2019/103576 1»（：1^1{2018/014725 【Name of invention】 Positive electrode additive, manufacturing method thereof, positive electrode and lithium secondary battery comprising the same 【Technical field】 Mutual citation with related application(s) This application is filed on November 27, 2017 in Korean Patent Application No. 10-2017-0159731 and It claims the benefit of priority based on Korean Patent Application No. 10-2018-0147752 filed on November 26, 2018, and all contents disclosed in the literature of the relevant Korean patent applications are included as part of this specification. The present invention relates to a positive electrode additive, a method for manufacturing the same, and a positive electrode and lithium secondary battery including the same. 【Background description】 In a lithium secondary battery, an electrode active material capable of reversible insertion and desorption of lithium ions is applied to the cathode and the anode, respectively, and the lithium ions are transferred through an electrolyte, and electrical energy is achieved by oxidation and reduction reactions at each electrode. Create By the way, during the initial charging and discharging of lithium secondary batteries, lithium ions that are inserted into the negative electrode (battery charge) and then desorbed (battery discharge) and lithium ions that cannot be recovered (battery discharged) again after being removed from the positive electrode (battery charge) are each This inevitably occurs, which is related to the irreversible capacity of the two electrodes. As the difference in irreversible capacity between the two electrodes increases, the initial efficiency of the positive electrode decreases, and the energy density during driving of the battery gradually decreases, thereby reducing the battery life. 【Detailed description of the invention】 【Technical task】 In one embodiment of the present invention, there is provided a positive electrode additive capable of canceling the irreversible capacity imbalance of the two electrodes, increasing the initial charging capacity of the positive electrode, and suppressing the generation of gas in the battery. 【Technical solution】 2019/103576 Advantages and features of the embodiments of the present invention, and a method of achieving them, will become apparent with reference to the embodiments described below in detail. However, the present invention is not limited to the embodiments disclosed below, but may be implemented in various forms different from each other, and only these embodiments make the disclosure of the present invention complete, and are common in the technical field to which the present invention pertains. It is provided to fully inform those skilled in the art of the scope of the invention, and the invention is only defined by the scope of the claims. Unless otherwise defined, technical terms and scientific terms used in the present invention have meanings that are commonly understood by those of ordinary skill in the art to which this invention belongs. In addition, it has the same technical configuration and operation as in the prior art. Repeated explanations for this will be omitted. In the entire specification of the present application, when a part is said to be “connected” with another part, this includes not only the case that it is “directly connected” but also the case that it is “electrically connected” with another element in the middle. do. Throughout this specification, when a member is positioned “on” another member, this includes not only a case where a member is in contact with another member, but also a case where another member exists between the two members. Throughout the present specification, when a part "includes" a certain component, it means that other components may be further included rather than excluding other components that do not have a specific contrary description. The terms "about", "substantially", etc. of the degree used throughout the specification of the present application are used in or close to the numerical value when manufacturing and material tolerances specific to the stated meaning are presented, To assist, accurate or absolute figures are used to prevent unfair use of the stated disclosure by unconscionable infringers. The term of degree are used throughout the present specification, "- (a) step" or steps " is " ~ step for " do not mean . In the entire specification of the present application, the term "combination (s)" included in the expression of the Makushi form means a mixture or combination of one or more selected from the group consisting of components described in the expression of the Makushi form, The above configuration 2019/103576 1»（：1^1{2018/014725 It means to include one or more selected from a group of elements. In the entire specification of the present application, the description of "show and/or 3" means "show or 3, or show and 8". Anode additive In one embodiment of the present invention, the entire composition is represented by the following formula (1) core; And it is located on the surface of the core, and provides a coating layer containing a) compound; containing, a positive electrode additive: [Formula 1] ｛，凡+ My Girlfriend｝ ·切（New 0）｝ ·｛7（½0）｝ In Formula 1, M is one or more metal elements that form a divalent cation or a trivalent cation, for example, and may be one or more metal elements selected from the group including and, and is -0.2£show0.2, and 0.5< 1)<1.0, -0.2致£0.2, 0.7<)｛<1.0, 0今<0.15, and 0 ¾¾ ( ¾02 (wherein 0.90 <& <1.8, 0 <1? <0.9, 0 <(： £ 0.5 and 0.001 <(1 <0.1.); In the above formula, 0.90 < & <1.8, 0 <<0.9, 0 <0 <0.5, 0 me) , Hexaphosphate triamide, nitrobenzene derivative, sulfur, quinone imine dye, N-substituted oxazolidinone, N,N-substituted imidazolidine, ethylene glycol dialkyl ether, ammonium salt, pyrrole, 2-methoxy ethanol, trichloride Aluminum may be added. In some cases, a halogen-containing solvent such as carbon tetrachloride or ethylene trifluoride may be further included to impart non-flammability, or carbon dioxide gas may be further included to improve high-temperature storage characteristics. In addition, FEC (Fluoro-Ethylene Carbonate), PRS (Propene sultone), etc. may be further included. In one specific example, lithium salts such as LiPF 6, LiC10 4, LiBF 4 and LiN(S0 2 CF 3) 2 are used as a linear carbonate of EC or PC as a highly dielectric solvent and DEC, DMC or EMC as a low viscosity solvent. The non-aqueous electrolyte containing a lylium salt can be prepared by adding it to a mixed solvent of carbonate. The lithium secondary battery of the embodiment may be implemented as a battery module including the same as a unit cell, a battery pack including the battery module, and a device including the battery pack as a power source. At this time, a specific example of the device may be an electric vehicle, a hybrid electric vehicle, a plug-in hybrid electric vehicle, or a power storage system, but is not limited thereto. 【Effects of the Invention】 In the lithium secondary battery to which the positive electrode additive of one embodiment is applied to the positive electrode, the initial irreversible capacity of the negative electrode is decreased, the initial capacity and efficiency of the positive electrode are effectively increased, and the decrease in energy density during driving is suppressed, so that the lifespan characteristics are excellent. have. 【Simple explanation of the drawing】 1 is for each lithium secondary battery of Preparation Examples 1 to 3, and Comparative Example 1 2019/103576 1»（：1^1{2018/014725 This is a graph showing the initial charge and discharge characteristics. Fig. 2 is a graph showing the amount of gas generated according to the charge/discharge orders (1 to 4 & 0 (added)) for each of the cells of Examples 1 to 8 and each of the cells of Preparation Examples 1 to 3 and Comparative Example 1 . . 3 is a graph recorded by measuring initial (1) charge/discharge characteristics for each of the cells of Examples 1 to 8 and each of the cells of Production Examples 1 to 3 and Comparative Example 1. FIG. 4 is a graph recorded by measuring initial (1 charge/discharge characteristics and long-term charge/discharge (~200*) characteristics for each of the batteries of Comparative Examples 2 to 4 and Examples 7 and 8). 【Forms for the implementation of the invention】 Hereinafter, the action and effect of the invention will be described in more detail through specific examples of the invention. However, this is presented as an example of the invention, and the scope of the invention is not limited by any meaning. 1. Lilium Nickel Oxide, Nickel Oxide 0 0), and Litum Oxide 0, Check the benefits of cores containing them ＜Production Example 1:｛（1] 2] '410 2）｝-｛＞ 0》｝ .｛2（1^ 20）｝, table= 0.86, l= 0.07, 1= 0.07, table (1) Manufacturing of core Ni (OH) 2 , a nickel hydroxide precursor, was heat-treated for 10 hours in an inert atmosphere of 600 X: to obtain a nickel-based oxide 0. The nickel-containing oxide new 0 Lyrium oxide (1山0) and 1: bolbi (0 of 1.1 : 20 ) mixed in, and 680 ° (:. In (inert atmosphere) was heat-treated for 18 hours At this time, heating and cooling The speed was fixed at 5°0 per minute. After the above heat treatment is over, b (knee 2 sha 0 2）｝_｛5＜ 0)｝ ｛2（0 20）｝, = 0.86, 0.07, 2= 0.07 was finally obtained, and this was taken as Production Example 1. The above formula is calculated from Experimental Example 1 to be described later. (2) Manufacture of anode and lithium secondary battery (coin half cell) A positive electrode was manufactured by applying the core of Preparation Example 1 as a positive electrode additive, and a lylium secondary battery including the prepared positive electrode was manufactured. Specifically, the core (anode additive) of Preparation Example 1 {o .86( Li 2 Ni0 2))· {0.07 N10}-{o . o 7 U 2 0}, a conductive material (Super-P, Denka Black) and a binder (PVdF) were mixed in an organic solvent (NMP) in a weight ratio of 85: 10: 5 (anode additive: conductive material: binder), After preparing a slurry-like positive electrode mixture, the positive electrode mixture was coated on an aluminum current collector and dried in a vacuum oven at 120 °C for 30 minutes to prepare a positive electrode. Lithium metal (Li-metal) is used as the counter electrode, and ethylene carbonate (EC, Ethylene Carbonate): dimethyl carbonate (DMC, Demethyl Carbonate) was dissolved in a solution of 2% by weight of VC in a mixed solvent having a volume ratio of 1:2. Each of the above components was used, and a 2032 half coin cell was manufactured according to a conventional manufacturing method. (1) Preparation of core Except for the mixing of the nickel-based oxide Ni◦ and the lylium oxide (Li 20) in a molar ratio of 1:1.2, the rest were the same as in Preparation Example 1, { x( Li 2 Ni0 2)} {y( Ni0)} { z( Li 20)}, x= 0.80, y= 0.10, z= 0.10 were obtained, and this was used as the core of Preparation Example 2 (anode additive). . The formula is calculated from Experimental Example 1 described later. (2) Manufacture of positive electrode and lithium secondary battery (coin half cell) Except that the core of Preparation Example 2 (anode additive) was used instead of the core of Preparation Example 1 (anode additive), the remainder of the positive electrode and lithium secondary battery of Preparation Example 2 were manufactured in the same manner as Preparation Example 1. (1) manufacture of core Except that the nickel-based oxide NiO was mixed with lithium oxide (Li 20) in a molar ratio of 1:1.3, the rest were the same as in Preparation Example 1, { x( Li 2 Ni0 2)} {y( Ni0) } { z ( Li 20 )}, x = 0.76, y = 0.12, z = 0.12 was obtained, and the above formula is an experimental example to be described later It is calculated from 1. (2) Manufacture of anode and lithium secondary battery (coin half cell) Except that the core of Preparation Example 3 (positive electrode additive) was used instead of the core of Preparation Example 1 (anode additive), the remainder of the positive electrode and lithium secondary battery of Preparation Example 3 were manufactured in the same manner as Preparation Example 1 . (1) Preparation of positive electrode additive After preparing the positive electrode additive prepared in the same manner as in Preparation Example 1, the unreacted nickel oxide NiO and litum oxide () were filtered through a sieve of 400 mesh, and the space group was Irrnnm. (Orthorhombic) x ( Li 2 Ni0 2) having a crystal structure , x = 0.86 was finally obtained, which was used as the positive electrode additive of Comparative Example 1. (2) Manufacture of anode and lithium secondary battery (coin half cell) Except for the fact that the positive electrode additive of Comparative Example 1 was used instead of the positive electrode additive of Preparation Example 1, the remainder of the positive electrode and lithium secondary battery of Comparative Example 1 were manufactured in the same manner as Preparation Example 1. For each core (positive electrode additive) of Preparation Examples 1 to 3 and Comparative Example 1, Cu Ka XRD (X-Ray Diffraction) analysis by X-ray (Xm) was performed, and the results are recorded in Table 1 below. Specifically, lithium nickel oxide and the nickel oxide (NiO) are crystalline and can be detected by XRD (X-Ray Diffiaction) by Fe Ka X-ray (X-ra). In particular, the quantitative analysis was obtained through XRD (X-Ray Diffiaction) immediate post intensity (intensity) calculation. [Table 1] In Comparative Example 1, it is already known that the point group has an orthorhombic crystal structure of Immm. However, from the result of the structural analysis in Table 1, Comparative Example 1 and Preparation Examples 1 to 3 It can be seen that it has the same crystal structure. Accordingly, it can be seen that Preparation Examples 1 to 3 also include a compound represented by Li 2+a Ni b M b02+c . From the results of the quantitative analysis in Table 1 , it can be confirmed that Li 20 was not detected in Comparative Example 1. However, in Preparation Examples 1 to 3, 7% by weight of the total amount (100% by weight) (Production Example 1), 10 In weight% (Production Example 2) and 12% by weight (Production Example 3), it can be confirmed that Li 2 ◦ was detected , respectively . < Experimental Example 2: Evaluation of initial charge/discharge characteristics of a battery in which the core was applied as an anode additive> For each of the cells of Preparation Examples 1 to 3 and Comparative Example 1, the initial charge/discharge characteristics were evaluated under the following conditions. The evaluation results are reported in FIG. 1 and Table 2 below. Charge: 0.1C, CC/CV, 4.25 V, 0.05C cut-off Discharge: 0.1C, CC, 2.5 V, cut-off According to FIG. 1 and Table 2 below, compared to Comparative Example 1, it can be seen that the initial irreversible capacity of the negative electrode in Preparation Examples 1 to 3 decreased, and the initial efficiency of the positive electrode increased. [Table 2] In Preparation Examples 1 to 3, in order to confirm the effect of improving the initial performance of the battery by the core in the positive electrode additive of one embodiment, a positive electrode mixture was prepared by using each positive electrode additive in the same amount as a conventional positive electrode active material. And lithium secondary batteries were manufactured. As described above, the core irreversibly releases lylium ions and oxygen at ° before initial charging of the battery, for example 2.5 to 4.25 V (VI 0/0+), and then reversibly intercalates lithium ions. And it can be converted into a composition capable of desorption. Accordingly, as in Preparation Examples 1 to 3, the additive core may be used as an additive for compensating the initial irreversible capacity of the negative electrode, and as an active material that enables reversible insertion and desorption of lithium. However, because of the U content and its structural limitations, it may have a small reversible capacity compared to a conventional positive electrode active material. Therefore, in the case of improving the initial performance of the battery and securing long-term life characteristics, depending on the desired battery characteristics , With the positive electrode additive of one embodiment including the core, the positive electrode active material may be mixed and used at an appropriate mixing ratio. II. Identification of the advantages of positive electrode additives including core and phosphorus compound coating layers including lithium oxide nickel oxide, nickel oxide 10), and lithium oxide (I山) (1) Preparation of positive electrode additive All the processes were the same as in Preparation Example 1, and { x( Li 2 Ni0 2)} { y(Ni0)} _{z(Li 20)}, x= 0.86, y= 0.07, z= 0.07 was finally obtained. And, this was used as the core of Example 1. The core of Example 1 and ammonium phosphate (ammonium phosphate, NH 4 H 2 P0 4) were mixed, and the mixture was heat-treated in an inert atmosphere of 700 for 10 hours to obtain the positive electrode additive of Example 1. However, at the time of mixing, the first ammonium phosphate was made to be 2000 ppm with respect to the total amount of the mixture. (2) Manufacture of anode and lithium secondary battery (coin half cell) Except for the fact that the positive electrode additive of Example 1 was used instead of the core of Preparation Example 1 (positive electrode additive), the remainder of the positive electrode and lithium secondary battery of Example 1 were prepared in the same manner as Preparation Example 1. (1) Preparation of positive electrode additive When mixing the core of Example 1 with the first ammonium phosphate, with respect to the total amount of the mixture, except for the point that the first ammonium phosphate was 500 ppm, the rest were the same as in Example 1, and the positive electrode additive of Example 2 Obtained. (2) Manufacture of anode and lithium secondary battery (coin half cell) Except that the positive electrode additive of Example 2 was used instead of the positive electrode additive of Example 1, the remainder of the positive electrode and lithium secondary battery of Example 2 were manufactured in the same manner as in Example 1. (1) Preparation of positive electrode additive When mixing the core of Example 1 with the first ammonium phosphate, with respect to the total amount of the mixture, except for the point that the amount of the first ammonium phosphate is 4000 ppm, the rest are in Example 2019/103576 1»（：1^1{2018/014725 In the same manner as in 1, the positive electrode additive of Example 3 was obtained. (2) Manufacture of anode and lylium secondary battery (coin half cell) Except that the positive electrode additive of Example 3 was used instead of the positive electrode additive of Example 1, the remainder of the positive electrode and lithium secondary battery of Example 3 were manufactured in the same manner as in Example 1. (1) Preparation of positive electrode additive When mixing the core of Example 1 with the first ammonium phosphate, with respect to the total amount of the mixture, the first ammonium phosphate was 8,000 , except for the point, and the rest were the same as in Example 1 to obtain the positive electrode additive of Example 5. I did. (2) Manufacture of anode and lylium secondary battery (coin half cell) Except that the positive electrode additive of Example 5 was used instead of the positive electrode additive of Example 1, the remainder of the positive electrode and lithium secondary battery of Example 5 were manufactured in the same manner as in Example 1. (1) Preparation of positive electrode additive In the same manner as in Example 1, except that the core of Preparation Example 2 was used instead of Preparation Example 1, the positive electrode additive of Example 7 was obtained. (2) Manufacturing of anode and retum secondary battery (coin half cell) Except that the positive electrode additive of Example 7 was used instead of the positive electrode additive of Example 1, the remainder of the positive electrode and lithium secondary battery of Example 7 were manufactured in the same manner as in Example 1. (1) Preparation of positive electrode additive Except that the core of Preparation Example 3 was used instead of Preparation Example 1, the rest were the same as those of Example 1 to obtain the positive electrode additive of Example 8. (2) Manufacture of anode and lithium secondary battery (coin half cell) Except that the positive electrode additive of Example 8 was used instead of the positive electrode additive of Example 1, the remainder of the positive electrode and lithium secondary battery of Example 8 were manufactured in the same manner as in Example 1. For the positive electrode additive of Example 1, through XPS analysis, XPS analysis was performed to determine whether a coating layer was formed on the surface of the core of Preparation Example 1 and, if so, what its components were. More specifically, for the positive electrode additive of Example 1, as a result of the immediate binding energy (Binding Energy) by XPS analysis, the peak at about 134 eV was blackened. This is the binding energy of Li 3 P0 4 widely known in the art ( Binding Energy). Therefore, the positive electrode additive of Example 1 , through a coating layer forming process using NH 4 H 2 P0 4 as a coating raw material, LiOH and NH 4 H 2 P0 4, which is a lylium by-product present on the core surface of Preparation Example 1, reacted. It can be seen that a coating layer containing Li 3 P0 4 is formed on the surface of the core . Here, only the positive electrode additive of Example 1 was confirmed, but Examples 2 to 8 using the same raw materials and processes as in Example 1 were also formed on the surface of each core with a coating layer of the same components as in Example 1, but only the coating amount It is inferred to be different. For each of the positive electrode additives of Examples 1 to 8 and each of the cores of Preparation Examples 1 to 3 and Comparative Example 1, the initial pH and the Li byproduct and content remaining on the surface were immediately determined. The measurement results are shown in Table 3 below. However, in the measurement, the initial pH was a pH titration method, 10 g of each positive electrode additive was added to 100 ml of H 20 , stirred for 5 minutes, and then 0.1N HC1 titration was performed. Based on the initial inflection point during pH titration, the amount of the base portion was measured as the content of LiOH, and the content of the total Li by-product was measured respectively, and the value obtained by subtracting the content of LiOH from the content of the total Li by-product was Li It was calculated as the 2 C0 3 content. Here, each content represents each content of 011 and 1山0¾, and the total amount of these lylium by-products, based on the total amount (100% by weight) of the positive electrode additive or the core. Table 3] 2019/103576 1»(：1/10公018/014725 From Table 3 above, as the amount of Li 20 in the core increases, the lithium by-product content increases, but it can be seen that by forming a phosphorus) compound like each of the anode additives of Examples 1 to 8, the lithium by-product can be reduced. Furthermore, in Examples 1 to 8, it can be seen that as the coating amount of the phosphorus) compound increases, the ritum by-product is more effectively reduced. For each of the cells of Examples 1 to 8 and each of the cells of Preparation Examples 1 to 3 and Comparative Example 1, the initial (1 st cycle) The amount of gas generated during charging and the amount of gas generated according to the charge/discharge order (l st ~ 4 th cycle) were measured. Specifically, electrochemical mass spectrometry. (Differential electrochemical mass spectrometer, DEMS) was used to measure the gas pressure emitted when each battery was charged in real time. Charge: 0.1 C, CC/CV, 4.25 V, 0.05C cut-off Discharge: 0.1C, CC, 2.5 V， cut-off The measurement results are shown in Table 4 below and shown in FIG. 2. [Table 4] For each of the cells of Examples 1 to 8 and each of the cells of Preparation Examples 1 to 3 and Comparative Example 1, the following conditions were initially used. The charge and discharge characteristics were evaluated. The evaluation results are recorded in Fig. 3 and Table 5 below. Charge: 0.1C, CC/CV, 4.25V, 0.05C cut-off Discharge: 0.1C， CC, 2.5 V, cut-off According to Table 5 below, compared to Comparative Example 1, it can be seen that the initial irreversible capacity of the negative electrode in Preparation Examples 1 to 3 decreased and the initial efficiency of the positive electrode increased. Furthermore, in preparation for Preparation Examples 1 to 3 In Examples 1 to 8, it can be seen that the initial efficiency of the positive electrode is further increased. However, if the coating content is too high, there is a possibility of reducing the initial charging capacity, and it will be necessary to control it within 500 to 9000 ppm. [Table 5] 2019/103576 1»（：1^1{2018/014725 In addition to Table 5, if a comprehensive review of Tables 3 and 4 and FIGS. 2 and 3 above, the cores of Preparation Examples 1 to 3 are voltage at the time of initial charging of the battery, for example 2.5 to By irreversibly releasing lithium ions and oxygen at 4.25 V 01 ni/0+), compared to Comparative Example 1, the initial irreversible capacity of the negative electrode was reduced and the initial efficiency of the positive electrode was increased. It can be seen that there is a limit to increasing the initial efficiency of On the other hand, in Examples 1 to 8, it can be seen that by forming a coating layer on the cores of Preparation Examples 1 to 3, the initial efficiency of the positive electrode can be further improved. This, while each of the positive electrode additives of Examples 1 to 8 has the effect of the core (i.e., decreases the initial irreversible capacity of the negative electrode, increases the initial efficiency of the positive electrode) as it is, but has the effect of removing lithium by-products by the coating layer and suppressing gas generation. Therefore, it can be seen that the initial characteristics of the battery are further improved. On the other hand, in Examples 1 to 8, in order to confirm the effect of improving the initial performance of the battery in the positive electrode additive of one embodiment, a positive electrode mixture was prepared by using each positive electrode additive in the same amount as a conventional positive electrode active material, and the positive electrode and lithium A secondary battery was prepared. However, in the case of improving the initial performance of the battery and securing long-term life characteristics, according to the desired battery characteristics, a positive electrode active material may be mixed with the positive electrode additive of one embodiment at an appropriate mixing ratio. 2019/103576 1»（：1^1{2018/014725 III. Examples of the actual application form of the anode additive including the core and phosphorus compound coating layer containing Lithum Nickel Oxide, Nickel Oxide 10) and Lithum Oxide (1止0) In a form in which the positive electrode additive of Example 1 was actually applied, a positive electrode was manufactured by applying the positive electrode additive of Example 1 together with the positive electrode active material, A lithium secondary battery including the prepared positive electrode was manufactured. Specifically, the positive electrode additive of Example 1 ｛Core: Preparation Example 1, coating amount: 200 (v ) 1]1 ), the positive electrode active material (LiNio . 8Coo . 1Mno . 1O2）, conductive material hawk -! » , Denka Black) and a binder wire were mixed within to prepare a slurry-like positive electrode mixture, and then the positive electrode mixture was coated on an aluminum current collector and dried in a vacuum oven of 120 占for 30 minutes, and Example 7 and Each anode of 8 was prepared. However, in Examples 7 and 8, the weight ratio of the positive electrode additive of Example 1: the positive electrode active material: the conductive material: the binder was 4.825:91.675:1.5:2 (Example 7) and 9.65:86.85:1.5:2.0, respectively (Example 7) Example 8). Using the anodes of Examples 7 and 8 instead of the anode of Example 1, each 2032 half-cell 0 1 0 0 1) was manufactured in the same manner as in Example 1 . No positive electrode additive was used, and the same amount of positive electrode active material as that of the positive electrode additive of Example 1 (1 () .8 (: 0 ()). 11\1|| (). 102 ), a positive electrode was manufactured in the same manner as in Example 1, and a lithium secondary battery including the prepared positive electrode was manufactured. In the form of actually applying the positive electrode additive of Preparation Example 1, a positive electrode was manufactured by applying the positive electrode additive of Preparation Example 1 together with the positive electrode active material, A recom secondary battery including the prepared positive electrode was manufactured. Specifically, the positive electrode additive (core: Preparation 1, Bare) of Preparation Example 1, the positive electrode active material NCM (LiNio.sCoo.1Mno.1O2), a conductive material (Super-P, Denka Black), and a binder (PVdF) were organically used. After mixing in a solvent (NMP) to prepare a slurry-like positive electrode mixture, the positive electrode mixture was coated on an aluminum current collector and dried in a vacuum oven at 120 for 30 minutes to prepare each positive electrode of Comparative Examples 3 and 4. However, in Comparative Examples 3 and 4, the weight ratio of the positive electrode additive of Preparation Example 1: the positive electrode active material: the conductive material: the binder was 4.825:91.67:1.5:2 (Production Example 3) and 9.65:86.85:1.5:2.0 (Production Example 1), respectively. I made it yes. Each anode of Comparative Examples 3 and 4 was used instead of the anode of Example 1, and each 2032 half coin cell was produced in the same manner as in Example 1. Specifically, charging and discharging of the batteries of Comparative Examples 2 to 4 and Examples 7 and 8 were performed under the following conditions at room temperature of 25 ° C. The results are shown in Fig. 4 and Table 6 below. Charge： 0.2C, CC/CV, 4.25V, 0.005C cut-of f Di scharge: 0.2C, CC, 2.5 V, cut-of f According to FIG. 4 and Table 6, when only the positive electrode active material was applied (Comparative Example 2), the positive electrode additive of Preparation Example 1 or the positive electrode additive of Example 1 was mixed and applied with the positive electrode active material (Comparative Examples 3 and 4). , Examples 7 and 8), it was confirmed that both the initial charging capacity and the life characteristics of the battery were improved. In addition, when the weight ratio of the additive: the active material is the same, when applying the positive electrode additive of Example 1 rather than the positive electrode additive of Preparation Example 1, it is confirmed that the initial charging capacity and life characteristics of the battery are further improved. [Table 6] 2019/103576 1»(：1^1{2018/014725 When the above results are combined with Experimental Examples 1 to 6, cores commonly applied to Comparative Examples 3 and 4, Examples 7 and 8 (lithium nickel oxide, nickel oxide (^0), and lithium oxide (nickel 20 )) Included Core) has the advantage of compensating for the initial irreversible capacity of the negative electrode and increasing the initial charging capacity of the positive electrode by irreversibly releasing lithium ions and oxygen in priority over the positive electrode active material in voltage during the initial charging of the battery. I can confirm. However, when the core is not coated, there is a limit to increase the initial efficiency of the anode due to the presence of lylium by-products, and when the core is coated with a phosphorus compound, the effect of the core (ie, decrease in the initial irreversible capacity of the cathode, anode It can be seen that the initial characteristics of the battery have been further improved since it has the effect of removing retum by-products by the coating layer and suppressing gas generation while maintaining the initial efficiency increase). Further, according to Fig. 4 and Table 6, when the number of cycles of the battery is the same, it can be seen that the capacity retention rates of Examples 7 and 8 are remarkably high compared to the capacity retention rates of Comparative Examples 2 to 4. 2019/103576 1»（：1^1{2018/014725 This difference in the capacity maintenance rate is makin even more severe the more the cycle proceeds the number of cells increase , in particular , in Comparative Example 2 of 100 cycles after driving in case of the initial capacity is maintained, only the capacity of 92.8%, 200 cycles after driving is 89.5% It can be seen that only the capacity of is maintained. On the other hand, in the case of Examples 7 and 8, compared to the respective initial capacity, it can be seen that 94.8% or more of the capacity is maintained after 100 cycles of driving, and 92.5% or more of the capacity is maintained even after 200 cycles of driving. This is one implementation. If the battery cycle proceeds in a state where the initial capacity of the positive electrode is increased by the positive electrode additive of the example, it means that the lost capacity decreases. In addition, as mentioned above, the positive electrode additive of one embodiment in the voltage during the initial charging of the battery. After irreversibly releasing lithium ions and oxygen, it is converted into a composition capable of reversible insertion and desorption of lithium ions, which means that it partially contributes to capacity realization even during the battery cycle. Further, it can be seen that the initial characteristics and long-term driving characteristics of the battery are different depending on the presence or absence of the additive surface coating under the condition that the core composition of the additive, the mixing ratio of the additive and the active material are the same. Specifically, it was confirmed that the initial characteristics and long-term driving characteristics of the battery of Example 7 were improved compared to Comparative Example 3, and the initial characteristics and long-term driving characteristics of the battery of Example 8 were improved as compared to Comparative Example 4. This is, under the condition that the core composition of the additive, the mixing ratio of the additive and the active material are the same, and when the additive surface is coated, lithium by-products ( 20 ¾, 1^011, etc.) remaining on the surface of the core are removed to generate gas in the battery. This can be seen as the effect of suppression. Meanwhile, among Examples 7 and 8, the initial charge capacity and life characteristics of the battery were further improved in Example 8, in which a positive electrode mixture having a higher positive electrode additive content was used. This means that the use of the positive electrode mixture having a high positive electrode additive content of one embodiment can further improve the initial charging capacity of the battery and thus more effectively improve the life of the battery. Therefore, as mentioned above , the battery In the case of improving the initial performance of and securing long-term life characteristics, it may be possible to mix and use the positive electrode active material with the positive electrode additive of one embodiment at an appropriate mixing ratio according to the desired battery characteristics. 【Scope of claim】 [Claim 1] Core represented by the following formula (1) in the overall composition; And Located on the surface of the core, phosphorus) a coating layer containing a compound; containing, Anode additive: [Formula 1] { x( Li 2+a Ni b Mi. b02+c)} · {y( NiO)} · { z( Li 20)} In Formula 1, Is at least one of the metal elements forming a divalent cation or a trivalent cation, -0.2£a£0.2, 0.5 £b £1.0, -0.2£c£0.2, 0.7空 <1.0, 0