KR101499428B1 - Positive electrode materials for Lithium secondary battery using spherical cobalt hydroxide - Google Patents

Abstract

The present invention relates to a cathode material for a nonaqueous lithium secondary battery using spherical cobalt hydroxide and a method of producing a spherical cobalt hydroxide in which a dissimilar metal is uniformly substituted using a precipitation reaction in a liquid phase, So as to suppress the structural collapse and improve the life characteristic. According to the present invention, the cobalt raw material, the hydroxyl group raw material, the substitutional dissimilar metal raw material, and the amine raw material are represented by the following chemical formula: Co _1-x M _x (OH) ₂ (0.00 < _x ≦ 0.10, M = Al, Mg, So that spherical cobalt hydroxide having a particle size of 15 to 30 mu m can be prepared. The prepared cobalt hydroxide may be heat-treated at a temperature ranging from 500 to 800 ° C. to produce spherical cobalt oxide having a particle size of 10 to 25 μm. The cathode material produced by using such cobalt oxide exhibits excellent life characteristics even under the condition of high voltage charging and discharging of 4.5V.

Description

[0001] The present invention relates to a positive electrode material for a non-aqueous lithium secondary battery using spherical cobalt hydroxide,

The present invention relates to a cathode material for a non-aqueous lithium secondary battery, and more particularly, to a cathode material for a non-aqueous lithium secondary battery using a spherical cobalt hydroxide capable of minimizing a side reaction with an electrolyte even when used at high voltage, And a cathode material for a lithium secondary battery.

2. Description of the Related Art With the spread of portable electric and electronic devices, development of a new secondary battery such as a nickel metal hydride battery or a lithium secondary battery is actively under way. Among them, the lithium secondary battery is a battery using carbon such as graphite as an anode active material, using an oxide containing lithium as a cathode active material, and using a non-aqueous solvent as an electrolyte. Since lithium is a metal having a very high ionization tendency, development of a battery having a high energy density is possible because high voltage can be expressed.

Lithium transition metal oxides containing lithium are mainly used as the positive electrode active material used therein, and more than 90% of layered lithium transition metal oxides such as cobalt, nickel, and ternary systems in which cobalt, nickel, and manganese coexist are used have.

However, the layered lithium transition metal oxide, which is widely used as a cathode active material, has a problem in that cobalt ions are eluted for a side reaction with electrolyte in a non-abnormal state (overcharge and high temperature state) and an irreversible resistance layer is formed on the surface, . In order to overcome the drawbacks of layered lithium metal oxides and to use them for a longer period of time, studies have been conducted to minimize the specific surface area from the step of preparing the precursor and to suppress the side reaction with the electrolyte solution .

In order to solve this problem, it has been attempted to prepare a cathode material having a large particle size in order to improve the lifetime characteristics by minimizing a side reaction with the electrolyte. However, due to the nature of the layered material, There is a disadvantage in that it is not effectively reduced.

Accordingly, an object of the present invention is to provide a cathode material for a non-aqueous lithium secondary battery using a spherical cobalt hydroxide having a particle size of 20 탆 or more and having improved life characteristics so as to realize a high energy density.

Another object of the present invention is to provide a cathode material for a nonaqueous lithium secondary battery using spherical cobalt hydroxide having excellent sphericity and internal compactness of cobalt hydroxide produced by adding a functional complexing agent in a liquid phase step in a cobalt oxide manufacturing process There is.

In order to achieve the above object, the present invention provides a cathode material for a non-aqueous lithium secondary battery comprising spherical cobalt hydroxide prepared by coprecipitation of an aqueous solution containing a cobalt raw material, a hydroxyl group raw material, a substitute dissimilar metal raw material, and an amine raw material do.

In the cathode material for a non-aqueous lithium secondary battery according to the present invention, the cobalt hydroxide has a composition ratio of Co _1-x M _x (OH) ₂ (0.00 < _x ≦ 0.10, M = Al, Mg or Ti) And the particle size may be 15 to 30 mu m.

In the cathode material for a non-aqueous lithium secondary battery according to the present invention, the concentrations of the cobalt raw material, the hydroxyl group raw material, the substitutional dissimilar metal raw material, and the amine raw material are 0.5 to 2 M, respectively, and the cobalt raw material, And the pH of the mixed aqueous solution is maintained at 10 to 12 by coprecipitating the dissimilar metal raw material and the amine raw material at a ratio of 1: 1.8 to 2.5: 0.1 or less: 0.05 to 0.50.

In the cathode material for a non-aqueous lithium secondary battery according to the present invention, the amine-based material may include ethylenediamine, urea, or succinonitrile (SN).

In the cathode material for a non-aqueous lithium secondary battery according to the present invention, the cobalt raw material may include cobalt metal, manganese oxalate, manganese acetate, manganese nitrate, or manganese sulfate. The dissimilar metal of the dissimilar metal raw material may include aluminum (Al), magnesium (Mg), or titanium (Ti).

The present invention also provides a process for producing spherical cobalt hydroxide, which is prepared by coprecipitation of an aqueous solution containing a cobalt raw material, a hydroxyl group raw material, a substitutional dissimilar metal raw material, and an amine raw material and then heat treating the cobalt hydroxide, Of cobalt oxide and a positive electrode material for a non-aqueous lithium secondary battery.

In the cathode material for a non-aqueous lithium secondary battery according to the present invention, the cobalt oxide has a composition ratio of Co _3-y M _y O ₄ (0.00 < _y ? 0.30, M = Al, Mg or Ti) Lt; / RTI &gt;

In the cathode material for a non-aqueous lithium secondary battery according to the present invention, the heat treatment during the production of the cobalt oxide may be performed at 500 to 800 ° C.

The present invention also provides a process for producing a spherical cobalt hydroxide prepared by coprecipitation of an aqueous solution containing a cobalt raw material, a hydroxyl group raw material, a substitutional dissimilar metal raw material, and an amine raw material and then subjecting the cobalt hydroxide to heat treatment, Of lithium cobalt oxide prepared by preparing lithium cobalt oxide, cobalt oxide, lithium cobalt hydroxide, lithium cobalt oxide, and lithium cobalt oxide.

In the cathode material for a non-aqueous lithium secondary battery according to the present invention, the heat treatment during the production of the cobalt oxide may be performed at 500 to 800 ° C., and the heat treatment during the production of the lithium cobalt oxide may be performed at 900 to 1100 ° C.

In the cathode material for a nonaqueous-based lithium secondary battery according to the present invention, the lithium source includes lithium carbonate, lithium hydroxide, lithium acetate, lithium sulfate, lithium sulfite, lithium acetate, lithium fluoride, lithium chloride, lithium bromide or lithium iodide .

And the present invention _{also, LiCo 1-y M y O} 2 (0.00 <y≤0.10, M = Al, Mg or Ti) having a composition ratio of, spherical and a mean particle size of 15 ~ 25㎛ a non-aqueous lithium secondary battery positive electrode Material.

According to the present invention, a cobalt hydroxide having a high density of highly spherical highly uniformly substituted heterometallic metal and a cobalt oxide through heat treatment thereof is produced through a coprecipitation process using a functional complexing agent containing an amine-based raw material. The produced lithium cobalt oxide can be produced to have a high sphericity in the form of a uniformly substituted heterogeneous element. The prepared cathode material has a capacity of 80% or more of the initial capacity even after 50 charge / Expression is possible.

Also, the cathode material according to the present invention has a high sphericity and has a very low specific surface area, so that a side reaction with an electrolyte at a high temperature can be remarkably suppressed.

1 is a flowchart illustrating a method of manufacturing a cathode material for a non-aqueous lithium secondary battery according to the present invention.
FIG. 2 is an internal shape image of a spherical cobalt hydroxide which is a cathode material for a nonaqueous-based lithium secondary battery manufactured by the manufacturing method of Example 1 in the manufacturing method of FIG.
3 is an internal shape image of a spherical cobalt hydroxide which is a cathode material for a nonaqueous lithium secondary battery manufactured by the manufacturing method of Comparative Example 1. Fig.
Fig. 4 is a particle image of cobalt hydroxide, cobalt oxide and lithium cobalt oxide cathode material prepared by the manufacturing method of Example 1. Fig.
FIG. 5 is a particle image of a lithium cobalt oxide cathode material prepared by the production method of Example 2, cobalt hydroxide, cobalt oxide, and cobalt oxide.
6 is a graph showing charge / discharge lifetime characteristics of a cathode material manufactured by the manufacturing method of Example 1, Example 2, and Comparative Example 1 at a high temperature of 60 캜.

In the following description, only parts necessary for understanding the embodiments of the present invention will be described, and the description of other parts will be omitted so as not to obscure the gist of the present invention.

The terms and words used in the present specification and claims should not be construed as limited to ordinary or dictionary meanings and the inventor is not limited to the meaning of the terms in order to describe his invention in the best way. It should be interpreted as meaning and concept consistent with the technical idea of the present invention. Therefore, the embodiments described in the present specification and the configurations shown in the drawings are merely preferred embodiments of the present invention, and are not intended to represent all of the technical ideas of the present invention, so that various equivalents And variations are possible.

Hereinafter, embodiments of the present invention will be described in detail with reference to the accompanying drawings.

A method of manufacturing a cathode material for a non-aqueous lithium secondary battery according to the present invention will now be described with reference to FIG. 1 is a flowchart illustrating a method of manufacturing a cathode material for a non-aqueous lithium rechargeable battery according to the present invention.

Referring to FIG. 1, a method for producing a cathode material for a non-aqueous lithium secondary battery according to the present invention includes a cobalt hydroxide manufacturing step (S10) and a cobalt oxide manufacturing step (S20) Step S40 may be further included. Here, in step (S10) of producing cobalt hydroxide, spherical cobalt hydroxide substituted with a dissimilar metal is prepared by coprecipitation of an aqueous solution containing a cobalt raw material, a hydroxyl group raw material, a substitutional dissimilar metal raw material and an ethylenediamine raw material. Next, the cobalt hydroxide is heat-treated in the step (S20) of producing cobalt oxide to prepare a spherical high-density cobalt oxide substituted with a dissimilar metal. Lithium cobalt oxide is prepared by mixing lithium carbonate in cobalt oxide and heat-treating it in the step of preparing lithium cobaltate (S30). Finally, in the pulverizing step (S40), lithium cobalt oxide as a cathode material is pulverized and pulverized.

The method for manufacturing the cathode material for a non-aqueous lithium secondary battery according to the present invention will now be described in detail.

First, the cobalt raw material, the hydroxyl raw material, the substitutional heterobaric raw material, and the ethylenediamine raw material are continuously fed into the coprecipitation reactor while controlling the pH to prepare spherical hydroxides Cobalt is produced. That is, the concentrations of the raw materials are controlled so as to be in the ranges of 0.5 to 2.0M, respectively, so that the ratio of the cobalt raw material: substitutional dissimilar metal raw material: hydroxyl group raw material: amine raw material = 1: 0.00-0.1: 1.8-2.5: 0.05-0.50 And the reaction is carried out for 50 to 100 hours to prepare cobalt hydroxide. If the ratio is out of the above range, the pH is out of the range of 10 to 12, so that uniform precipitation between cobalt and the dissimilar metal does not occur and independent precipitation occurs, so that a uniformly substituted hydroxide can not be obtained. Also, when the reaction time is less than 50 hours, the particle formation is relatively low, so that particles of 5 μm or less are produced, and the spheroidization of the particles is also very low.

At this time, spherical cobalt hydroxide having a particle size of 15 to 30 mu m can be prepared by precipitating the cobalt hydroxide having a composition ratio of formula (1) in the step (S10) of producing cobalt hydroxide.

The cobalt raw material includes at least one of cobalt metal, manganese oxalate, manganese acetate, manganese nitrate, and manganese sulfate, but is not limited thereto.

The dissimilar metals of the dissimilar metal raw materials include aluminum (Al), magnesium (Mg), titanium (Ti) and the like. For example, when aluminum is used as the dissimilar metal, the dissimilar metal raw material includes at least one of aluminum nitrate and aluminum chloride, but is not limited thereto.

As the amine-based raw material, ethylenediamine, urea, succinonitrile (SN) may be used, but the present invention is not limited thereto.

Next, spherical cobalt hydroxide is heat-treated in the step (S20) of producing cobalt oxide to prepare cobalt oxide for a cathode material according to Formula (2). At this time, the heat treatment is performed at 500 to 800 ° C in an air atmosphere to produce the final spherical cobalt oxide. In this case, when the heat treatment is performed at a temperature of 500 ° C or lower, sufficient heat treatment for the spherical precursor is not performed, so that hydrogen ions may not be removed 100%. On the other hand, when the heat treatment is performed at 800 ° C. or higher, the spherical precursor is reacted more than necessary and the spherical shape is broken. When the spherical shape disappears, the reaction rate with the lithium raw material will be lowered in the future, and lithium cobalt oxide can not be effectively produced.

The cobalt oxide produced in the cobalt oxide manufacturing step (S20) is a spherical cobalt oxide having a composition ratio of formula (2) and an average particle size of 10 to 25 占 퐉. The cobalt oxide according to formula (2) is a precursor for the cathode material finally prepared according to the present invention.

The cobalt oxide produced in the lithium cobalt oxide manufacturing step (S30) may be reacted with a lithium source to prepare a cathode material which is lithium cobalt oxide substituted with a dissimilar metal. That is, lithium cobalt oxide cathode material for a nonaqueous lithium secondary battery can be manufactured through heat treatment after mixing lithium raw material with the prepared cobalt oxide.

The lithium cobalt oxide produced in the lithium cobalt oxide manufacturing step (S30) is a spherical lithium cobaltate having a composition ratio of the formula (3) and an average particle size of 15 to 25 占 퐉.

The lithium source includes at least one of lithium carbonate, lithium hydroxide, lithium acetate, lithium sulfate, lithium sulfite, lithium acetate, lithium fluoride, lithium chloride, lithium bromide and lithium iodide.

At this time, the heat treatment is performed at 900 to 1100 ° C in an air atmosphere to produce the final lithium cobalt oxide. At this time, when the heat treatment is performed at 900 ° C or less, sufficient heat treatment is not performed, and the usable capacity is lowered to 120 mAhg ^-1 or less. On the other hand, when the heat treatment is performed at a temperature of 1100 ° C or more, a reaction occurs more than necessary, and large particles having a primary particle size of 25 μm or more are generated and the output characteristic is lowered.

On the other hand, in order to produce a cathode plate after the cobalt oxide lithium production step (S30), the heat-treated cathode material can be pulverized and pulverized. The pulverization is carried out in a conventional manner. Examples of the crushing means include a trigger, a ball mill, a vibrating mill, a satellite ball mill, a tube mill, a rod mill, a jet mill, a hammer mill, and the like, and if necessary, a desired particle size distribution is obtained through classification. The average particle size of the powder of the cathode material of the present invention is preferably within a range of 15 to 25 mu m.

The lithium secondary battery to which the cathode material of the present invention is applied is not different from the conventional lithium secondary battery manufacturing method in terms of the cathode material. The production of the positive electrode plate and the structure of the lithium secondary battery will be briefly described, but the present invention is not limited thereto.

The positive electrode plate may be prepared by adding one or two or more kinds of additive components which are generally used as a conductive agent, a binder, a filler, a dispersant, an ion conductive agent, a pressure enhancer, etc. to the powder of the positive electrode material of the present invention , And slurry or paste is made with a suitable solvent (organic solvent). The thus obtained slurry or paste is coated on the electrode supporting substrate by using a doctor blade method, dried, pressed with a rolling roll, or the like, and used as a cathode plate.

Examples of the conductive agent include graphite, carbon black, acetylene black, Ketjen Black, carbon fiber, metal powder and the like. As the binder, PVdF, polyethylene and the like can be used. The electrode supporting substrate (also referred to as current collector) may be formed of a foil, a sheet, or a carbon fiber, such as copper, nickel, stainless steel, or aluminum.

A lithium secondary battery is fabricated using the thus-produced positive electrode. The shape of the lithium secondary battery may be a coin, a button, a sheet, a cylindrical shape, or a square shape. The anode material, the electrolyte, and the separator of the lithium secondary battery are to be used in existing lithium secondary batteries.

As the negative electrode material, a carbon material such as graphite or a composite oxide of a transition metal, or the like, may be used. In addition, silicon, tin, and the like can also be used as a negative electrode material.

As the electrolytic solution, either a non-aqueous liquid electrolyte in which a lithium salt is dissolved in an organic solvent, an inorganic solid electrolyte, or a composite material of an inorganic solid electrolyte can be used.

Examples of the solvent of the non-aqueous liquid electrolyte include esters such as ethylene carbonate, propylene carbonate, dimethyl carbonate, diethyl carbonate and methyl ethyl carbonate, lactones such as butyl lactone, 1,2-dimethoxyethane and ethoxymethoxyethane Nitriles such as ethers and acetonitrile, or the like can be used.

Examples of the lithium salt of the non-aqueous liquid electrolyte include LiAsF ₆ , LiBF ₄ , LiPF ₆ , and the like.

As the separation membrane, a porous film made of polyolefin such as PP and / or PE or a porous material such as nonwoven fabric can be used.

Examples and Comparative Examples

The cobalt oxide according to Example 1 was prepared as follows.

A 1.5M solution of cobalt sulfate, a 1.5M solution of sodium hydroxide, a 1.5M solution of aluminum nitrate and a 1.5M solution of ethylenediamine were added to the coprecipitation reactor at a rate of 20 cc / Thereby preparing spherical cobalt hydroxide substituted with a metal. The cobalt hydroxide thus prepared was kept in air at 750 ° C for 10 hours to prepare the cobalt oxide for cathode material according to the final Example 1.

Lithium carbonate was dry-mixed with cobalt oxide so that the ratio of lithium ion to cobalt ion was 1.05, and maintained at 950 ° C for 15 hours in air to prepare a cathode material according to the final embodiment 1.

The powder of the cathode material according to Example 1 was classified so as to have an average particle diameter of 15 to 25 占 퐉. A slurry was prepared by using 94 wt% of an anode material, 3 wt% of acetylene black as a conductive agent, and 3 wt% of PVdF as a binder in NMP as a solvent. The slurry was applied to an aluminum foil having a thickness of 20 mu m, dried and compacted by a press, and dried in a vacuum at 120 DEG C for 16 hours to prepare an electrode with a disk having a diameter of 16 mm.

A lithium metal foil punched with a diameter of 16 mm was used as a counter electrode, and a PP film was used as a separator. As the electrolytic solution, a mixed solution of 1: 1 v / v of EC / DME of 1M LiPF ₆ was used. After the electrolyte was impregnated into the separator, the separator was sandwiched between the working electrode and the counter electrode, and the case of the SUS product was evaluated as a test cell for electrode evaluation.

The cathode materials according to Example 2, Example 3, Comparative Example 1 and Comparative Example 2 were prepared under the conditions as shown in Table 1. [

sample
ID Feedstock (1.5M) Particle shape 4.5V 60 ° C
Life characteristics
(50 charge / discharge cycles)
[%] Remarks Co raw material Substituent NaOH Ethylene
Diamine ammonia One 0.98 0.02 2.05 0.05 0.00 Spherical, medium density 84 Example 2 2 0.98 0.02 2.05 0.10 0.00 Spherical, high density 93 Example 1 3 0.98 0.02 1.95 0.20 0.00 Old-fashioned, 80 Example 3 4 0.98 0.02 1.95 0.50 0.00 Non-spherical 70 Comparative Example 2 5 0.95 0.05 2.05 0.00 0.50 Spherical, porous 77 Comparative Example 1

The internal shape of the cathode material prepared according to Example 1 is as shown in FIG. Fig. 2 is an internal shape image of cobalt hydroxide, which is a precursor for a cathode material for a nonaqueous-based lithium secondary battery manufactured by the manufacturing method of Example 1 in the manufacturing method of Fig. FIG. 2 is an enlarged image of the inner shape of cobalt hydroxide from (a) to (c).

Referring to FIG. 2, it has a very high sphericity and relatively high density. Thus, it is possible to manufacture a high-density cathode material when a reaction is performed through heat treatment with lithium carbonate for the preparation of the final cathode material. Such high level of sphericity can minimize the specific surface area, and chemical stability can be imparted to the anode material even under high temperature charging and discharging conditions of 60 캜, and excellent lifetime characteristics are exhibited. A particle shape image of cobalt hydroxide, cobalt oxide and lithium cobalt oxide cathode material prepared by the manufacturing method of Example 1 is shown in Fig. 4 (d) is an enlarged view of (c).

On the other hand, the internal shape of the cathode material manufactured according to Comparative Example 1 is as shown in FIG. 3 is an internal shape image of cobalt hydroxide which is a precursor for a cathode material for a nonaqueous lithium secondary battery produced by the method of Comparative Example 1. Fig. It is easy to diffuse the lithium species into the cobalt oxide when the reaction through the heat treatment with the lithium carbonate is performed for the final cathode material production in the future because of the spherical porosity. However, in Comparative Example 1, the density and spheroidization degree are lower than those in Example 1.

A particle shape image of cobalt hydroxide, cobalt oxide and lithium cobalt oxide cathode material prepared by the manufacturing method of Example 2 is shown in Fig. It can be confirmed that the density of the second embodiment is slightly lower than that of the first embodiment, but the density and the sphericity are improved as compared with the first comparative example. 5 (d) is an enlarged view of (c).

As shown in Table 1, the cathode material prepared by the manufacturing method of Example 3 has improved denseness and sphericity as compared with Comparative Example 1.

Therefore, the lithium cobalt oxide prepared from the cobalt hydroxide produced by the manufacturing method of the present Example 1 has a high degree of sphericity of 15 to 20 탆, and capacity expression of 85% or more of the initial capacity even after 50 cycles of charging / discharging at a high temperature of 60 캜 . That is, the improvement of the performance of the cathode material can be achieved by using a coprecipitation reactor in a liquid phase to optimally control the process conditions and using a higher level of functional complexing agent such as ethylenediamine, It was possible to produce cobalt hydroxide and cobalt oxide having high density and high sphericity.

Charge-discharge output characteristics of the test cell for evaluating the electrode at room temperature with the cathode material prepared from the cobalt hydroxide according to Example 1, Example 2 and Comparative Example 1 were measured as shown in Fig. 6 is a graph showing charge / discharge lifetime characteristics at a high temperature of 60 占 폚 of the cathode material produced by the manufacturing method of Example 1, Example 2, and Comparative Example 1. FIG.

Referring to Table 1 and FIG. 6, it can be seen that the capacity decrease relative to the initial capacity is significant after the charge / discharge cycle of the battery of Comparative Example 1 is 50 times as compared with that of Example 1. [ That is, it can be confirmed that the cathode material according to Example 1 exhibits excellent charge / discharge characteristics even at 60 ° C under high temperature charging / discharging conditions as compared with the cathode material according to Comparative Example 1.

Thus, it can be confirmed that the cathode material according to Example 1 has 93% of the initial capacity after 50 charge / discharge cycles at 60 DEG C at a high temperature as compared with the cathode material according to Comparative Example 1. [ In the case of Comparative Example 1, 77% of the initial capacity can be confirmed after 50 charge / discharge cycles. In the case of Example 2, 84% of the initial capacity can be confirmed after 50 cycles of charging and discharging. In Example 3, 80% of the initial capacity can be confirmed after 50 charge / discharge cycles.

That is, since the cathode material according to Example 1 was produced from a hydroxide having a high degree of sphericity and a high density, the cathode material thus prepared exhibited a capacity expression of 80% or more of the initial capacity even after 50 charge / discharge cycles at a high temperature of 60 ° C You can see that it is possible.

It should be noted that the embodiments disclosed in the present specification and drawings are only illustrative of specific examples for the purpose of understanding, and are not intended to limit the scope of the present invention. It will be apparent to those skilled in the art that other modifications based on the technical idea of the present invention are possible in addition to the embodiments disclosed herein.

Claims (15)

Wherein the concentrations of the cobalt raw material, the hydroxyl group raw material, the substitutional dissimilar metal raw material (M) and the amine raw material are 0.5 to 2M, and the cobalt raw material, the hydroxyl group raw material, the substitution dissimilar metal raw material and the amine raw material are mixed at a ratio of 1: 1.8 to 2.5: And a spherical cobalt hydroxide having an average particle size of 15 to 30 占 퐉 which is prepared by maintaining the pH of the mixed aqueous solution at 10 to 12 while coprecipitating at a ratio of more than 0: 0.05 to 0.50 for 50 to 100 hours,
The cobalt hydroxide,
And a composition ratio of Co _1-x M _x (OH) ₂ (0.00 < _x ? 0.10, M = Al, Mg, or Ti). delete delete The method according to claim 1,
Wherein the amine-based raw material comprises ethylene diamine, urea, or succinonitrile (SN). 5. The method of claim 4,
Wherein the cobalt raw material comprises cobalt metal, manganese oxalate, manganese acetate, manganese nitrate or manganese sulfate. Spherical cobalt hydroxide having an average particle size of 15 to 30 탆 was prepared by coprecipitation of an aqueous solution containing a cobalt raw material, a hydroxyl group raw material, a substitutional dissimilar metal raw material (M) and an amine raw material, and then the cobalt hydroxide was heat- A spherical cobalt oxide substituted with a dissimilar metal,
Wherein said cobalt hydroxide is used in an amount of 0.5 to 2M for each of the cobalt raw material, the hydroxyl group raw material, the substitutional dissimilar metal raw material and the amine raw material, and the cobalt raw material, the hydroxyl group raw material, the substitutional dissimilar metal raw material, 0.1 or less and more than 0: 0.05 to 0.50 for 50 to 100 hours, while maintaining the pH of the mixed aqueous solution at 10 to 12,
The cobalt hydroxide,
And a composition ratio of Co _1-x M _x (OH) ₂ (0.00 < _x ? 0.10, M = Al, Mg, or Ti). delete delete 7. The method according to claim 6,
Co _3-y M _y O ₄ (0.00 < _y ? 0.30, M = Al, Mg, or Ti) and has an average particle size of 10 to 25 μm. The method according to claim 6,
Wherein the cobalt oxide is heat-treated at 500 to 800 ° C. A spherical cobalt hydroxide having an average particle size of 15 to 30 占 퐉 produced by coprecipitation of an aqueous solution containing a cobalt raw material, a hydroxyl group raw material, a substitutional dissimilar metal raw material (M) and an amine raw material was prepared and then the cobalt hydroxide was heat- Lithium cobalt oxide prepared by preparing a spherical cobalt oxide substituted with a dissimilar metal, mixing the lithium source with the cobalt hydroxide, and heat-treating the mixture,
Wherein said cobalt hydroxide is used in an amount of 0.5 to 2M for each of the cobalt raw material, the hydroxyl group raw material, the substitutional dissimilar metal raw material and the amine raw material, and the cobalt raw material, the hydroxyl group raw material, the substitutional dissimilar metal raw material, 0.1 or less and more than 0: 0.05 to 0.50 for 50 to 100 hours, while maintaining the pH of the mixed aqueous solution at 10 to 12,
The cobalt hydroxide,
And a composition ratio of Co _1-x M _x (OH) ₂ (0.00 < _x ? 0.10, M = Al, Mg, or Ti). 12. The method of claim 11,
The heat treatment during the production of the cobalt oxide is performed at 500 to 800 ° C,
Wherein the heat treatment at the time of preparing the lithium cobalt oxide is performed at 900 to 1100 占 폚. 12. The method of claim 11,
Wherein the lithium source comprises lithium carbonate, lithium hydroxide, lithium acetate, lithium sulfate, lithium sulfite, lithium acetate, lithium fluoride, lithium chloride, lithium bromide, or lithium iodide. 12. The method of claim 11,
The amine-based raw material includes ethylenediamine, urea or succinonitrile (SN)
Wherein the cobalt raw material comprises cobalt metal, manganese oxalate, manganese acetate, manganese nitrate or manganese sulfate. The lithium secondary battery according to claim 11,
_{LiCo 1-y M y O 2} (0.00 <y≤0.10, M = Al, Mg or Ti) having a composition ratio of, spherical and a mean particle size of 15 ~ 25㎛ a non-aqueous lithium secondary battery positive electrode material.

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