a separator, ethylene carbonate and diethyl carbonate in which 1 M LiPF ₆ was dissolved in a liquid electrolyte solution The mixed solvent (1: 1 volume ratio) of the coin type half cell of the 2032 standard was produced according to the conventional manufacturing process of a lithium battery. The coin-type half-cell thus manufactured was subjected to constant current charging at 4.5C at 0.05C at 2.7 to 4.5V, further constant voltage charging at 1 / 100C, and then discharged to 2.7V at 0.05C. It was. The charge and discharge characteristics are shown in FIG. 5, and the initial discharge capacity was 118 mAh / g.

It will be understood by those skilled in the art that various changes in form and details may be made therein without departing from the spirit and scope of the invention as defined by the appended claims.

1 is a 50,000 magnification SEM photograph of secondary particles prepared according to Example 1 of the present invention.

Figure 2 is a 50,000-micrograph SEM image of the positive electrode active material prepared according to Example 1 of the present invention.

Figure 3 is a graph showing the measurement of the X-ray diffraction intensity of the positive electrode active material prepared according to Example 1 of the present invention.

Figure 4 is a graph showing the measurement of the BET of the positive electrode active material prepared according to Example 1 of the present invention.

5 is a graph showing charge and discharge characteristics of a half cell including a cathode active material prepared according to Example 1 of the present invention.

Claims (15)

Represented by the following formula (1), the primary particles having an average size of 10 to 20nm includes spherical secondary particles having an average size of 1 to 3㎛ assembled, On the surface of the secondary particles is formed a carbon coating layer of 1 to 10 nm thick Cathode active material for lithium secondary battery. [Chemical Formula 1] Li _a Mn _1-x M _x PO _4-y Z _y Wherein M is Fe, Co, Ti, Ni, Cu, Zn, Zr, Nb, Mo, or a combination thereof, Z is F, S or a combination thereof, 0.85 ≦ a ≦ 1, 0 ≤ x ≤ 0.9, 0 ≤ y ≤ 0.5) The method according to claim 1, The carbon coating layer is formed of amorphous carbon positive electrode active material for a lithium secondary battery. delete A lithium aqueous material, manganese raw material and phosphorus raw material are added to water to prepare an aqueous metal solution; Adding a chelating agent and a first carbon raw material to the aqueous metal solution to prepare a mixed solution; Preparing primary particles represented by Chemical Formula 1 by first thermal treatment while ultrasonically spraying the mixed solution; Secondarily heat treating the primary particles to produce secondary particles; Mixing the secondary particles with a second carbon raw material; And Tertiary heat treatment of the mixture; The manufacturing method of the positive electrode active material for lithium secondary batteries of Claim 1 containing. 5. The method of claim 4, The concentration of the aqueous metal solution is a method for producing a positive electrode active material for lithium secondary battery is 0.5 to 2M. 5. The method of claim 4, The mixing ratio of the lithium raw material, manganese raw material and phosphorus raw material is a Li: Mn: P is adjusted to 0.85: 1: 1 to 1: 1: 1 molar ratio manufacturing method of a positive electrode active material for lithium secondary batteries. 5. The method of claim 4, Method for producing a positive electrode active material for a lithium secondary battery which is further adding a compound containing F or S in the metal aqueous solution manufacturing step. 5. The method of claim 4, The chelating agent is citric acid, ascorbic acid, polyvinyl alcohol, urea, or a combination thereof. 5. The method of claim 4, The first carbon raw material is a sucrose, glucose, cellulose or a combination thereof independently of each other a method for producing a positive electrode active material for a lithium secondary battery. 5. The method of claim 4, The second carbon raw material is sucrose, glucose, polyvinyl alcohol, polypyrrole, pitch, acetylene black, carbon black, or a combination thereof. 5. The method of claim 4, The ultrasonic spray is a manufacturing method of a positive electrode active material for a lithium secondary battery that is performed using a vibrator of 1.7 to 2.5MHz. 5. The method of claim 4, The primary heat treatment is a method for producing a cathode active material for a lithium secondary battery that is carried out at 300 to 700 ℃. 5. The method of claim 4, The secondary heat treatment is a method for producing a positive active material for a lithium secondary battery that is carried out at 500 to 700 ℃. 5. The method of claim 4, The tertiary heat treatment is a method for producing a positive electrode active material for a lithium secondary battery that is carried out at 500 to 700 ℃. A positive electrode comprising the positive electrode active material of claim 1 or 2; A negative electrode comprising a negative electrode active material; And Nonaqueous electrolyte &Lt; / RTI &gt;

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