[1]Mutual citations and related application (s) [2]This application claims the benefit of priority based on the composite 31 Korea Patent Application No. 10-2017-0013613 and No. 10-2017-0013649 January 2017, and all information disclosed in the literature of Korea that patent application is herein It is included as a part of. [3]The present invention is a core-to a method of manufacturing the same and a lithium secondary battery positive electrode active material including a lithium cobalt oxide in the shell structure. [4] BACKGROUND [5] The rapidly increasing demand for secondary batteries as an energy source, as the technical development and demand for mobile devices increases, and can, in such a secondary battery shows a high energy density and operating potential, a long cycle life, self-discharge rate is low lithium secondary battery It is commercially available and widely used. [6] In addition, research on electric vehicles, hybrid electric vehicles to replace vehicles that use fossil fuels, such as a gasoline car, diesel car of the main causes of air pollution in accordance with the interest in environmental issues grows progress much . As a power source, such as those electric vehicles, hybrid electric vehicles, but mainly nickel hydrogen metal secondary battery is used, and the study has been actively conducted to use a lithium secondary battery of high energy density and discharge voltage, and in some commercialization. [7] A cathode material of the present lithium secondary battery, LiCoO 2 , Ternary (NMC / NCA), LiMnO 4 , LiFePO 4 is used and the like. LiCoO in a double two cases, even present LiCoO because it also clearly present advantages such as high rolling density 2 is a section in which a plurality is used, a situation that research for increasing the operating voltage in order to develop high-capacity secondary batteries is in progress. However, LiCoO 2 has a charging and discharging current as low as about 150 mAh / g, there is a problem that the crystal structure is unstable, the lifetime characteristics degrade rapidly to the voltage 4.3V or more, it has a risk of fire due to the reaction with the electrolyte solution . [8] To solve this problem, conventionally, the LiCoO 2 to dope the metal such as Al, Ti, Mg, Zr, or, LiCoO 2 a technique for coating a metal such as Al, Ti, Mg, Zr on the surface of the often used, but , this prior art are disclosed there, and all only method for doping the doping elements within ~ 50ppm 8000ppm, there was a problem not still maintaining structural integrity in a high voltage in excess of 4.5V, if the coating layer made of the metal, during the charge and discharge Li interfere with the movement of ions or, LiCoO 2 by reducing the capacity, and even reduced the performance of the secondary battery, there is still a problem with the reliability and service life characteristics at high temperature and high voltage. [9] Thus, the situation with high life characteristics even under high temperature environment and high-voltage high, the need for the enhanced lithium cobalt oxide-based positive electrode active material of development stability. [10] Detailed Description of the Invention SUMMARY [11] An object of the present invention is to solve the technical problem, which has been requested from the problems, and of the prior art. [12] The inventors of the present application are at the end of extensive research and various experiments in depth, as will be described later, contains lithium-cobalt doped oxide and a shell lithium cobalt doped oxide, each independently of three kinds of dopants doped in the core, the dopants are leading to the case that a certain condition is met, improves the structural stability of the crystal structure in the operating voltage range of 4.5V exceeds the crystal structure is maintained bar, completed the present invention finding exhibits a high high-voltage characteristics. [13] Problem solving means [14] Accordingly, the secondary battery positive electrode active material according to the invention, the core-as cathode active material for a lithium secondary battery including a lithium cobalt oxide in the doped shell structure, [15] Lithium cobalt oxide doped with a lithium cobalt oxide doping of the core and the shell is characterized in that it satisfies each of the following, and each comprise three kinds of dopants independently (a) or (b). [16] (I) satisfies the following conditions, the ratio of an average oxidation number (1) of the dopant present in the average oxidation number, and a shell of dopant present in the core, or; [17] 0.7 ≤ t (percentage) = OC / OS <0.95 (1) [18] Here, the OC is the average oxidation state of the dopant present in the core, OS is the average oxidation state of the dopant present in the shell. [19] (Ii) a dopant for the core are, +2 metal (M1), a +3 metal (M2), and +4 metal (M3) in the oxidation state of the oxidation number of oxidation states, the amount of the M1, M2, and M3 It is, satisfies the following conditions (2), based on the molar ratio; ', And the M1 dopant of said shells, +2 metal (M1'), a +3 metal (M2 in the oxidation number "), and +4 metal (M3), the oxidation number of oxidation states, M2 ', and M3 the content of the "satisfy the following condition (3), based on the molar ratio. [20] 2 ≤ r (molar ratio) = CM1 / (CM2 + CM3) ≤ 3 (2) [21] 0.5 ≤ r '(molar ratio) = CM1' / (CM2 '+ CM3') <2 (3) [22] Here, the content of M1 is CM1, CM2 is the content of M2, CM3 is the content of M3, CM1 'is M1' content, CM2 and the content "of the M3 'content, the CM3' is M2 '. [23] As a general positive electrode active material when using lithium cobalt oxide for the cell drive of 4.35V, 4.4V, 4.45V at a high voltage, a lithium cobalt oxide is doped, such as Al, Ti, Zr, Mg, P, Ca, F, Co or as a coating hayeoteotda implement structural durability and surface stability at a high voltage environment. Specifically, lithium cobalt oxide is an essential characteristic as Li x CoO 2 in the in the x <50 situation Co 3 + is Co 4 + , small Co as oxide to the 4 + increases the structural stress due to the ionic radius of, and continues to When reduced to the vicinity of x = 20 and by filling a structural change in the structure occurs in H1-3 O3 in structure from the coin half-cell reference voltages 4.53V area. These structural changes are identified becomes a disadvantage of the efficiency, the discharge rate characteristics and life characteristics in the stand over 4.55V as occurs during the charge and discharge irreversible. Of course, in the conventional cell 4.2V 4.45V jyeoteuna development of the charge-discharge place without significant change seobuteo O3 structure (of course, but a change of a mono-clinic phase, which is a reversible life, there is no influence), at least 4.5V battery in order to drive a problem arises to prevent structural changes of the above H1-3. [24] Thus, at the end of extensive study in depth the inventors of the present invention are the core-as lithium cobalt doped oxide of the shell structure, the lithium cobalt doped lithium cobalt doped oxide of the oxide and the shell of the core are three kinds of dopants, each having a different oxidation number branches while satisfying the conditions (1) to adjust their average oxidation number so that it has an average oxidation number ratio of the scope of the dopant doped in the core and the shell, or by adjusting the content ratio of the dopant condition (2) and (3) when the to meet, the high temperature, has been found that by suppressing the change in the surface structure under the high voltage improves the structural stability of the positive electrode active material particle by the life characteristic is remarkably improved. [25] In the context of this application, the drive voltage is written to the half-coin-cell basis. [26] Here, when the t (percentage) is to get out of range of the condition (1), wherein r (molar ratio), or r '(molar ratio) is out of the condition 2 or the condition (3), a lot of changes in the non-reversible crystal structure It takes place, and thus also in the life characteristic disadvantage appears bars, can not be obtained an effect of the present invention desired. [27] More specifically, t (percentage) of the condition (1) is an r (molar ratio) of 0.8 ≤ t [113] MgO 4mol, Al 2 O 3 1mol, TiO 2 1mol composition of to Co 3 O 4 , and Li 2 CO 3 , dry the mixed, then, firing at 1050 in a furnace for 10 hours, the Mg, Al, Ti-doped lithium cobalt doped oxide Li 1 . 02 Co 0 . 94 Mg 0 . 04 Al 0 . 01 Ti 0 . 01 O 2 was prepared. [114] [115] [116] 0.6mol MgO, Al 2 O 3 4mol, TiO 2 1mol of the composition to Co 3 O 4 , Li 2 CO 3 with a dry mixed, then, firing at 1050 in a furnace for 10 hours, the Mg, Al, Ti-doped lithium cobalt doped oxide Li 1 . 02 Co 0 . 944 Mg 0 . 006 Al 0 . 04 Ti 0 . 01 O 2 was prepared. [117] [118] [119] Co 3 (SO 4 ) 4 , magnesium sulfate (MgSO 4 ), aluminum sulfate (Al 2 (SO 4 ) 3 ), sulfuric acid, titanium (Ti (SO 4 ) 2 a) Co: Mg: Al: Ti = 0.94: 0.04: 0.01: was dispersed in a mixed aqueous solution mixed with 0.01, by co-precipitation with sodium hydroxide (Co 0 . 94 Mg 0 . 04 Al 0 . 01 Ti 0 . 01 ) (OH) 2 to obtain the precursor particles. [120] The molar ratio of the total of elemental particles in the precursor 100g Li: M (Co, Mg , Al, Ti) = 1.02: LiOH.H such that the molar ratio of 1 2 was added to O 41g were mixed using a ball mill with zirconia balls the mixture to primary firing at a high temperature 12 hours under an air atmosphere at 1010 Mg, Al, lithium cobalt oxide doped with Ti-doped Li 1 . 02 Co 0 . 94 Mg 0 . 04 Al 0 . 01 Ti 0 . 01 O 2 was prepared. [121] [122] [123] 3mol MgO, Al 2 O 3 0.4mol, TiO 2 0.2mol, Co 3 O 4 , and Li 2 CO 3 with a dry mixed, then, firing at 1050 in a furnace for 10 hours, the Mg, Al, Ti-doped lithium cobalt doped oxide Li 1.02 Co 0.964 Mg 0.03 Al 0.004 Ti 0.002 O 2 was prepared. [124] [125] [126] 3mol MgO, Al 2 O 3 0.5mol, TiO 2 0.5mol, Co 3 O 4 and Li 2 CO 3 , dry mixed, then, firing at 1050 in a furnace for 10 hours, Mg, Al, Ti-doped lithium cobalt doped oxide Li 1.02 Co 0.96 Mg 0.03 Al 0.005 Ti 0.005 O 2 was prepared. [127] [128] [129] 0.5mol MgO, Al 2 O 3 1mol, TiO 2 0.5mol, Co 3 O 4 and Li 2 CO 3 , dry mixed, then, firing at 1050 in a furnace for 10 hours, Mg, Al, Ti-doped lithium cobalt doped oxide Li 1.02 Co 0.98 Mg 0.005 Al 0.01 Ti 0.005 O 2 was prepared. [130] [131] [132] Co 3 (SO 4 ) 4 , magnesium sulfate (MgSO 4 ), aluminum sulfate (Al 2 (SO 4 ) 3 ), sulfuric acid, titanium (Ti (SO 4 ) 2 a) Co: Mg: Al: Ti = 0.96: 0.03: 0.005: dispersed in a mixed aqueous solution mixed with 0.005 and, by co-precipitation with sodium hydroxide (Co 0 . 96 Mg 0 . 03 Al 0 . 005 Ti 0 . 005 ) (OH) 2 to obtain the precursor particles. [133] The molar ratio of the total of elemental particles in the precursor 100g Li: M (Co, Mg , Al, Ti) = 1.02: LiOH.H such that the molar ratio of 1 2 was added to O 41g were mixed using a ball mill with zirconia balls the mixture to primary firing at a high temperature 12 hours under an air atmosphere at 1010 Mg, Al, lithium cobalt oxide doped with Ti-doped Li 1 . 02 Co 0 . 96 Mg 0 . 03 Al 0 . 005 Ti 0 . 005 O 2 was prepared. [134] [135] [136] 1.3mol MgO, Al 2 O 3 0.1mol, TiO 2 0.2mol, Co 3 O 4 and Li 2 CO 3 with a dry mixed, then, firing at 1050 in a furnace for 10 hours, the Mg, Al, Ti-doped lithium cobalt doped oxide Li 1.02 Co 0.984 Mg 0.013 Al 0.001 Ti 0.002 O 2 was prepared. [137] [138] [139] Preparative Example 1 is manufactured by doping the lithium cobalt oxide and 200 g mol Mg0.6, Al 2 O 3 1mol, TiO 2 1mol, Co 3 O 4 and Li 2 CO 3 after the dry mixing, 10 hours at 950 in a furnace during firing, Mg, Al, lithium cobalt oxide doped with Ti-doped Li 1.02 Co 0.944 Mg 0.006 Al 0.04 Ti 0.01 O 2 is Li 1 . 02 Co 0 . 94 Mg 0 . 04 Al 0 . 01 Ti 0 . 01 O 2 core formed in the core, was prepared the positive electrode active material of the shell structure. [140] [141] [142] The embodiment in the lithium cobalt doped oxide prepared in 1 the average particle diameter is 50 nm of Al 2 O 3 and the relative to the positive electrode active material, the total mass of more than 0.05 wt% and mixed for at 570 six hours secondary firing, the aluminum 500 ppm a coating layer was formed. In this case, the aluminum coating layer was formed in an average thickness of approximately 50 nm. [143] [144] [145] Preparative Example The lithium cobalt oxide-doped 200 g prepared from the 5 and, 3mol MgO, Al 2 O 3 0.5mol, TiO 2 0.5 mol, Co 3 O 4 and Li 2 CO 3 and then dry mixing, at 950 in the furnace 10 baked for a time is Mg, Al, Ti-doped lithium cobalt oxide doped with Li 1.02 Co 0.977 Mg 0.008 Al 0.01 Ti 0.005 O 2 is Li 1 . 02 Co 0 . 96 Mg 0 . 03 Al 0 . 005 Ti 0 . 005 O 2 core formed of the core-shell structure of the cathode active material was prepared. [146] [147] [148] The embodiment having an average particle diameter of 50 nm of Al in the lithium cobalt doped oxide prepared in Example 3 2 O 3 by firing during the after adding 0.05% by weight, based on the positive electrode active material total mass mix 570 6 hours Second, aluminum 500 ppm a coating layer was formed. In this case, the aluminum coating layer was formed in an average thickness of approximately 50 nm. [149] [150] [151] Preparative Example 1 is manufactured by doping the lithium cobalt oxide and 200 g mol Mg0.4, Al 2 O 3 1mol, TiO 2 2mol, Co 3 O 4 and Li 2 CO 3 after the dry mixing, 10 hours at 950 in a furnace during firing, Mg, Al, lithium cobalt oxide doped with Ti-doped Li 1.02 Co 0.944 Mg 0.004 Al 0.01 Ti 0.02 O 2 is Li 1 . 02 Co 0 . 94 Mg 0 . 04 Al 0 . 01 Ti 0 . 01 O 2 core formed in the core, was prepared the positive electrode active material of the shell structure. [152] [153] [154] Preparative Example 2 A lithium cobalt doped oxide 200 g and manufactured, MgO 0.076 g, Al 2 O 3 0.267 g, TiO 2, 0.43 g, Co 3 O 4 50 g, and Li 2 CO 3 20.475 g, and then the dry mixture and fired in a furnace at 950 for 10 hours, Mg, Al, lithium cobalt oxide doped with Ti-doped Li 1.02 Co 0.957 Mg 0.013 Al 0.02 Ti 0.01 O 2 is Li 1 . 02 Co 0 . 944 Mg 0 . 006 Al 0 . 04 Ti 0 . 01 O 2 core formed in the core, was prepared the positive electrode active material of the shell structure. [155] [156] [157] Preparative Example 4 and lithium cobalt oxide-doped 200 g prepared, 0.07 g MgO, Al 2 O 3 0.53 g, TiO 2 -1.73 g, Co 3 O 4, 50 g, and Li 2 CO 3 20.475 g of dry mixing one after that, by firing in a furnace at 950 for 10 hours Al, the Ti is doped with lithium cobalt oxide doped with Li 1.02 Co 0.908 Mg 0.012 Al 0.04 Ti 0.04 O 2 is Li 1 . 02 Co 0 . 964 Mg 0 . 03 Al 0 . 004 Ti 0 . 002 O 2 core formed of the core-shell structure of the cathode active material was prepared. [158] [159] [160] Preparative Example 6 as the lithium cobalt doped oxide 200 g manufactured, MgO 0.48 g, Al 2 O 3 0.13 g, TiO 2 0.216 g, Co 3 O 4 50 g, and Li 2 CO 3 20.475 g, and then the dry mixture and fired in a furnace at 950 for 10 hours, Mg, Al, lithium cobalt oxide doped with Ti-doped Li 1.02 Co 0.97 Mg 0.02 Al 0.005 Ti 0.005 O 2 is Li 1 . 02 Co 0 . 98 Mg 0 . 005 Al 0 . 01 Ti 0 . 005 O 2 core formed of the core-shell structure of the cathode active material was prepared. [161] [162] Table 1 shows the average oxidation number (up to the first decimal-old), and the ratio of the doping element of the Examples 1-4, and Comparative Examples 1 to 4. [163] [164] TABLE 1 OC THE t Example 1 2.5 3.1 0.81 Example 2 2.5 3.1 0.81 Example 3 2.4 2.9 0.83 Example 4 2.4 2.9 0.83 Example 5 2.5 3.5 0.72 Comparative Example 1 3.1 2.9 1.07 Comparative Example 2 2.2 3.3 0.67 Comparative Example 3 3 2.5 1.2 [165] [166] Table 2 and 3 shows the content and the content ratio of the doping element in Example 1 to 4 and Comparative Examples 1 to 4. [167] [168] TABLE 2 CM1 CM2 CM3 r Example 1 4 1 1 2 Example 2 4 1 1 2 Example 3 3 0.5 0.5 3 Example 4 3 0.5 0.5 3 Example 5 4 1 1 2 Comparative Example 1 0.6 4 1 0.12 Comparative Example 2 3 0.4 0.2 5 Comparative Example 3 0.5 1 0.5 0.33 [169] [170] TABLE 3 CM1' CM2' CM3' r' Example 1 0.6 4 1 0.12 Example 2 0.6 4 1 0.12 Example 3 0.8 1 0.5 0.53 Example 4 0.8 1 0.5 0.53 Example 5 0.4 1 1 0.2 Comparative Example 1 1.3 2 1 2.3 Comparative Example 2 1.2 4 4 0.15 Comparative Example 3 2 0.5 0.2 2.85 [171] [172] [173] Example 1 and 3, and compare the use of the oxide particles prepared in Examples 1 to 4 as a positive electrode active material, natural graphite was used as a conductive material and PVdF as a binder. The positive electrode active material: binder: a conductive material in the weight ratio 96: 2: gave mixed well in NMP such that the second was coated on Al foil having a thickness of 20 ㎛ and dried at 130 to positive electrode was prepared. The cathode is a lithium foil, EC: DMC: DEC = 1 : 2: 1 1M of LiPF in the solvent 6 were prepared half coin cells using the electrolytic solution containing the. [174] Had a half coin cells prepared above, with an upper limit voltage with 0.5C to 4.55V at 25, respectively, and by filling cycle once to discharge to a lower limit voltage of 3V to 1.0C again, measuring the capacity maintenance rate of 50 cycles, the the results are shown in Figure 1a and 1b. [175] When Fig. 1a and FIG. 1b, the capacity maintenance rate of the battery using the embodiment of the positive electrode active material according to the present invention the capacity of the battery using the positive electrode active material of Comparative Example can not, satisfaction any conditions relative to represent the retention ratio of 90% or more capacity retention was not life property up to about 85% is not good, embodiments which satisfy the conditions of the present invention, examples of which can know the offered better high-voltage high-temperature life characteristics, which can be expected that the difference is accelerated the more cycle is in progress . [176] Above has been described with reference to embodiments of the invention, those skilled in the art that the invention would be possible that various and modifications within the scope of the invention as disclosed in the accompanying claims. [177] Industrial Applicability [178] As described above, the positive electrode active material according to the invention, each independently doping are three kinds of dopants in the lithium-cobalt-doped lithium cobalt doped oxide of the oxide and the shell of the core, to an average oxidation number ratio of the doped dopant of claim 1 condition (1) is an improved structural stability of the crystal structure in the operating voltage range of 4.5V by more than satisfies the effect that the crystal structure is maintained bar indicates high voltage properties, life property improves to maintain structural stability at high temperatures have. Claims [Claim 1]The core-to as a cathode active material for a lithium secondary battery including a lithium cobalt doped oxide of the shell structure, and lithium-cobalt-doped lithium cobalt doped oxide of the oxide and the shell of the core comprises three kinds of dopants, each independently from each other, (a) or (b) the positive electrode active material which satisfies: (a) satisfies the following conditions, the ratio of an average oxidation number (1) of the dopant present in the average oxidation number, and a shell of dopant present in the core, or; 0.7 ≤ t (percentage) = OC / OS <0.95 (1) Here, the OC is the average oxidation state of the dopant present in the core, OS is the average oxidation state of the dopant present in the shell. (B) a dopant for the core are, +2 metal (M1), a +3 metal (M2), and +4 metal (M3) in the oxidation state of the oxidation number of oxidation states, the amount of the M1, M2, and M3 It is, satisfies the following conditions (2), based on the molar ratio; ', And the M1 dopant of said shells, +2 metal (M1'), a +3 metal (M2 in the oxidation number "), and +4 metal (M3), the oxidation number of oxidation states, M2 ', and M3 the content of the "satisfy the following condition (3), based on the molar ratio. 2 ≤ r (molar ratio) = CM1 / (CM2 + CM3) ≤ 3 (2) 0.5 ≤ r '(molar ratio) = CM1' / (CM2 '+ CM3') <2 (3) Here, the CM1 is the content of M1 , CM2 is the content of M2, CM3 is the content of M3, CM1 'is M1' content, CM2 and the content "of the M3 'content, the CM3' is M2 '. [Claim 2] The method of claim 1, wherein, t (percentage) at said (i) is 0.8 ≤ t