TW200818581A - Positive electrode active material for nonaqueous electrolyte secondary battery and method for producing the same - Google Patents

Abstract

Disclosed is a highly safe positive electrode active material which is excellent in charge/discharge cycle characteristics, while having a high discharge capacity even at a high operating voltage. Also disclosed are a method for producing such a positive electrode active material, and a nonaqueous electrolyte secondary battery comprising such a positive electrode active material. Specifically disclosed is a positive electrode active material for nonaqueous electrolyte secondary batteries which is characterized by being composed of a surface-modified lithium-containing complex oxide particle represented by the following general formula: LipNxMyO2 (wherein N represents at least one element selected from the group consisting of Co, Mn and Ni; M represents an element selected from the group consisting of transition metals other than the element N, alkaline earth metals and aluminum; and 0.9 ≤ p ≤ 1.1, 0.9 ≤ x < 1.1, 0 ≤ y ≤ 0.3). The positive electrode active material for nonaqueous electrolyte secondary batteries is further characterized in that the surface layer thereof contains titanium, and the atomic ratio of the titanium content to the element N content within 5 nm from the surface is not less than 0.6.

Description

[Technical Field] The present invention relates to a positive electrode active material used in a nonaqueous electrolyte battery for a lithium ion battery or the like, a method for producing the same, and a lithium secondary battery including the above positive electrode active material. [Prior Art] In recent years, with the rapid development of information-related devices and communication devices such as laptops and mobile phones, there is a relatively high demand for non-aqueous electrolyte batteries such as small, lightweight, lithium-ion batteries having high energy density. The positive electrode active material for a non-aqueous electrolyte battery is a composite oxide of lithium and a transition metal such as LiC〇02, LiNi02, LiNi0.8Co0.2O2, LiNi1/3C〇i/3Mn1/3〇2, and LiMn204. . Among them, a lithium-cobalt composite oxide (Li Co 02 ) is used as a positive electrode active material, and a lithium secondary battery using a carbon such as a lithium alloy, graphite or carbon black as a negative electrode is particularly widely used as a lithium battery having a high voltage of 4 V. Cartridge energy density battery. Further, attention has been focused on a positive electrode active material called a lithium nickel cobalt (Li-Ni-Co) composite oxide or a lithium nickel cobalt manganese (Li-Ni-Co-Mn) composite oxide. These positive electrode active materials are characterized by adjusting the battery characteristics of charge and discharge cycle characteristics, speed characteristics, safety, and the like by adjusting the addition amount of nickel, cobalt or manganese. However, the positive electrode active material using any lithium-containing composite oxide cannot satisfy all of the discharge capacity, charge and discharge cycle characteristics, speed characteristics, and safety during charging (abbreviated as An-4 - 200818581 in this specification) Characteristics of sex). In order to solve such problems, the following techniques are known. For example, when it is proposed to coprecipitate cobalt and titanium, a coprecipitate can be obtained, and the coprecipitate is mixed with lithium carbonate, and then the obtained lithium-containing composite oxide is fired at 995 ° C (refer to the patent). Literature 1). Further, it is proposed to impregnate a lithium-containing composite oxide having a isopropyl tris(N-aminoethyl-aminoethyl) titanate coupling agent, and then calcination at 900 ° C. Composite oxide (refer to Patent Document 2). In addition, it is proposed to add water and a titanium ammonium oxalate to the synthesized lithium-containing composite oxide in advance, and then to form a lithium-containing composite oxide coated with titanium oxide on the surface of the particles by stirring, spray drying, pulverization, and heat treatment (refer to Patent Document 3). Further, it is proposed to adsorb a titanium-containing composite oxide obtained by heat-treating at a temperature of 500 ° C after adsorbing a titanium hydroxide colloid on the surface of a particle (see Patent Document 4), or to add lithium to an acetone solution in which a titanium oxide gel is dispersed. The surface-modified lithium nickel composite oxide obtained by heat-treating the nickel composite oxide after being heated, dried, and dried at 500 ° C (refer to Patent Document 5) 〇 In addition, in an ethanol solution of Ti(OC2H5)4 The lithium-containing composite oxide obtained by dispersing and drying the lithium-containing composite oxide is subjected to heat treatment (see Patent Documents 6 and 7). [Patent Document 1] Japanese Patent Laid-Open Publication No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. Japanese Laid-Open Patent Publication No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. When the lithium-containing composite oxide powder obtained in the documents 1 to 7 is used as a positive electrode active material of a nonaqueous electrolyte secondary battery such as a battery, the discharge capacity and the charge/discharge cycle characteristics are insufficient in the above-described respective characteristics, and it is not sufficient at the same time. To meet the characteristics of safety and the like, it is required to further improve. Further, when the negative electrode of the lithium secondary battery is lithium, in general, the charging voltage is 4·3 V', the charging voltage is increased, and the amount of the positive electrode active material available is increased to further increase the discharge capacity. For example, when the charging voltage is 4.3 V, the utilization rate of the positive active material is 50 to 60%, but when the charging voltage is 4.5 V, the above utilization rate can be increased to about 70%, and the discharge capacity is further increased. The lithium-containing composite oxide obtained in the above Patent Documents 1 to 7 does not sufficiently have a charge-discharge cycle characteristic at a charging voltage of 4.3 V, and the charge-discharge cycle characteristics are deteriorated at a high operating voltage of 4.5 V. The situation. An object of the present invention is to provide a positive electrode active material for a nonaqueous electrolyte battery which has high safety, high discharge capacity, high charge and discharge cycle characteristics, and a method for producing the same, and a lithium containing the positive electrode active material. A non-aqueous electrolyte battery such as a battery. -6 - 200818581 The inventors of the present invention have further intensively studied and found that surface-modified lithium containing a higher specific concentration of titanium in a specific surface region thereof by a lithium-containing composite oxide particle having a specific composition The positive electrode active material formed by the composite oxide particles can achieve the above object. In other words, it has been found that by using the positive electrode, it is possible to achieve high safety, high discharge capacity even at high operating voltage, and excellent charge and discharge cycle characteristics. In the present invention, the mechanism for obtaining any excellent characteristics by the lithium-containing composite oxide particles is not clear, but it can be estimated as follows. In other words, in the non-aqueous electrolyte secondary battery such as a lithium secondary battery, when the charge and discharge are repeated, the decomposition reaction of the electrolytic solution is caused at the interface between the lithium-containing composite oxide particles and the electrolytic solution to generate a gas containing carbon dioxide. However, when a lithium-containing surface-modified composite oxide particle containing a relatively high concentration of titanium in the surface region is used, by reacting the active site on the surface of the lithium-containing composite oxide particle with titanium, the above electrolyte can be suppressed. Decomposition reaction maintains high operating voltage, high volume halo density and high safety. At the same time, when there is a high concentration of titanium in the surface layer of the lithium-containing composite oxide particles, the active component in the lithium-containing composite oxide particles can be inhibited from eluting from the electrolyte, and the operating voltage is 4.3 V even at 4.5. Under the extremely high operating voltage of V, the charge-discharge cycle characteristics can be significantly improved. Further, the above-mentioned conventional lithium-containing composite oxide particles are titanium-containing, and the content of titanium is not large, and in particular, the titanium content of the surface layer is not large. For example, the lithium-containing composite oxide particles described in the above-mentioned Patent Document 1 are calcined at a high temperature of 995 ° C after the addition of the titanium powder. Therefore, the additive element is solid-dissolved and diffused to be a particle inside the particle. The surface contains 50% of titanium in the range of 50 200818581 ~ 100nm. In other words, the surface layer of the lithium-containing composite oxide described in Patent Document 1 is within 5 nm, and the atomic ratio of titanium is as high as about 0.5 for the element N. Further, the element N represents cobalt, manganese and nickel contained in the lithium-containing composite oxide particles, and in the examples of Patent Document 1, it is indicated. The lithium-containing composite oxide described in Patent Document 2 is chemically modified on the surface of the particles by a titanium coupling agent, and then heat-treated at a high temperature of 900 ° C. The surface layer of the lithium-containing composite oxide is within 5 nm. The atomic ratio is, for example, as described in the literature, and is about 0.08 for element N. In the lithium-containing composite oxide described in Patent Document 3, the atomic ratio of titanium is within 5 nm of the surface layer, as described in the literature, and is about 0.16 for the element N. Further, in Patent Document 4, a titanium hydroxide colloidal aqueous solution is used, and in Patent Document 5, an acetone solution of a titanium oxide sol is used, and a titanium compound is modified on the surface of the particles, followed by heat treatment at 500 °C. When the sol gel method is used, it is difficult to contain titanium in a thin and specific ratio on the surface of the particles, and the surface layer of the lithium-containing composite oxide particles is within 5 nm, and the atomic ratio of titanium is as high as about 0.5 for the element N. In Patent Document 6 and Patent Document 7, after the titanium compound is modified on the surface of the particle by using an ethanol solution of Ti(OEt) 4, the heat treatment is performed only when the concentration of Ti(OEt) 4 in the ethanol solution is extremely low. 5。 The surface layer of the surface-modified lithium-containing composite oxide obtained within 5nm, the atomic ratio of titanium is about 〇. Accordingly, the present invention is based on the above novel findings and has the gist of the following -8 - 200818581. (1) A positive electrode active material for a nonaqueous electrolyte secondary battery, characterized by a lithium-containing composite oxide particle represented by a general formula LipNxMy02 (wherein N is at least one element selected from the group consisting of Co, Μη, and Ni, Μ ^ is a _ element selected from the group consisting of a transition metal other than the element lanthanum, an alkaline earth metal, and aluminum, 0.9gp$11, 0.9'x&lt;ll, 0'yS0.3), and contains titanium on the surface layer thereof, and The surface layer has a titanium content of 5 nm or less, and is composed of a composite oxide particle containing surface-modified lithium having an atomic ratio of 0.6 or more. (2) The positive electrode active material for a nonaqueous electrolyte secondary battery according to the above aspect, wherein the lithium-containing composite oxide particles are at least one selected from the group consisting of lithium cobaltate, lithium nickel cobaltate, lithium nickel cobalt aluminate, and nickel cobalt. The particles of the group consisting of lithium manganate and the titanium contained in the entire surface of the composite oxide particles containing the surface-modified lithium, the atomic ratio of the element N and the element Μ is 〇.〇00 5~ 0.10. (3) The positive electrode active material for a nonaqueous electrolyte battery according to (1) or (2), wherein the surface-modified lithium composite oxide particles have an average particle diameter (D50) of 5 to 25 μ? The positive electrode active material for a nonaqueous electrolyte battery according to any one of the above aspects, wherein the surface-modified lithium composite oxide particles contain a carbon compound on the surface layer. (5) The positive electrode active material for a nonaqueous electrolyte secondary battery according to (4), wherein the carbon compound is a partial thermal decomposition product of a carbon-containing titanium complex. -9- 200818581 (6) A lithium secondary battery, which is a lithium secondary battery including a positive electrode and a negative electrode and a non-aqueous electrolyte, wherein the positive electrode system is used in any one of (1) to (5). Positive electrode active material. (7) The method for producing a positive electrode active material for a nonaqueous electrolyte secondary battery according to any one of the aspects of the present invention, characterized in that the lithium-containing composite oxide particles represented by the general formula LipNxMy〇2 are contained. (wherein N is at least one element selected from the group consisting of Co, Μη, and Ni, and the lanthanide is an element selected from transition metals other than element lanthanum, alkaline earth metals, and aluminum' 〇·9$ρ^1·1 〇·9'χ&lt;1·1, 0SyS0.3) is impregnated with an aqueous solution containing a titanium complex having a pH of 1 to 12, and then mixed and dried to obtain a titanium complex impregnated particle. Step 1, and step 2 of subjecting the titanium complex compound impregnated particles obtained in the step 1 to heat treatment in an oxygen-containing atmosphere. (8) The method for producing a positive electrode active material for a nonaqueous electrolyte secondary battery according to (7), wherein the heat treatment in the step 2 is carried out at 200 to 450 °C. (9) The method for producing a positive electrode active material for a nonaqueous electrolyte secondary battery according to the above aspect, wherein the titanium complex compound is a carbon-containing titanium complex. (1) The method for producing a positive electrode active material for a nonaqueous electrolyte secondary battery according to the above aspect, wherein the carbon-containing titanium complex compound is titanium lactate. [Effect of the Invention] According to the present invention, it is possible to provide a composite oxide containing surface-modified lithium which does not have high safety, has an operating voltage of high -10 - 18,815,581, high discharge capacity, and excellent charge and discharge cycle characteristics. A positive electrode active material formed of particles, a method for producing the positive electrode active material, and a nonaqueous electrolyte secondary battery using the positive electrode active material. [Best Mode for Carrying Out the Invention] The surface-modified lithium-containing composite oxide particles of the present invention are obtained by modifying the surface of the lithium-containing composite oxide particles of the base material with a titanium compound. The lithium-containing composite oxide particles forming the base material are represented by the general formula LipNxMy〇2 (wherein N is at least one element selected from the group consisting of Co, Μη, and Ni, and the lanthanide is selected from the group consisting of the element N Elements of transition metals, alkaline earth metals and aluminum, 〇· 9 ' p S 1 · 1, 0.9 SX &lt; 1.1, 0^y^0.3 ). In the formula, the element N is as described above, wherein cobalt alone, nickel alone, a combination of nickel-cobalt, a combination of nickel-cobalt-aluminum, a combination of nickel-cobalt-manganese is preferred, and in terms of practicality A combination of cobalt alone and nickel-cobalt-manganese is preferred. Further, a part of oxygen (e.g., 〇·1 to 5 mol%) may be substituted with a fluorine atom to improve battery characteristics. Further, in the formula, P and X are 0, preferably 0.95SpS1.5; 0.9$&amp;&lt;1.1, preferably 〇.95':^&lt;1.〇5. By adding the element ^^, the battery characteristics can be further improved. Further, when the element cerium contains an alkaline earth metal or a compound, y is preferably in the range of 0. When an excessive amount of an element such as titanium is present in the interior of the lithium-containing composite oxide particles, the amount of discharge is lowered. The element μ represents the above-mentioned element, and preferably a 2 to 4 valent element selected from the group consisting of A1, Mg, Zr, Ti, Mo, Ca, and the like. Further, in the case of capacity, safety, and charge-discharge cycle characteristics, it is more preferable that at least one selected from the group consisting of Ti, Zr, Mg, and Α1 is used. At this time, a specific example of a lithium-containing composite oxide such as LiNi0.8Co0.HAU.05O2

LiNi〇.6Co〇iMn〇.25Al〇.〇5〇2, LiNii/3C〇i/3Mni/3〇2, LiNi〇8Co〇.2〇2, LiNio.4Mno.4Coo.2O2 or Lii.osfMnojNiojCoo.do wO〗 and so on. A commercially available lithium-containing composite oxide can also be used. In the surface-modified lithium composite oxide particles of the present invention, the content of titanium on the surface layer within 5 nm from the surface of the particle φ is required to be 0.6 or more for the element N. When the content of titanium is within the predetermined range, the effects of the present invention described above can be attained. Here, the content of titanium on the surface layer within 5 nm of the surface of the composite oxide particle containing the surface-modified lithium is as described above in the present invention in the vicinity of the surface of the surface-modified lithium-containing composite oxide particle. It is extremely important that the content of titanium within 5 nm of the surface layer of the particles can be easily determined by XPS analysis (X-ray photoelectron spectroscopy) as follows. Φ In addition, in the present specification, "the atomic ratio of titanium to the element N on the surface layer within 5 nm of the surface of the composite oxide particle containing the surface-modified lithium" is simply referred to as "the surface of the composite oxide particle containing lithium". The atomic ratio (Ti/N)". 'The atomic ratio of the surface of the lithium-containing composite oxide particle in the present invention (

Ti/N) is 0.6 or more, preferably 0.7 or more, more preferably 0.8 or more, and particularly preferably 1.0 or more, and most preferably 1.2 or more. Further, the upper limit 値 is not particularly limited, and the atomic ratio (Ti/N) is preferably 15 or less, more preferably 1 2 or less, and most preferably 10 or less. -12- 200818581 In the present invention, the atomic ratio (Ti/N) of the surface of the lithium-containing composite oxide particles is analyzed by XPS analysis (X-ray photoelectron spectroscopy). The XPS analysis analyzes the proportion of elements or elements contained in layers that are very close to the particle surface. Further, an example of an XPS analyzer is an ESCA 5400 (no monochromatic type) manufactured by PHI Corporation. Further, in the present invention, high sensitivity detection can be performed, and it is preferable to use peaks of other elements as much as possible and peaks which are not repeated. Specifically, it is preferable to use a 2p peak having a high sensitivity when analyzing titanium. Further, when analyzing cobalt, manganese or nickel, it is preferred to use a peak of 2p3 which is highly sensitive. In addition, in the elemental analysis of the powder surface, each of the ΕΡΜΑ (X-ray microanalyzer) analysis or EDS (energy dispersive X-ray spectroscopy) analysis is used to obtain a correlation from the surface of the particle to the surface layer of 50 to 100 nm. An analysis of the information of elements in the deep range. Therefore, when the atomic ratio (Ti/N) of the surface of the particle of the lithium-containing composite oxide of the present invention is measured, the titanium contained in the composite oxide particle containing the surface-modified lithium of the present invention is not required. For the total amount of the element N and the element Μ, the atomic ratio is preferably 0.0005 to 0.10, more preferably 0.0008 to 0.08. When titanium is contained in the elemental yttrium, the titanium contained in the entire composite oxide particles containing the surface-modified lithium has an atomic ratio of Ν. 〇1 〇 〇 〇8 in terms of the total amount of the element Ν and the element Μ. good. In addition, when the element Μ does not contain titanium, the titanium contained in the entire composite oxide particles containing the surface-modified lithium is more preferably 原子·〇〇〇8 to 0.03 in terms of the atomic ratio of the element Ν and the element Μ. good. -13- 200818581 Moreover, the surface layer may also contain elements other than titanium. When an element other than titanium is present in the surface layer, a preferred element such as magnesium. Further, the surface-modified composite oxide particles of the present invention further contain a carbon compound on the surface layer. The carbon compound is preferably a partial thermal decomposition product of a carbon-containing titanium complex having at least a carbon-oxygen double bond structure. Among them, the carbon-oxygen double bond is more preferably a carbonate group or a carbonyl group. a specific compound containing at least one selected from the group consisting of citric acid, titanium tartrate, oxalic acid, titanium malonate, titanium maleate, titanium malate, titanium hydride, titanium lactate, and titanium glyoxylate. Thermal decomposition products are preferred. Among them, the thermal decomposition product is more preferably a part of titanium lactate. Further, in the present specification, the partial thermal decomposition product means a structure having a carbon-oxygen double bond structure and thermally decomposing a titanium complex compound on the surface of the composite oxide particles partially containing surface-modified lithium. Fig. 1 is an infrared absorption (IR) spectrum of the lithium-containing composite oxide synthesized in Example 2 or Example 4. The IR spectrum of the surface-modified lithium-containing composite oxide synthesized in Example 2 had a strong absorption peak in the range of 1300 to 1700 CHT1. The absorption peak is an absorption peak derived from a carbon-oxygen double bond, and indicates that a carbon compound exists on the surface layer. Further, the carbon compound means a partial thermal decomposition product of a carbon-containing titanium complex used as a raw material. Further, in the IR spectrum of the lithium-containing composite oxide synthesized in Example 4, there was no strong absorption peak derived from the above carbon-oxygen double bond. In addition, the second figure is a measure of the change in weight (TG and DTG) and the change in calorific value (DTA) when heat is applied to the powder (dry powder) in which titanium lactate is dried. As can be seen from Fig. 2, when the dry powder of titanium lactate is heated to a range of 20 0 to 45 ° C, the weight of the dry powder is drastically reduced, and the intense heat reaction is accompanied by -14-200818581. In other words, in the temperature range, the titanium lactate causes partial thermal decomposition, and a gas such as carbon dioxide is released to carry out a decarbonation reaction. Further, it is understood that the thermal decomposition reaction is almost completed at 450 °C or higher. In this stage, the titanium coordination compound is converted into titanium oxide or titanium hydroxide. Thus, it can be seen that in the surface layer of the surface-modified lithium-containing composite oxide particles synthesized by heat treatment at 350 ° C in Example 2, a titanium compound having a carbon-oxygen double bond is present. A carbon compound is present on the surface layer, and the carbon compound is a partial thermal decomposition product of the carbon-containing titanium complex compound used as a raw material. Thereby, the charge-discharge cycle characteristics can be improved, but the reason and mechanism for further improving the charge-discharge cycle characteristics are not clear. The surface-modified lithium-containing composite oxide particles of the present invention have a pH 含 of 1 to 1 2 for impregnating the titanium-containing complex compound with respect to the lithium-containing composite oxide such as LiNi1/3C〇1/3Mn1/302 synthesized in advance. The aqueous solution (referred to as the aqueous solution of Ti in the present specification) is mixed and dried, and is obtained by heat treatment. Further, it is preferable that the pH of the Ti aqueous solution is 1 to 8. The titanium compound which is a raw material of the Ti aqueous solution is not particularly limited. However, in terms of improving the solubility of titanium present in the titanium-containing aqueous solution used for surface modification, a coordination compound of titanium is preferred. Further, when the titanium complex is dissolved in water, it is a compound which is coordinated to form a complex compound on titanium. Further, after the heat treatment, in order to retain the above-mentioned carbon compound on the surface of the composite oxide particle containing surface-modified lithium, the titanium compound is preferably a carbon-containing titanium complex compound to have a carbonyl group or a carbonic acid-15. - 200818581 The carbon-containing titanium coordination compound is more preferred, and the organic acid titanium coordination compound having a carbonyl group or a carbonic acid group is preferred. Specifically, the titanium compound is preferably at least one selected from the group consisting of titanium citrate, titanium tartrate, titanium oxalate, titanium malonate, titanium maleate, titanium malate, titanium gluconate, titanium lactate and titanium phthalate. Among them, the titanium compound is more preferably titanium lactate. The presence of the carbon preferably has a tendency to further improve the charge-discharge cycle characteristics of the composite oxide containing surface-modified lithium. Further, the Ti aqueous solution may contain a carboxylic acid. When the carboxylic acid is contained in the Ti aqueous solution, the carboxylic acid is preferably a carboxylic acid having a carbon number of 2 to 8 in terms of solubility in an aqueous solution, and at least one selected from the group consisting of citric acid, tartaric acid, oxalic acid, and acrylic acid. , maleic acid, malic acid, grape acid, lactic acid and titanium glyoxylate are better. The content of the carboxylic acid in the Ti aqueous solution is preferably 〜·〇 5 to 30% by weight, more preferably 〇·1 to 20% by weight. When the carboxylic acid is contained in the Ti aqueous solution, the solubility of the titanium complex contained in the Ti aqueous solution in water is improved, and the titanium complex which is not easily dissolved in the Ti aqueous solution tends to be precipitated.

The concentration of titanium in the Ti aqueous solution is preferably at a high concentration in the subsequent step by removing the aqueous medium by drying. However, when the concentration of titanium in the aqueous solution is too small, the viscosity is changed, and the contact with the above-mentioned base material or the rationality of the aqueous solution tends to be complicated. Therefore, the concentration of the solution in the Ti aqueous solution is 0. 01 to 20% by weight is more preferable, and more preferably 5% by weight. For the lithium-containing composite oxide particles of the base material, in the step of impregnating the aqueous solution of Ti, the amount of the aqueous solution of Ti is used for the base material used to modulate -16-200818581 to 0. The range of 1 to 80% by weight is preferably adjusted to be 1 to 75% by weight, more preferably 30 to 70% by weight. When the amount of the Ti aqueous solution used is within the above range, when the positive electrode active material of the present invention is synthesized in a large amount, the problem of the performance unevenness of the positive electrode active material can be solved between batches, and the mass production can be stably performed. The tendency of the positive electrode active material is preferred. The method of impregnating the Ti-containing aqueous solution of the lithium-containing composite oxide particles of the base material is not particularly limited, and specifically, a method in which the Ti aqueous solution is sprayed in the particle powder of the base material by a sprayer can be used, or can be contained. A method of impregnating a particle powder of a base material into a Ti aqueous solution in a container, stirring it, and so on. The specific agitator used for stirring, such as a 2-axis rotary kneading machine, an axial mixer, a stirring mixer, a vortex mixer, a barrel mixer, a fixed air machine, a stage mixer, and the like. In the step of mixing and drying the lithium-containing composite oxide particles of the base material, the step of mixing and drying is preferably carried out at 50 to 200 ° C, preferably at a temperature of 80 to 14 ° C. It is more preferably in the range of 0·1 to 10 hours. In order to impregnate the residual aqueous medium in the particles after drying, the titanium medium is removed in the subsequent firing step, and it is not necessary to completely remove it in this stage, but the water is vaporized in the heat treatment step. A large amount of energy must be used in order to remove as much as possible. Further, in the step of impregnating the Ti aqueous solution and further mixing and drying to obtain the titanium complex compound impregnated particles, the impregnation, mixing, and drying may be carried out in an individual order, or may be carried out by using a classification mixer at the same time. -17- 200818581 In addition, as far as possible, the water medium is removed from the titanium complex compound impregnated particles, and is preferably used in an oxygen-containing gas atmosphere by a temperature of 200 to 45 ° C, usually 〇 1 to 24 hours. The surface-modified lithium-containing composite oxide of the present invention can be obtained by heat-treating the titanium complex compound impregnated particles. Further, when the impregnated powder is subjected to heat treatment, the positive electrode active material of the surface-modified lithium-containing composite oxide particles of the present invention obtained as described above is preferably in a temperature range of from 250 to 4001, and the average particle diameter thereof is D50) is preferably 5~25μηη, more preferably 8~20μηη, and the specific surface area is 0·1~1. 0m2/g is better, with 0. 2~0. 8m2/g is better. In addition, 2 Θ = 65 is determined by X-ray diffraction with CuKot as the line source. The diffraction peak width of the (110) plane of 1±1° is 値. 〇8~0. 30° is better, with 0. 09~0. 25° is better. The compaction density is 2·40~3. 50g/cm3 is preferred, with 2. 50~3. 30g/cm3 is better. In the present invention, the compacted density means that the surface-modified lithium composite oxide particles are 0. The apparent density of the particles when pressed at a pressure of 3 tons/cm2. Further, the amount of lithium ion elution of the surface-modified lithium-containing composite oxide of the present invention is preferably 0.6% by mole or less. 〇1~0. 50% Mo is better, with 0. 01~0·40 mol% is the best. In the present invention, the amount of lithium ion eluted can be measured as described below. First, a powder of 10 g of the positive electrode active material was added to 90 g of water, and the resulting aqueous solution was stirred for 30 minutes to be dispersed. Then, the aqueous solution was filtered, and the obtained filtrate was titrated with hydrochloric acid. When the amount of lithium ion elution is in the above range, the positive electrode active material powder is dispersed in a slurry of a dispersion medium such as N-methylpyr-18-200818581-rrolidone during the positive electrode processing. It is preferable that the gelation tends not to be formed, and the positive electrode processing is made easier. Further, the tendency to improve the charge and discharge cycle characteristics is preferable. In the present invention, the 'average particle size means that the particle size distribution is determined on a volume basis'. In the 100% cumulative curve, the cumulative curve is the particle size at 50%, and the volume basis is accumulated at 50% diameter (D50). The particle size distribution is determined by the frequency distribution and the cumulative volume distribution curve measured by the laser scattering particle size distribution measuring apparatus. The measurement of the particle size is carried out by sufficiently dispersing the powder in an aqueous medium by ultrasonic treatment or the like, and measuring the particle-degree distribution (for example, using a micro-tracking HR A (X-100) manufactured by Nikkiso Co., Ltd.). Further, in the present specification, the above average particle diameter is referred to as an average particle diameter (D50) or D50. Further, D10 indicates the particle diameter at the point where the cumulative curve is 10%, and D90 indicates the particle diameter at the point where the cumulative curve is 90%. A method of producing a positive electrode for a lithium secondary battery using the positive electrode active material of the present invention can be carried out in a usual manner. For example, a carbon-based conductive material such as acetylene black, black lead or kitchen black is mixed with the powder of the positive electrode active material of the present invention, and mixed with a bonding material to form a positive electrode mixture. Among the above bonding materials, polyfluorinated vinylidene, polytetrafluoroethylene, polyamine, carboxymethylcellulose, acrylic resin or the like is preferably used. The slurry of the above-mentioned positive electrode mixture is dispersed in a dispersion medium such as N-methylpyrrolidone, and coated, dried, and pressure-rolled on a positive electrode current collector such as aluminum foil to form a positive electrode active material layer on the positive electrode current collector. In the lithium secondary battery using the positive electrode active material of the present invention as a positive electrode, the electrolyte contained in the battery or the electrolyte contained in the polymer electrolyte is such that one or more selected from the group consisting of C104_, CF3SO3-, BF4, and PF6- are used in -19-200818581. As the anion lithium salt, AsF6·, SbF6_, CF3C02_'(CF3S02)2N_ or the like is preferable. An electrolyte solution or a polymer electrolyte of the battery, which contains 0 in a solvent or a solvent-containing polymer. 2~2. An electrolyte composed of the above lithium salt at a concentration of 0 mol/L is preferred. When it is out of this range, the ion conductivity is lowered and the electrical conductivity of the electrolyte is lowered. More preferably, it is selected from 0. 5~1. 5 mol / L. The separator is preferably a porous polyethylene or a porous polypropylene film. Further, the solvent of the electrolyte solution is preferably a carbonate. The carbonate can be used in a ring shape or a chain shape. A cyclic carbonate such as propylene carbonate, ethylene carbonate (EC) or the like. A chain carbonate such as dimethyl carbonate, diethyl carbonate (DEC), ethyl methyl carbonate, methyl propyl carbonate, methyl isopropyl carbonate or the like. These carbonates may be used singly or in combination of two or more. It can also be mixed with other solvents. Further, depending on the material of the negative electrode active material, when the chain carbonate and the cyclic carbonate are used, the discharge characteristics, the charge and discharge cycle characteristics, and the charge and discharge efficiency can be improved. In addition, a fluorinated ethylene-hexafluoropropylene copolymer may be added to the organic solvent (for example, Aaron Kem (trans)), fluorinated ethylene-perfluoro A propyl vinyl ether copolymer was added with the following solute as a gel polymer electrolyte. The negative electrode active material of the lithium battery using the positive electrode active material of the present invention as a positive electrode is a material capable of occluding and releasing lithium ions. The material for forming the negative electrode active material is not particularly limited, and examples thereof include lithium metal, lithium alloy, carbon material, carbon compound, carbon ruthenium compound, ruthenium oxide compound, vulcanization -20 - 200818581 titanium, boron carbide compound, and periodic table 14 The metal of Group 15 is used as the oxide of the main body. The carbon material can be used to thermally decompose organic matter under various thermal decomposition conditions, or artificial black lead, natural black lead, soil black lead, expanded black lead, scaly black lead, and the like. Further, as the oxide, a compound mainly composed of tin oxide can be used. As the negative electrode current collecting system, copper foil, nickel foil, or the like is used. The shape of the lithium secondary battery using the positive electrode active material of the present invention is not particularly limited. Depending on the application, a sheet shape (ie, a film shape), a folded shape, a rolled back type bottomed cylindrical shape, a button shape, and the like are selected. [Embodiment] The present invention will be specifically described below, but the present invention is not limited by the examples and explained. Examples 1 to 3, 6, 6, 8, 10, 12, 14 and 16 are examples of the present invention, and Examples 4, 5, 7, 7, 9, 1 and 13 Examples 1 5 and 17 are comparative examples. [Examples] [Example 1] A sulfate aqueous solution containing nickel sulfate, cobalt sulfate and manganese sulfate, an aqueous ammonium sulfate solution, and an aqueous sodium hydroxide solution were used to adjust the pH of the slurry in the reaction tank to 11 · 0, and the temperature was Stirring was carried out at 50 ° C and each was continuously supplied to the reaction tank. The amount of liquid in the reaction system was adjusted by an excessive flow reaction, and the excessively flowing coprecipitated slurry was filtered, washed with water, and then dried at 8 Torr to obtain a nickel-cobalt-manganese composite hydroxide powder. -21 - 200818581 Next, by dispersing the composite hydroxide powder in a 6% by weight aqueous solution of sodium persulfate containing 3% by weight of sodium hydroxide, stirring at 20 ° C for 12 hours to synthesize nickel-cobalt-manganese composite A carbonyl hydroxide slurry. Further, the composite carbonyl hydroxide slurry is filtered, washed with water, and then dried to obtain a composite carbonyl hydroxide powder having a specific surface area of 9. 6 m2 / g, the average particle size is 1〇. 101!1. In the obtained composite carbonyl hydroxide powder, lithium carbonate powder having a uniform φ average particle diameter of 20 μm was mixed and fired at 1 000 ° C for 16 hours in an atmosphere having an oxygen concentration of 40% by volume. From the pulverization, a base material composed of a lithium-containing composite oxide having a composition of LimXNimComMnwOmO; When the powder X-ray diffraction spectrum using the CuKa line was measured for the base material, it was found to be a structure similar to the rhombohedral system (R-3m). Further, the measurement system was a RINT 2100 model manufactured by Rigaku Corporation. When the particles of the base material powder were observed by SEM, it was found that a plurality of primary particles agglomerated to form secondary particles, and the shape thereof was approximately spherical or elliptical. • Then, in 〇. 61g titanium content is 8. 2% by weight of aqueous titanium lactate solution was added to 49. 3 9g water, modulating pH 値2. 1 Ti aqueous solution. The above base material was immersed in 50 g of the above Ti aqueous solution, and then slowly mixed to obtain a mixed powder. Further, the mixed powder was dried at 120 ° C for 4 * hours to prepare a titanium complex impregnated particles. The dried coordinating compound impregnated particles are heated in an oxygen-containing gas atmosphere at 350 ° C for 12 hours, and the average particle diameter is 1 〇. 3μηι, D10 is 5. 2μιη, D90 is 14. 3μιη, specific surface area is 0. The surface-modified lithium composite oxide particles of the present invention having a spherical shape of about 5 m 2 /g. -22-200818581 The obtained surface-modified lithium-containing composite oxide particles were subjected to a X-ray diffraction spectrum using a ray diffraction apparatus (RINT 2100, manufactured by Rigaku Corporation). In the X-ray diffraction using the powder of the CuKa line, the diffraction peak width of the (110) plane of 2Θ = 65·1±1° is 〇·225°. The pressed density of the particles is 2. 7g/cm3. Further, the titanium contained in the entire surface of the surface-modified lithium-containing chemical particles has an atomic ratio of 0 to the total amount of nickel, manganese and cobalt. 0 0 1. With respect to the obtained surface-modified lithium-containing composite oxide particles, when the atomic ratio (Ti/N) of the surface of the lithium-containing composite oxide particles was measured by XP S analysis, (Ti/N) = 0. 7 1. In addition, the amount of lithium ion elution is 0. 2 1 mole %. The surface-modified lithium-containing composite oxide particles are mixed with acetylene fluorene and polyfluorinated vinylidene powder in a weight ratio of 90/5/5, and N-methylpyrrolidone is added to prepare a slurry, and the aluminum foil having a thickness of 20 μ? Apply a single side with a spatula. A positive electrode sheet for a lithium battery was produced by drying and rolling and rolling three times. Then, the above-mentioned positive electrode body sheet was used as a positive electrode through a perforator, a metal lithium foil having a thickness of 500 μm was used as a negative electrode, a 20 μm nickel foil was used as a negative electrode current collector, and a porous polypropylene having a thickness of 25 μm was used as a separator, and used. A solution of LiPF6/EC + DEC (1:1) at a concentration of 1 ( (refers to a mixed solution of EC to DEC by a ratio of 1^1^6 as a solute. The following solvents are also used as such Benchmark.) As an electrolyte, four stainless steel simple sealed cell type lithium batteries were assembled in an argon small toolbox. With respect to the above one battery, 1 g of the positive electrode active material was charged to 4 · 3 V at a load current of -23-200818581 3 0 m A at 25 ° C, and 1 g of the positive electrode active material was discharged to 3 〇 11 八 load current to 2 . 5 V ' to obtain the initial discharge capacity. Further, regarding the battery, a charge and discharge cycle test was performed 30 times. The result is in 25 art, 2. 5 ~ 4. The initial weight capacity density of the positive active material of 3 V was 159 m Ah/g, and the capacity retention rate after 30 charge and discharge cycles was 98. 5%. In addition, regarding a battery, in addition to making the charging voltage from 4. 3V was changed to 4. 5V, 25 times of charge and discharge cycle test, the result of the same operation, 2. 5~4. The initial weight capacity density of the positive electrode active material of 5 V was 175 m Ah/g, and the capacity retention rate after the 25 charge and discharge cycles was 94. 9%. In addition, regarding the other battery system, each has 4. 3 V and 4. 5 V was charged for 10 hours, disassembled in a small argon gas kit, and the charged positive electrode sheet was taken out, and the positive electrode sheet was washed, perforated to a diameter of 3 mm, and sealed in an EC and aluminum capsule, and The temperature was raised at a rate of 5 ° C /min using a scanning differential calorimeter, and the heat start temperature was measured. As a result, 4. The heating start temperature of the heating curve of the 3V charging product is 233 °C, 4. The 5 V charger is 198 °C. [Example 2] As in the case of Example 1, the synthetic base material has Lii. 02(Nii/3C〇i/3Mni/3)0. A lithium-containing composite oxide composed of 98〇2. Then, at 3. 03g titanium content is 8. 2% by weight of aqueous titanium lactate solution is added to 4. 9 7 g of water was prepared to prepare a T i aqueous solution of p Η値2. 100 g of the above base material was immersed in 50 g of the above Ti aqueous solution, and then slowly mixed to obtain a mixed powder. Further, the mixed powder was dried at 120 ° C for 4 - 24 to 2008 18581 hours to prepare a titanium complex impregnated particles. The dried coordination compound impregnated particles are heated in an oxygen-containing gas atmosphere at 350 ° C for 12 hours, and the average particle diameter is 1 〇 · 5 μιη, D 1 0 is 5 · 5 μπι, and D9 0 is 14 ·6μπι, specific surface area is 〇. The surface-modified lithium composite oxide particles of the present invention having a spherical shape of about 5 m 2 /g. - The obtained surface-modified lithium-containing composite oxide particles were measured for the X-ray diffraction spectrum in the same manner as in Example 1. Powder X-ray diffraction using CuKa line • Medium, 2Θ = 65·1 Soil 1. The diffraction peak width of the (110) plane is 0. 226. . The pressed density of the particles is 2. 69g/cm3. Further, the titanium contained in the entire surface-modified lithium-containing compound particles has an atomic ratio of 0 to a total of nickel, manganese and cobalt. 0 0 5. Further, in relation to the obtained surface-modified lithium-containing composite oxide particles, when the atomic ratio (Ti/N) of the surface of the lithium-containing composite oxide particles was measured by XPS analysis in the same manner as in Example 1, (Ti/N) ) =1. 50. In addition, the amount of lithium ion elution is 0. 29 moles %. # As described above, in the IR spectrum of Fig. 1, since there is a strong absorption peak in the range of 1 3 00 to 1 700 CHT1, it is known that the surface layer of the surface-modified lithium composite oxide has carbon- A carbon compound having an oxygen double bond is present. Further, as is apparent from Fig. 2, the titanium lactate was subjected to a decomposition reaction at 300 to 45 ° C, and the decomposition reaction was almost completed at 500 °C. In addition, in the surface layer of the surface-modified lithium-containing composite oxide particles synthesized by heat treatment at 3 50 ° C in Example 2, a carbon compound was present. Further, it is understood that a partial thermal decomposition product of a carbon-containing titanium complex compound using a carbon compound as a raw material of -25 - 200818581 is used. The positive electrode sheet was prepared and evaluated in the same manner as in Example 1 except that the composite oxide containing the surface-modified lithium was used. As a result, at 25 ° C, 2 · 5 ~ 4. The initial weight capacity density of the positive active material of 3 V was 159 mAh/g, and the capacity retention rate after 30 charge and discharge cycles was 9 8. 3 %. In addition, at 25 ° C, 2. 5~4. The initial weight capacity density of the positive active material of 5 V was 175 mAh/g, and the capacity retention rate after 25 charge and discharge cycles was 9 5. 1 %. Further, the temperature was raised at a rate of 5 ° C /min using a scanning differential calorimeter, and the result of the heat generation start temperature was measured. The heating start temperature of the 3V charging product has a heating start temperature of 23 5 °C, 4. The heating start temperature of the 5V charging product is 200 〇C. [Example 3] Φ In the same manner as in Example 1, a lithium-containing composite oxide having a composition of a base material was synthesized. Then, the titanium content at 6 · 0 5 g is 8. 2% by weight of aqueous lactate solution was added to 43. 95 g of water was prepared to prepare a Ti aqueous solution of pH 値2. The above base material was immersed in 50 g of the above Ti aqueous solution, and then slowly mixed to obtain a mixed powder. Further, the mixed powder was dried at 120 ° C for 4 hours to obtain a titanium complex impregnated particles. The dried coordinating compound impregnated particles are heated in an oxygen-containing gas atmosphere at 350 ° C for 12 hours, and the average particle diameter is 10. 7μιη, D10 is 6. 1μπι, D90 is -26- 200818581 15·〇μιη, specific surface area is 0. The surface-modified lithium composite oxide particles of the present invention having a spherical shape of about 5 m 2 /g. The X-ray diffraction spectrum of the obtained surface-modified lithium-containing composite oxide particles was measured in the same manner as in Example 1. In the powder X-ray diffraction using the CuKa line, the diffraction peak width of the (110) plane of 2Θ = 65·1±Γ is 0. 230. . The pressed density of the particles is 2. 69g/cm3. Further, the titanium contained in the entire surface-modified lithium-containing compound particles has an atomic ratio of 0 to a total of nickel, manganese and cobalt. 01. In addition to the above-mentioned τ, the obtained surface-modified lithium-containing composite oxide particles were measured for the atomic ratio (Ti/N) of the surface of the lithium-containing composite oxide particles by XPS analysis in the same manner as in Example 1 (Ti /N) =3. 30. In addition, the amount of lithium ion elution is 0. 38 moles %. The positive electrode sheet was prepared and evaluated in the same manner as in Example 1 except that the composite oxide containing the surface-modified lithium was used. As a result, at 25 ° C, 2 · 5 ~ 4. The initial weight capacity density of the 3V positive electrode active material was 157 mAh/g, and the capacity retention rate after 30 charge and discharge cycles was 98. 2%. In addition, at 25 ° C, 2. 5~4. The initial weight capacity density of the positive active material of 5 V was 173 mAh/g, and the capacity retention rate after performing 25 charge and discharge cycles was 95. 1%. In addition, the temperature of the heating start temperature was measured by a scanning differential calorimeter at a rate of 5 ° C / min. The heating start temperature of the 3 V charging product is 234 ° C, 4. The heating start temperature of the 5V rechargeable product is 2 01〇C. -27- 200818581 [Example 4] In the same manner as in Example 1, the synthetic base material has LiuHNimComMm/Do. A lithium-containing composite oxide composed of MC^. The base material has an average particle size of 1 〇.  5 μιη and D10 are 5. 3μιη, D90 is 1 3. 5 μιη, specific surface area is 0. 4 9 m2 / g of the primary particles are mostly agglomerated and formed into particles of secondary particles. About the composite oxide particles, an X-ray diffraction spectrum was prepared using an X-ray diffraction apparatus (RINT 2100, manufactured by Rigaku Corporation). In the powder X-ray diffraction using the CuKa line, the diffraction peak width of the (110) plane of 2Θ = 65·1 soil 1° is 0. 225°. The pressed density of the particles is 2. 70g/cm3. Further, in the case of the lithium-containing composite oxide particles of the above-mentioned base material, when surface element analysis was carried out by XPS analysis in the same manner as in Example 1, titanium was not detected. Further, as described above, in the IR spectrum of Fig. 1, since the absorption peak is strong in the range of 1 3 00 to 1 700 CHT1, it is understood that the composite oxide of lithium is free of carbon having a carbon-oxygen double bond. Compound. Using a lithium-containing composite oxide particle of a base material, a positive electrode sheet was produced in the same manner as in Example 1, and a battery was assembled for evaluation. As a result, the initial weight capacity density of the positive electrode active material at 25 ° C and 2 · 5 to 4 · 3 V was 160 mAh/g, and the capacity retention rate after 30 charge and discharge cycles was 9 5. 0%. Further, the initial weight capacity density of the positive electrode active material at 25 ° C and 2 · 5 to 4 · 5 V was 1 75 mAh/g, and the capacity retention rate after performing 25 charge and discharge cycles was 9 1. 0%. -28- 200818581 In addition, the temperature of the heating start temperature was measured by a scanning differential calorimeter at a rate of 5 ° C / min. The heating start temperature of the 3V charging product is 232 ° C, 4. The heating start temperature of the 5V rechargeable product is 199 〇C 〔 [Example 5] Same as Example 1 "The synthetic base material has Lii. G2 (Nii/3C〇i/3Mni/3) G. A lithium-containing composite oxide composed of 98〇2. Then, in 〇. 〇6g titanium content is 8. 2% by weight of aqueous titanium lactate solution was added to 49. 94g water, modulation! )11値2. 5 of 14 aqueous solution. The above base material was immersed in 50 g of the above Ti aqueous solution, and then slowly mixed to obtain a mixed powder. Further, the mixed powder was dried at 1, 20 ° C for 4 hours to obtain a titanium complex impregnated particles. The dried coordination compound impregnated particles were heated in an oxygen-containing gas atmosphere at 3 50 ° C for 12 hours, and the average particle diameter was 10. 4μιη, D10 is 5. 0μηι, D90 is 14. 1μιη, specific surface area is 0. The surface-modified lithium composite oxide particles of the present invention having a spherical shape of about 48 m 2 /g. The X-ray diffraction spectrum of the obtained surface-modified lithium-containing composite oxide particles was measured in the same manner as in Example 1. In the powder X-ray diffraction using the CuKa line, 2Θ = 65. 1 士 1. The diffraction peak width of the (110) plane is 0. 224. . The pressed density of the particles is 2. 70g/cm3. Further, the titanium contained in the entire surface-modified lithium-containing compound particles has an atomic ratio of 0 to a total of nickel, manganese and cobalt. 0 0 0 1. Further, in the case of the obtained surface-modified lithium-containing composite oxide particles, -29-200818581, when the atomic ratio (Ti/N) of the surface of the lithium-containing composite oxide particles is measured by XPS analysis in the same manner as in Example 1, (Ti/N ) =0. 18. In addition, the amount of lithium ion elution is 0. 20 moles %. The positive electrode sheet was prepared and evaluated in the same manner as in Example 1 except that the composite oxide containing the surface-modified lithium was used. ‘ Result, at 25°c, 2. 5~4. The initial weight capacity density of the positive active material of 3 V was 160 mAh/g, and the capacity after the 30 charge and discharge cycles was maintained at φ rate of 9. 2 %. In addition, at 25 ° C, 2. 5~4. The initial weight capacity density of the positive active material of 5 V was 173 mAh/g, and the capacity retention rate after the charge and discharge cycle of 25 times was 91. 2%. Further, the temperature was raised at a rate of 5 ° C /min by a scanning type differential calorimeter, and the result of the heat generation start temperature was measured. The heating start temperature of the 3 V charging product is 234 ° C, 4. The heating start temperature of the 5V rechargeable product is 201 °C ° [Example 6] 197. The average particle size of 18g is 12. ; ^ 111, cobalt content is 61. 0% by weight of cobalt hydroxide, 〇·16 g of aluminum hydroxide, 〇·1 2 g of magnesium hydroxide, mixed with '75·91§ lithium carbonate powder having a specific surface area of I2m2/g, in an oxygen-containing gas environment After firing at 990 ° C for 14 hours, it was prepared by disintegration to obtain LUCoojw AluHMg. (4) A base material composed of a lithium-containing composite oxide composed of 1). Then 'in the 〇. 〇6g titanium content is 8. 2% by weight of aqueous titanium lactate -30- 200818581 50 g of water was added to prepare a Ti aqueous solution of pH 値2.5. One 〇〇g of the above-mentioned base material was immersed in the above Ti aqueous solution, and then slowly mixed to obtain a mixed powder. Further, the mixed powder was dried at 120 ° C for 4 hours to obtain a titanium complex impregnated particle. The dried coordination compound impregnated particles were heated in an oxygen-containing gas atmosphere at 3 50 ° C for 12 hours, and the average particle diameter was 12·0 μιη, and D10 was 6. 7μπι, D90 is 18·8μχη, and the specific surface area is 0. The surface-modified lithium composite oxide particles of the present invention having a spherical shape of about 25 m 2 /g. The X-ray diffraction spectrum of the obtained surface-modified lithium-containing composite oxide particles was measured in the same manner as in Example 1. In the powder X-ray diffraction using the CuKa line, 2Θ = 66. 5±1. The diffraction peak width of the (110) plane is 0. 108. . The pressed density of the particles is 3. 0 2 g/cm3. Further, the titanium contained in the entire surface-modified lithium-containing compound particles has an atomic ratio of 0 to a total of nickel, manganese and cobalt. 0 0 1. Further, in relation to the obtained surface-modified lithium-containing composite oxide particles, when the atomic ratio (Ti/N) of the surface of the lithium-containing composite oxide particles was measured by XPS analysis in the same manner as in Example 1, (Ti/N) ) =1. 26. In addition, the amount of lithium ion elution is 0. 09 mole%. The positive electrode sheet was prepared and evaluated in the same manner as in Example 1 except that the composite oxide containing the surface-modified lithium was used. As a result, at 25 ° C, 2. 5~4. The initial weight capacity density of the positive active material of 3 V was 157 mAh/g, and the capacity retention rate after 30 charge and discharge cycles was 99. 8%. In addition, at 25 ° C, 2. 5~4. The initial weight of the positive active material of 5V is 200818581. The capacity density is 184mAh/g, and the capacity retention rate after performing 25 charge and discharge cycles is 97. 0%. Further, the temperature was raised at a rate of 5 ° C /min by a scanning type differential calorimeter, and the result of the heat generation start temperature was measured. The heating temperature of the 3V charging product has a heating start temperature of 158 ° C, 4. The heating start temperature of the 5V rechargeable product is 146 〇 C ° [Example 7] Make 1 96. The average particle size of 99g is 12. Ιμηι, cobalt content is 61. 0% by weight of cobalt hydroxide, 0. 1 6g aluminum hydroxide, 0. 12g magnesium hydroxide, and 〇. 16g titanium oxide, 75. 91g specific surface area is 1. 2m2/g of lithium carbonate powder is mixed and fired in an oxygen-containing gas atmosphere at 990 °C for 14 hours, and then obtained by containing Li(C〇〇. 997Al〇. 〇〇iMg(). 〇()iTi〇. 含i) A lithium-containing composite oxide composed of 〇2. The lithium-containing composite oxide has an average particle diameter of 1 〇. 3μιη, D10 is 6. 4μιη, D90 is 1 5 · 4μπι, and the specific surface area is 0. About 26 m 2 /g of a spherical shape X The X-ray diffraction spectrum of the obtained surface-modified lithium-containing composite oxide particles was measured in the same manner as in Example 1. Use the powder of the CuKot line. In the X-ray diffraction, the width of the diffraction peak of the (110) plane is 2Θ = 66·5. 097. . The pressed density of the particles is 3. 0 9 g/cm3. Further, the titanium contained in the entire surface-modified lithium-containing material particles has an atomic ratio of 0 to a total amount of cobalt, aluminum, magnesium, and titanium. 001. Further, in the case of the obtained surface-modified lithium-containing composite oxide particles, -32-200818581, when the atomic ratio (Ti/N) of the surface of the lithium-containing composite oxide particles was measured by XPS analysis in the same manner as in Example 1, (Ti/N ) =0. 15. In addition, the amount of lithium ion elution is 0. 1 0% by mole. The positive electrode sheet was prepared and evaluated in the same manner as in Example 1 except that the composite oxide containing the surface-modified lithium was used. * The result is at 2 5 °C, 2 · 5~4. The initial weight capacity density of the positive electrode active material of 3 V was 159 mAh/g, and the capacity after the 30 charge and discharge cycles was maintained at φ rate of 9 6 · 9 %. In addition, at 2 5 °C, 2. 5~4. The initial weight capacity density of the positive active material of 5 V was 185 mAli/g, and the capacity retention rate after 25 charge and discharge cycles was 8 3. 0%. Further, the temperature was raised at a rate of 5 ° C /min by a scanning type differential calorimeter, and the result of the heat generation start temperature was measured. The heating start temperature of the 3V charging product is 1S5°C, 4. The heating start temperature of the 5V rechargeable product is 145 〇C. [Example 8] At 51. In the water of 03g, 1. 20 g of magnesium hydroxide was dispersed, stirred, and dissolved in a small amount of 5 · 4 6 g of citric acid. Then, join 1 2. 3 1 g of a 4 % by weight aluminum aluminum lactate aqueous solution was mixed to prepare an aqueous solution (Al-Mg solution) containing aluminum and magnesium. Make 1 96. 62g average particle size is 12·0μχη, and the content of Ming is 60. In the case of the above-mentioned A1 - M g, it is easy to carry out impregnation and mixing, and drying at 120 ° C for 4 hours to obtain a carbonyl-33-200818581 cobalt hydroxide powder containing aluminum and magnesium. By making 77. 72g specific surface area is 1. 2 m 2 /g of lithium carbonate powder was mixed with the above-mentioned aluminum and magnesium cobalt oxyhydroxide powder, and fired in an oxygen-containing gas atmosphere at 990 ° C for 14 hours, and then pulverized to obtain Lil. G2 (C〇G. 98Al〇. 〇lMg〇 ()l)G. A block-shaped composite oxide having a composition of 98 〇 2 is used as a base material. Then, in 〇. Add 6g of water to 6g of magnesium hydroxide, stir and add a small amount of bismuth. 14 g of citric acid was dissolved. Then, join 0. 06g titanium contains - the amount is 8. 2% by weight of an aqueous solution of titanium lactate, adjusted to pH 値 2. An aqueous solution containing magnesium and titanium (Mg-Ti aqueous solution). After 100 g of the above-mentioned base material was immersed in the above Mg-Ti aqueous solution, it was slowly mixed to obtain a mixed powder. Further, the mixed powder was dried at 120 ° C for 4 hours to obtain a magnesium-titanium complex compound impregnated particles. The dried coordination compound impregnated particles were heated in an oxygen-containing gas atmosphere at 40 ° C for 12 hours, and the average particle diameter was 12·6 μιη, and D10 was 6. 8μιη, D90 is 19·0μιη, and the specific surface area is 0. About 30 m 2 /g of a spherical composite oxide particle containing surface-modified lithium. The X-ray diffraction spectrum of the obtained surface-modified lithium-containing composite oxide particles was measured in the same manner as in Example 1. In the powder X-ray diffraction using the CuKa line, 2Θ = 6 6. 5 The radius of the diffraction peak of the (110) plane is 0. 108. . The pressed density of the particles is 3. 03 g/cm3. Further, the magnesium and titanium contained in the entire surface-modified lithium-containing material particles have an atomic ratio of 0 to a total of cobalt, aluminum and magnesium. 002. Further, the titanium contained in the entire composite oxide particles containing surface-modified lithium is -34-200818581 W in a total amount of cobalt, aluminum and magnesium, and the atomic ratio is 0. 0 0 1. Further, in relation to the obtained surface-modified lithium-containing composite oxide particles, when the atomic ratio (Ti/N) of the surface of the lithium-containing composite oxide particles was measured by XPS analysis in the same manner as in Example 1, (Ti/N) ) = 1 · 1 7. In addition, the amount of lithium ion elution is 0. 20 moles %. The positive electrode sheet was prepared and evaluated in the same manner as in Example 1 except that the composite oxide containing the surface-modified lithium was used. As a result, at 25 ° C, 2. 5~4. The initial weight capacity density of the positive active material of 3 V was 151 mAh/g, and the capacity retention rate after 30 charge and discharge cycles was 9 9. 5 %. In addition, at 25 ° C, 2. 5~4. The initial weight capacity density of the positive active material of 5 V was 178 mAh/g, and the capacity retention rate after 25 charge and discharge cycles was 9. 2 %. In addition, the temperature was raised at a rate of 5 ° C /min using a scanning differential calorimeter, and the result of the heat start temperature was measured. The heating temperature of the 3V charging product has a heating start temperature of 159 ° C, 4. The heating start temperature of the 5V rechargeable product is 147〇C. [Example 9] 0 in 50 g of water. 06g of magnesium hydroxide was dispersed, stirred and added to each other in a small amount of 0. 14 g of citric acid was dissolved, and the pH was adjusted to 4. 0 mg of water solution. By making l〇〇g the Lii synthesized in Example 8. G2 (C〇Q. 98AlG, () iMg〇. ()i)(). The lithium-containing composite oxide having a composition of 98 Å was immersed in the above Mg aqueous solution, and slowly mixed at a slow -35 - 200818581 to obtain a mixed powder. Further, the mixed powder was dried at 120 ° C for 4 hours to obtain a magnesium complex impregnated particles. The dried coordination compound impregnated particles were heated in an oxygen-containing gas atmosphere at 400 ° C for 12 hours, and the average particle diameter was 11.8 μm and D10 was 6. 6μιη, D90 ' is 17·8μπι, and the specific surface area is 〇. A spherical surface repair of 23 m2/g.  A composite oxide particle decorated with lithium. The X-ray diffraction spectrum of the obtained surface-modified lithium-containing composite oxide particles was measured in the same manner as in Example 1 φ. Using the powder X-ray diffraction of the CuKa line, 20 = 66. 5 士1. The diffraction peak width of the (110) plane is 0. 10-4. . The pressed density of the particles is 3. 06g/cm3. Further, the magnesium contained in the entire surface-modified lithium-containing material particles has an atomic ratio of 0 for cobalt. 001 〇 In addition, the obtained surface-modified lithium-containing composite oxide particles were not detected in the surface element analysis by XPS analysis in the same manner as in Example 1. Moreover, the amount of lithium ion elution is 0. 24 moles %. • The positive electrode sheet was prepared and evaluated in the same manner as in Example 1 except that the composite oxide containing the surface-modified lithium was used. As a result, at 25 ° C, 2. 5~4. The initial weight capacity density of the 3V positive active material was 15 ImAh/g, and the capacity retention rate after 30 charge and discharge cycles was 9 9. 0%. In addition, at 25 ° C, 2. 5~4. The initial weight capacity density of the positive active material of 5 V was 1 80 m Ah/g, and the capacity retention rate after 25 charge and discharge cycles was 9 2. 5 %. In addition, the temperature of the starting temperature of the heat was measured by a scanning differential calorimeter at a rate of 5 ° C / min. The heating temperature of the 3V charging product has a heating start temperature of 154 ° C, 4. The heat generation start temperature of the 5V charge product was 144 ° C ° [Example 10] The lithium carbonate powder was mixed in a predetermined amount in the composite carbonyl hydroxide powder obtained in Example 1, and fired and pulverized in the same manner as in Example 1. A lithium-containing composite oxide having a composition of a synthetic base material. Then, in 〇. 61g titanium content is 8. 2% by weight of aqueous titanium lactate solution was added to 49. 3 9g water, modulating pH 値2. 1 Ti aqueous solution. 100 g of the above base material was immersed in 50 g of the above Ti aqueous solution, and then slowly mixed to obtain a mixed powder. Further, the mixed powder was dried at 120 ° C for 4 hours to obtain a titanium complex impregnated particles. The dried coordination compound impregnated particles are heated in an oxygen-containing gas atmosphere at 40 ° C for 12 hours, and the average particle diameter is ΙΙ. Ομηι, D10 is 6. 3μηι, D90 is 15·5μιη, and the specific surface area is 0. The composite oxide particles of the surface-modified lithium of the present invention having a spherical shape of about 49 m 2 /g. The X-ray diffraction spectrum of the obtained surface-modified lithium-containing composite oxide particles was measured in the same manner as in Example 1. Using the powder X-ray diffraction of the CuKa line, 20 = 65. 1 soil 1. The diffraction peak width of the (110) plane is 0. 199. . The pressed density of the particles is 2. 67g/cm3. Further, the titanium contained in the entire surface-modified lithium-containing material particles has an atomic ratio of 〇· 〇 〇 1 for the total amount of nickel, manganese and cobalt. Further, in the case of the obtained surface-modified lithium-containing composite oxide particles, the atomic ratio (Ti/N) of the surface of the lithium-containing composite oxide particles was measured by xps analysis in the same manner as in Example 1. (Ti/N) = 〇·7. In addition, the amount of lithium ion elution is 0. 38 moles %. The positive electrode sheet was prepared and evaluated in the same manner as in Example 1 except that the composite oxide containing the surface-modified lithium was used. As a result, at 2 5 °C, 2. 5~4. The initial weight capacity density of the positive active material of 3 V was 157 mAh/g, and the capacity retention rate after 30 charge and discharge cycles was 9 8. 5 %. In addition, at 25 ° C, 2. 5~4. The initial weight capacity density of the positive active material of 5 V was 173 mAh/g, and the capacity retention rate after the 25 charge and discharge cycles was 94. 5%. Further, the temperature was raised at a rate of 5 ° C /min by a scanning type differential calorimeter, and the result of the heat generation start temperature was measured. The heating start temperature of the 3V charging product has a heating start temperature of 231 °C, 4. The heating start temperature of the 5V charge product was 200 °C. [Example 11] A lithium-containing composite oxide having a composition of the base material was synthesized in the same manner as in Example 10. The average particle size of the base metal is 10. 8 μπι, D10 is 6·1μπι, and D90 is 1 5 .  1 μηι, specific surface area is 0. A powder of a primary particle of 47 m 2 /g which is mostly agglomerated and forms a secondary particle. About the composite oxide particles, an X-ray diffraction spectrum was prepared using an X-ray diffraction apparatus (RINT 2100, manufactured by Rigaku Corporation). In the powder X-ray diffraction of CuKa -38- 200818581 line, the diffraction wavelength of the (110) plane of the 2Θ = 65·1 soil is half the width of the peak. 197°. The pressed density of the particles is 2. 70g/cm3. Further, in the case of the lithium-containing composite oxide particles of the above-mentioned base material, when surface element analysis was carried out by XPS analysis in the same manner as in Example 1, titanium was not detected. Using the lithium-containing composite oxide particles of the above-mentioned base material, a positive electrode was prepared in the same manner as in Example 1, and a battery was assembled and evaluated. As a result, at 2 5 °C, 2. The initial weight capacity density of the positive electrode active material of 5 to 4 · 3 V was 1 59 nrAh/g, and the capacity retention rate after 30 charge and discharge cycles was 94. 9%. In addition, at 25 ° C, 2. 5~4. The initial weight capacity density of the positive active material of 5 V was 174 mAh/g, and the capacity retention rate after 25 charge and discharge cycles was 90. 0%. Further, the temperature was raised at a rate of 5 ° C /min by a scanning type differential calorimeter, and the result of the heat generation start temperature was measured. The heating start temperature of the 3V charging product is 23 0 ° C, and the heating start temperature of the 4·5 V charging product is 198 ° C ° [Example 1 2] The ratio of each element containing nickel, cobalt and manganese is adjusted to NkC. (KMn = 0. 50:0. 20:0. The nickel sulfate of 30 is mixed with the sulfate of cobalt sulfate and manganese sulfate. The aqueous solution, the aqueous solution of ammonium sulfate and the aqueous sodium hydroxide solution are used to make the pH of the slurry in the reaction tank to be 11. 0, stirring was carried out at a temperature of 50 ° C and each was continuously supplied to the reaction tank. The amount of liquid in the reaction system was adjusted by an excessive flow method, and the coprecipitated slurry flowing through -39 - 200818581 was filtered, washed with water, and then dried at 80 ° C to obtain a nickel-cobalt-manganese composite hydroxide powder. . Next, the nickel-cobalt-manganese composite carbonyl hydroxide slurry was synthesized by dispersing the composite hydroxide powder in a 6% by weight aqueous sodium persulfate solution containing 3% by weight of sodium hydroxide and stirring at 20 ° C for 12 hours. . Further, the composite carbonyl hydroxide slurry was filtered, washed with water, and then dried to obtain a composite carbonyl hydroxide powder. The composite carbonyl hydroxide powder has a specific surface area of 9. 4m2 / g, the average particle size is 9. 5μπι. The lithium carbonate powder having an average particle diameter of 20 μm was mixed in the composite carbonyl hydroxide powder thus obtained, and calcined in an oxygen-containing gas atmosphere at 970 ° C for 12 hours, and then pulverized. It is made to contain Lh. oKNio. sCoo. iMno. Oo. A base material composed of a lithium-containing composite oxide composed of ^C^. Regarding the base material, when the powder was further measured by the CuKa line and the diffraction spectrum of the powder, it was found to be a similar structure of the surface system (R-3m). Further, the RINT 2 100 model manufactured by Rigaku Corporation was used for the measurement. Regarding the particles of the base material powder, when the SEM observation is performed, most of the primary particles agglomerate to form secondary particles, and the shape thereof is approximately spherical or elliptical. Second, then, in 〇. 60g titanium content is 8. 2% by weight of titanium lactate aqueous solution was added 49. 40g water, modulating pH値2. 1 Ti aqueous solution. The above base material was immersed in 50 g of the above Ti aqueous solution, and then slowly mixed to obtain a mixed powder. Further, the mixed powder was dried at 120 ° C for 4 hours to obtain a titanium complex impregnated particles. The dried coordination compound impregnated particles are heated in an oxygen-containing gas atmosphere at 350 ° C for 12 hours, the average particle diameter is 9·2 μπι, D10 is 5·2 μιη, and D90 is -40-200818581 15· 0μιη, specific surface area is 0. The composite oxide particles of the surface-modified lithium of the present invention having a spherical shape of about 52 m 2 /g. The X-ray diffraction spectrum of the obtained surface-modified lithium-containing composite oxide particles was measured in the same manner as in Example 1. In the powder X-ray diffraction using the CuKoi line, 2Θ = 65. The diffraction peak width of the (±1) (110) plane is 0. 13 9. . The pressed density of the particles is 2. 65g/cm3. Further, the titanium contained in the entire surface-modified lithium-containing compound particles has an atomic ratio of 0 to a total of nickel, manganese and cobalt. 001. Further, in relation to the obtained surface-modified lithium-containing composite oxide particles, when the atomic ratio (Ti/N) of the surface of the lithium-containing composite oxide particles was measured by XPS analysis in the same manner as in Example 1, (Ti/N) ) =0. 69. In addition, the amount of lithium ion elution is 0. 59 moles %. The positive electrode sheet was prepared and evaluated in the same manner as in Example 1 except that the composite oxide containing the surface-modified lithium was used. As a result, at 25 ° C, 2. 5~4. The initial weight capacity density of the 3V positive electrode active material was 165 mAh/g, and the capacity retention rate after 30 charge and discharge cycles was 9.7 5%. Further, the temperature was raised at a rate of 5 ° C /min by a scanning type differential calorimeter, and the result of the heat generation start temperature was measured. The heating start temperature of the 3V charging product is 2〇2°C. [Example 1 3] In the same manner as in Example 12, the synthetic base material had Lii. Gi (NiG. 5C〇G. 2Mn(). 3) (). A lithium-containing composite oxide composed of 99〇2. The average particle size of the base metal is 8. 9Pm, -41 - 200818581 D10 is 5. A powder of 0 μιη, D90 of 1 4 · 9 μιη, and a specific surface area of Ο · 50 m 2 /g, in which primary particles are mostly agglomerated and particles of secondary particles are formed. With respect to the composite oxide particles, an X-ray diffraction spectrum was obtained using an X-ray diffraction apparatus (RINT 2 100 manufactured by Rigaku Corporation). In the powder X-ray diffraction using the CuKa line, 2Θ = 65. The diffraction peak of the (1) ( (110) plane has a half-turn width of 0. 135°. The pressed density of the particles is 2. 69g/cm3. Further, in the case of the lithium-containing composite oxide particles of the above-mentioned base material, when surface element analysis was carried out by XPS analysis in the same manner as in Example 1, titanium was not detected. Using the lithium-containing composite oxide particles of the above-mentioned base material, a positive electrode body was produced in the same manner as in Example 1, and a battery was assembled and evaluated. As a result, at 25 ° C, 2 · 5 ~ 4. The initial weight capacity density of the positive active material of 3 V was 168 mAh/g, and the capacity retention rate after 30 charge and discharge cycles was 9 6. 0%. In addition, the temperature of the heating start temperature was measured by a scanning differential calorimeter at a rate of 5 ° C / min. The heat generation curve of the 3 V charging product has a heating start temperature of 201 °C. [Example 1 4] The ratio of each element containing nickel, cobalt and manganese is adjusted to Ni: Co: Mn = 03 5:0. 40:0. 25 aqueous solution of nickel sulfate and cobalt sulfate and manganese sulfate mixed with water, ammonium sulfate aqueous solution and aqueous sodium hydroxide solution, so that the pH of the slurry in the reaction tank is 11. 0. The temperature was 50 ° C and the mixture was continuously supplied to the reaction tank. The amount of liquid in the reaction system was adjusted by an excessive flow method, and the coprecipitated slurry flowing in excess of -42 - 200818581 was filtered, washed with water, and then dried at 80 ° C to obtain a nickel-cobalt-manganese composite hydroxide powder. Next, the nickel-cobalt-manganese composite carbonyl hydroxide slurry was synthesized by dispersing the composite hydroxide powder in a 6% by weight aqueous solution of sodium persulfate containing 3% by weight of sodium hydroxide and stirring at 20 ° C for 12 hours. material. Further, the composite carbonyl hydroxide slurry was filtered, washed with water, and then dried to obtain a composite carbonyl hydroxide powder. The composite carbonyl hydroxide powder has a specific surface area of 9. 4m2 / g, the average particle size is 9. 5μπι. The lithium carbonate powder having an average particle diameter of 20 μm was mixed in the composite carbonyl hydroxide powder thus obtained, and calcined in an oxygen-containing gas atmosphere at 990 ° C for 12 hours, and then pulverized. It is made of LiKNimCOo. 4 (^11(). 25) (). A base material composed of a lithium-containing composite oxide composed of 9902. Regarding the base material, when the powder X-ray diffraction spectrum was measured using a CuKa line, it was found to be a similar structure of the surface system (R-3m). Further, RINT 2 00 type manufactured by Rigaku Electric Co., Ltd. was used for the measurement. When the particles of the base material powder are observed by SEM, most of the primary particles are agglomerated to form secondary particles, and the shape thereof is approximately spherical or elliptical. Second, then, in 〇. 60g titanium content is 8. 2 wt% of titanium lactate aqueous solution was added 49. 40 g of water to prepare pH 値 2. 1 Ti aqueous solution. The mixed powder was prepared by immersing the above-mentioned base material in 5 (1 of the above aqueous solution), and then mixing the mixture to prepare a mixed powder at 120 ° C for 4 hours to obtain a titanium compound. The compound is impregnated with particles. The dried coordination compound impregnated particles are heated in an oxygen-containing gas atmosphere at 350 ° C for 12 hours, and the average particle size is ΙΟ. Ιμηι, D10 is 5. 0μπι, D90 -43- 200818581 is 14·1μπι, and the specific surface area is 0. The surface-modified lithium composite oxide particles of the present invention having a spherical shape of about 46 m 2 /g. The X-ray diffraction spectrum of the obtained surface-modified lithium-containing composite oxide particles was measured in the same manner as in Example 1. In the powder X-ray diffraction using the CiiKa line, the diffraction peak width of the (110) plane of 2Θ = 65·1±Γ is 0. twenty two. . The pressed density of the particles is 2. 72g/cm3. Further, the titanium contained in the entire surface-modified lithium-containing compound particles has an atomic ratio of 0 to a total of nickel, manganese and cobalt. 0 0 1. Further, in relation to the obtained surface-modified lithium-containing composite oxide particles, when the atomic ratio (Ti/N) of the surface of the lithium-containing composite oxide particles was measured by XPS analysis in the same manner as in Example 1, (Ti/N) ) =0·72. In addition, the amount of lithium ion elution is 0. 35 moles %. The positive electrode sheet was prepared and evaluated in the same manner as in Example 1 except that the composite oxide containing the surface-modified lithium was used. As a result, at 25 ° C, 2. 5~4. The initial weight capacity density of the 3V positive electrode active material was 153 mAh/g, and the capacity retention rate after 30 charge and discharge cycles was 9.7 3%. Further, the temperature was raised at a rate of 5 ° C /min by a scanning type differential calorimeter, and the result of the heat generation start temperature was measured. The heating start temperature of the 3V charging product has a heating start temperature of 1 9 1 °C. [Example 1 5] In the same manner as in Example 14, the synthetic base material had Lii. oKNio. A lithium-containing composite oxide composed of hCocMoMnuOGMCb. The average particle size of the base material is 9·9 μηι, -44- 200818581 D10 is 4·9 μπι, D90 is 13·9 μπι, and the specific surface area is 0. A powder of a primary particle of 40 m 2 /g which is mostly agglomerated and forms a secondary particle. With respect to the composite oxide particles, an X-ray diffraction spectrum was prepared using an X-ray diffraction apparatus (RINT 2100 manufactured by Rigaku Corporation). In the powder X-ray diffraction using the CuKa line, 2 Θ = 65·1 ± 1. The diffraction peak of the (110) plane has a half-turn width of 0. 219°. The pressed density of the particles is 2. 75g/cm3. Further, in the lithium-containing composite oxide particles of the above-mentioned base material, when surface element analysis was carried out by XPS analysis in the same manner as in Example 1, titanium was not detected. Using the lithium-containing composite oxide particles of the above-mentioned base material, a positive electrode body was produced in the same manner as in Example 1, and a battery was assembled and evaluated. As a result, at 25 ° C, 2. 5~4. The initial weight capacity density of the positive active material of 3 V was 155 mAh/g, and the capacity retention rate after 30 charge and discharge cycles was 9 6. 0%. In addition, the temperature was raised by a scanning differential calorimeter at a rate of 5 t:/min, and the result of the heat start temperature was measured. The heat generation curve of the 3V charging product has a heating start temperature of 190 °C. [Example 1 6] The ratio of each element containing nickel, Ming and 锸 is adjusted to N i: C 〇 : Μ η = 〇·3 0:0. 30:0. The nickel sulfate of 40 is mixed with the sulfate of cobalt sulfate and manganese sulfate. The aqueous solution, the aqueous solution of ammonium sulfate and the aqueous solution of sodium hydroxide are used to make the slurry of the slurry in the reaction tank 1 . 0, the temperature was stirred at 5 ° C and each was continuously supplied to the reaction tank. The amount of liquid in the reaction system was adjusted by excessive flow, and the coprecipitated slurry flowing through -45-200818581 was filtered, washed with water, and then dried at 8 〇t: to obtain nickel-cobalt-manganese composite hydroxide. powder. Next, the nickel-cobalt-manganese composite carbonyl hydroxide was synthesized by dispersing the composite hydroxide powder in a 6% by weight aqueous solution of sodium persulfate containing 3% by weight of sodium hydroxide and stirring at 20 ° C for 12 hours. Slurry. Further, the composite carbonyl hydroxide slurry was filtered, washed with water, and then dried to obtain a composite carbonyl hydroxide powder. The composite carbonyl hydroxide powder has a specific surface area of l〇. 8m2 / g, the average particle size is 9. 0μπι. The lithium carbonate powder having an average particle diameter of 20 μm was mixed in the composite carbonyl hydroxide powder thus obtained, and calcined in an oxygen-containing gas atmosphere at 95 ° C for 12 hours, and then pulverized. A base material composed of a lithium-containing composite oxide having a composition is prepared. Regarding the base material, when the powder X-ray diffraction spectrum was measured using a CxiKa line, it was found to be a similar structure of the surface system (R-3m). Further, the RINT 2100 model manufactured by Rigaku Corporation was used for the measurement. When the particles of the base material powder were observed by SEM, most of the primary particles agglomerated into secondary particles, and the shape thereof was approximately spherical or elliptical. Second, then, in 〇. 61g titanium content is 8. 2% by weight of titanium lactate aqueous solution was added 49. 3 9 g of water, and a Ti aqueous solution of pH 値 2·1 was prepared. 100 g of the above-mentioned base material was immersed in 50 g of the above Ti aqueous solution, and then slowly mixed to obtain a mixed powder. Further, the mixed powder was dried at 120 ° C for 4 hours to obtain a titanium complex impregnated particles. The dried coordination compound impregnated particles are heated in an oxygen-containing gas atmosphere at 350 ° C for 12 hours, the average particle diameter is 9·0 μπι, D10 is 4·5 μπι, and D90 is -46-200818581 14 . 8μπι, specific surface area is 〇. The composite oxide particles of the surface-modified lithium of the present invention having a spherical shape of about 65 m 2 /g. The X-ray diffraction spectrum of the obtained surface-modified lithium-containing composite oxide particles was measured in the same manner as in Example 1. Using the powder X-ray diffraction of the CuKa line, 20 = 65. The diffraction peak width of the 1±1° (11〇) plane is 〇. 272°. The pressed density of the particles is 2. 5 1 g/cm3. Further, the yttrium contained in the entire surface of the surface-modified lithium-containing compound particles has an atomic ratio of 0 for nickel, manganese, and mineralization. 00 1. Further, the obtained surface-modified lithium-containing composite oxide particles t were measured for the atomic ratio (Ti/N) of the surface of the lithium-containing composite oxide particles by XPS analysis in the same manner as in Example 1, (Ti/N). ) =0. 70. In addition, the amount of lithium ion elution is 0. 3 7 moles %. The positive electrode sheet was prepared and evaluated in the same manner as in Example 1 except that the composite oxide containing the surface-modified lithium was used. As a result, at 25 ° C, 2. 5~4. The initial weight capacity density of the 3V positive active material was 140 mAh/g, and the capacity retention rate after 30 charge and discharge cycles was 9 7. 8 %. Further, the temperature was raised at a rate of 5 ° C /min by a scanning type differential calorimeter, and the result of the heat generation start temperature was measured. The heating start temperature of the 3V charging product has a heating start temperature of 240 °C. [Example 1 7] • In the same manner as in Example 16, the synthetic base material has Lii. 〇l (Ni〇. 3GC〇G. 3()Mn〇. 4G) G. A lithium-containing composite oxide composed of 99〇2. The base material has an average particle diameter of 8 · 5 μιη, -47-200818581 D10 of 4·5 μιη, D90 of 14·2 μιη, and a specific surface area of 〇. A powder of a primary particle of 62 m 2 /g which is mostly agglomerated and forms a secondary particle. With respect to the composite oxide particles, an X-ray diffraction spectrum was prepared using an X-ray diffraction apparatus (RINT 2100 manufactured by Rigaku Corporation). In the powder X-ray diffraction using the CuKa line, the diffraction peak of the (110) plane of 2Θ = 65·1 gΓ is half width. 27°. The pressed density of the particles is 2. 55g/cm3. Further, in the case of the lithium-containing composite oxide particles of the above-mentioned base material, when surface element analysis was carried out by XPS analysis in the same manner as in Example 1, titanium was not detected. Using the lithium-containing composite oxide particles of the above-mentioned base material, a positive electrode body was produced in the same manner as in Example 1, and a battery was assembled and evaluated. As a result, at 25 ° C, 2. 5~4. The initial weight capacity density of the positive active material of 3 V was 142 mAh/g, and the capacity retention rate after 30 charge and discharge cycles was 9.6 · 1%. In addition, the temperature was raised at a rate of 5 ° C /min using a scanning differential calorimeter, and the result of the heat start temperature was measured. The heating start temperature of the 3V charging product has a heating start temperature of 23 9 °C. [Industrial Utilization Price] According to the present invention, it is possible to provide a nonaqueous electrolyte composed of lithium-containing composite oxide particles which does not lower high safety, has high operating voltage, high discharge capacity, and excellent charge and discharge cycle characteristics. A positive electrode active material for a storage battery, a method for producing the positive electrode active material, and a nonaqueous electrolyte secondary battery using the positive electrode active material. -48- 200818581 Moreover, the application for the application No. 2006-212647 and the scope of patent application for the application of the application dated 20 06-2 03 99 3, filed on July 26, 2006, and August 3, 2006 The entire contents of the drawings and the disclosures of the present invention are applied to the disclosure of the present specification. [Fig. 1] shows the infrared absorption (IR) of the decorative lithium-containing composite oxide obtained in Example 2 (Example). ) Infrared absorption of the lithium-containing composite oxide obtained by the spectrum (A) and (Comparative Example) (spectrum (B) 〇 [_Fig. 2] shows the thermal weight differential weight of the dried titanium lactate (TG-DTA-DTG) The results of the analysis of the analysis. This patent 曰 专 及 及 及 及 及 4 4 4 4 4 4 4 IR IR IR IR IR IR

Claims (1)

200818581 X. Patent application scope 1. A positive electrode active material for a non-aqueous electrolyte storage battery, characterized by a lithium-containing composite oxide particle represented by a general formula LipNxMy02 (wherein N is at least one selected from the group consisting of Co, Μη and Ni) The element of the group, the lanthanide is 'an element selected from transition metals other than elemental lanthanum, alkaline earth metals and aluminum, 〇· 9 S p S 1 · 1, 〇 _ 9 ^ X &lt; 1 · 1, 0 S y S 0 · 3 ), which contains titanium on the surface layer, and the surface layer has a titanium content of 5 nm or less, and the element N has a surface-modified lithium composite oxide particle having an atomic ratio of 0.6 or more. . 2. The positive electrode active material for a non-aqueous electrolyte battery according to claim 1, wherein the lithium-containing composite oxide particles are at least one selected from the group consisting of lithium cobaltate, lithium nickel cobaltate, lithium nickel cobalt aluminate, and nickel cobalt. In the group of the lithium manganese oxide particles, the titanium contained in the entire surface-modified lithium composite oxide particles has an atomic ratio of 0.0005 to 0.10 〇 φ 3 for the total amount of the element N and the element yttrium. The positive electrode active material for a non-aqueous electrolyte battery according to claim 1 or 2, wherein the surface-modified lithium-containing composite oxide particles have an average particle diameter (D50) of 5 to 25 μm. The non-aqueous electrolyte according to any one of claims 1 to 3, wherein the composite oxide material containing surface-modified lithium contains a carbon compound on a surface layer thereof. 5. The positive electrode active material for a nonaqueous electrolyte secondary battery according to claim 4, wherein the carbon compound is a partial thermal decomposition product of a carbon-containing titanium complex. -50-200818581 6. A lithium secondary battery, which is a lithium secondary battery comprising a positive electrode and a negative electrode and a non-aqueous electrolyte, characterized in that the positive electrode is used as a positive electrode according to any one of claims 1 to 5. Active substance. The method for producing a positive electrode active material for a non-aqueous electrolyte battery according to any one of the first to fifth aspects of the present invention, characterized in that the lithium-containing composite oxide particles represented by the general formula LipNxMy02 are contained therein. N is at least one element selected from the group consisting of Co, Μη, and Ni, and the lanthanide is an element selected from the group consisting of transition metals other than element lanthanum, alkaline earth metals, and aluminum ' 0 · 9 $ p S 1 . 9 SX &lt; 1 · 1, 〇S y $ 0 · S), impregnated with a titanium complex, p Η値 is an aqueous solution of 1~1 2, and then mixed and dried to obtain a titanium complex impregnation Step 1 of the particles, and Step 2 of subjecting the titanium complex compound impregnated particles obtained in the step 1 to heat treatment in an oxygen-containing atmosphere. 8. The method for producing a positive electrode active material for a nonaqueous electrolyte secondary battery according to claim 7, wherein the heat treatment in the step 2 is carried out at 200 to 450 °C. 9. The method for producing a positive electrode active material for a nonaqueous electrolyte secondary battery according to claim 7 or 8, wherein the titanium complex compound is a carbon-containing titanium complex compound. The method for producing a positive electrode active material for a nonaqueous electrolyte secondary battery according to claim 9, wherein the carbon-containing titanium complex compound is titanium lactate. -51 -