TW541745B - Anode active matter and production method therefor, non-aqueous electrolyte secondary battery-use anode, and non-aqueous electrolyte secondary battery - Google Patents

Abstract

The present invention provides an anode active matter capable of producing a non-aqueous electrolyte secondary battery having a high energy density and being excellent in charge/discharge cycle characteristics, and a non-aqueous electrolyte secondary battery-use anode and non-aqueous electrolyte secondary battery using it. The anode active matter contains a composite oxide represented by a composition formula LiaMn0.5-xNi0.5-yMx+yO2 (0 < a &lt 1.3, -0.1 <= x-y <= 0.1, M is an element other than Li, Mn, Ni). Alternatively, the anode active matter contains a composite oxide represented by a composition formula iwMnx'Niy'Coz'O2 (in the tertiary state diagram, (x', y', z') is the value on the line or in the interior of the rectangle ABCD using A(0.51, 0.49, 0), B(0.45, 0.55, 0), C(0.25, 0.35, 0.4), D(0.31, 0.29, 0.4) as vertexes. 0 <= w/(x'+y'+z') <= 1.30).

Description

Leap year * January 13th (more) Zhengguanguan A7 V. Description of the invention (y (please read the precautions on the back before filling this page) X to form a porous, lithium-manganese-nickel composite oxide density Decreased. Although this temple exhibits high-efficiency discharge performance, the constituent elements are dissolved, which results in an increase in Λ @ J: the resistance increases, or the electrolytic solution undergoes oxidative decomposition to reduce storage performance, or the thermal stability during charging tends to decrease. &amp; It is learned that the total pore volume of the composite oxide is in the range of 0 · 0〇1 111 1 / g to 0 · 0 0 6 m 1 / g (specific surface area: 0.3 · 〇111 u / g ~ 1.6 m 2 / g), a battery with excellent quotient discharge performance and high charge-discharge cycle performance can be obtained. When the battery requires high-efficiency discharge performance represented by low-temperature high-efficiency discharge performance, as described above, even the battery The energy density has decreased, and the composite oxide also needs to increase the full pore volume, but batteries with too much full pore volume (specific surface area) have a problem of reduced charge and discharge cycle performance. Full pore volume (specific surface area) Larger materials are generally crystalline Or a material with a lot of fine cracks. The positive electrode active material according to the embodiment of the present invention has a composite oxide as described above. 'It is ideally a powder X-ray diffraction pattern using Cu κ α 2 2 β: 4 4. 1 ± Diffraction peaks at 1 ° to 20: 1 8 · 6 ± 1. Diffraction composite oxides whose relative intensity ratio of the peaks printed by the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs are 0 · 6 5 or more and 1 · 0 or less In this way, a battery with stable crystal structure and excellent charge-discharge cycle performance can be obtained. Although this effect is not clear, the diffraction peak pair of 2 β: 4 4. 1 ± 1 ° 2 0: 1 8 · 6 ± 1. The relative intensity ratio of diffraction peaks is an index of crystallinity. The higher the sintering temperature, the longer the sintering time, and the smaller the total pore volume, the greater the relative strength. Zhang scale is applicable to Chinese National Standard (CNS) Α4 specification (210x 297 mm) -33- 541745tern Yue ΐ ί 13 曰 13 month (see) Correction replacement page A7 Β7 V. Description of the invention (3 "(Please read the note on the back Please fill in this page again) It is difficult to obtain the target compound oxide Production problems, or the problem of battery performance degradation caused by the high density of particles. This may be caused by the increase in the growth rate of primary particles when the temperature exceeds 110 ° C, and the crystalline particles of the composite oxide are too large. In addition, the increase in the local defect amount of L i is also the cause of the formation of a unstable structure. At higher temperatures, element substitution between the surface occupied by the Li element and the surface occupied by the Mn, Ni, and C elements is extremely easy. Suppressing Li conduction causes a decrease in discharge capacity. The sintering temperature is more than 950 ton and 10 to 5 ° C, which can produce batteries with high energy density (discharge capacity) and excellent charge-discharge cycle performance. The sintering time is preferably 3 hours to 50 hours. The sintering time exceeds 50 hours, but the battery performance is substantially deteriorated due to the volatilization of Li. If the sintering time is less than 3 hours, the crystal growth is poor, and the battery performance is deteriorated. 0 Printed by the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs, "contains at least 1 ^ 1 Μ η-N The "i complex oxide precursor" is preferably a compound in which η and Ni are uniformly mixed. Also "L i-Mη-N i-Μ complex oxide precursor containing at least Li component, Mn component, N i component and M component" which] \ / [11, Ni and M are homogeneous compounds Better. There is no particular limitation as long as it is a manufacturing method that satisfies such conditions. Within the constitutional scope of the present invention, the stability of the crystalline structure that occludes and releases lithium ions must be high. Therefore, an alkali aqueous solution such as an aqueous sodium hydroxide solution is used. The co-precipitation method for precipitation of acidic aqueous solutions of η, Ν, and Μ "can produce a positive electrode active material having particularly high battery performance. As stated in Japanese Patent Application Publication No. 10- 丨 2 5 3 1 9, under the condition that the reaction system contains excessive ammonium ions for the metal, the Chinese paper standard (CNS) A4 specification (2 丨0X 297mm) -37- Continued) Replacement page A7 B7 V. Description of the invention (36) (Please read the notes on the back before filling out this page) In this description, 'M compound means li, M η, Compounds of elements other than Ni. Specific examples of M are the aforementioned ones. When M is a compound of a 1 'is a compound of aluminum nitrate' When M is a compound of M g, it is magnesium sulfate or the like, and when M is a compound of C 0, it is cobalt hydroxide, cobalt carbonate, cobalt sulfate, cobalt nitrate, or the like. The following is a description of manufacturing a co-precipitated product of M η and Ni that can be a constituent of a precursor of Li-Mη-Ni complex oxide (M ^ —Ni complex total spray) and the formation of Li-Mη- The co-precipitates of M i and Ni and M (μη-Ni-M composite co-precipitate) of the constituent components of the Ni-M composite oxide precursor. The production of Μ η-Ni complex co-precipitate is preferably a mixture of μ η and Ni uniformly, and the production of Μη-Ni-Μ complex co-precipitate is uniformly mixed with Mn, Ni and Μ. Co-precipitation is preferred. An example of the preparation of the Mn-Ni co-precipitated product is prepared by, for example, precipitating an acidic aqueous solution of Mn and Ni with sodium hydroxide. The production of Mn-Ni-M composite coprecipitate is made by the precipitation of sodium hydroxide in an acidic aqueous solution containing Mn, Ni and M elements and printed by the Consumer Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs. In this case, the metal in the reaction system contains excessive mirror ions; a uniform spherical shape and high-density precursor particles can be produced. .M η-N i composite co-precipitate, Μ η — N i-Μ composite co-precipitate can be prepared by batch or continuous precipitation method, in order to obtain uniform spherical and high-density precursor particles, use Continuous precipitation is preferred. The paper size of the positive electrode active material of the present invention with a specific co-precipitation step is applicable to the Chinese National Standard (CNS) A4 specification (210X29? Mm) -39-

A7 B7 — 1 · _- ~ — &quot; &quot; 丨 Ι · 丨 丨 — V. Description of the invention (38) Generally, according to the well-known powder mixing method, the starting materials are finely pulverized into submicron or micron particles, and added Li iodide and other lithium sources are sintered. It is also technically possible to obtain a composite oxide in which the elements in the lithium-manganese-nickel composite oxide are uniformly and solidly mixed, but the powder must be finely pulverized, or the powder must be sintered Complicated steps such as press molding. Even if it is available, the composite oxide is miniaturized and cannot satisfy the battery performance. The uniformly mixed state of Ni-Μ η will affect the thermal stability and charge-discharge cycle performance during charging, and the unevenly mixed state of Ni-Μ η may produce the disadvantage of poor thermal stability caused by LiNl02 in the past. And L 1-M η oxide such as L i 2 Μ 〇 3 and the like, a state in which particles with poor charge-discharge cycle performance exist locally. Sintering the M η compound, the Ni compound, and the ming compound together can obtain a L 1? 411. 1 ^ 3 (: 〇, .〇2 type complex oxide, but 1 ^ 11, Ni, C0 element The solid solution substitution is slow, and the composite oxide cannot be obtained sufficiently. Even if the sintering time is prolonged in order to obtain a sufficient composite oxide, the crystal growth of the composite oxide is excessive, and the specific surface area is reduced. Therefore, the discharge capacity of the battery tends to decrease. In the co-precipitation step of the method for producing a positive electrode active material of the present invention, the N i compound, the M n compound, and the M / compound are dissolved in water to uniformly mix the N i element, the M n element, and the M / element. Next, an alkaline compound is added to obtain a composite coprecipitate in a uniformly mixed state of each element. In the positive electrode active material obtained by this method, at least the N 1 element and the M η element are more uniformly mixed than in the past, so it can be estimated that a discharge capacity can be obtained Excellent battery. The above-mentioned composite co-precipitate is Ν 1 a paper size applicable to China National Standard (CNS) Α4 specification (210X 297 mm) (Please read the back first Please pay attention to this page and fill in this page) Order printed by the Intellectual Property Bureau Employee Consumer Cooperative of the Ministry of Economic Affairs -41-Month 1 Jealousy (correction) Replacement page 1 A7 B7 V. Description of the invention (67) 1 · 0 2. This mixture塡 Fill in an aluminum bowl and use an electric furnace to

The temperature is raised to 1000 ° C / hour to 10.0 ° C, and maintained at 1030 ° C (please read the precautions on the back before filling in this page) for 15 hours at 100 ° C / Cool down to 600 ° C per hour, then leave to cool. The obtained sintered body was pulverized and classified using a 7 5 # m sieve to obtain a lithium-nickel-manganese composite oxide (composite oxide A5) having D 5 0 = 1 0 · 2 // m. The specific surface area is 1.8 m / g. The total finely divided trough volume was 0.07 ml / g. As a result of X-ray diffraction measurement of this powder using Cu κ α rays, the diffraction peaks were the same as those of the composite oxide A 1, and it was found that a single phase having a high crystallinity having a layered structure belonging to the space group R 3 / m was synthesized. Lattice constant a =

2 · 8 8 9, lattice constant c = 14.3 0, crystal lattice volume V = 0 · 1 0 3 4 n m 3. A peak pair of 26 = 44 · 12 ° 20 = 18 · 60. The relative intensity ratio of the peaks is 0.77, and the half-widths of the peaks are 0.22 ° and 0.28 °, respectively. As a result of elemental analysis, this powder was not less than L i 1.02M110.5N i0.50. Printed by the Consumer Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs (composite oxide A 6; conventional powder mixing method) Electrolytic manganese dioxide powder (r — M η〇2, purity 9 2%) is pulverized by a wet pulverizer Into an average particle diameter of 2. 0 // m. The nickel hydroxide powder was pulverized with a wet pulverizer to an average particle diameter of 2.0 m. Manganese dioxide powder and nickel hydroxide powder were mixed in a state where the element ratio of nickel to manganese was 1: 1. The nickel-manganese mixed powder and lithium hydroxide monohydrate powder obtained by weighing are used. The paper size is applicable to the Chinese National Standard (CNS) A4 specification (210X 297 mm) -70-, and it is replaced by 3 (revised) Page ^ V. Description of the invention (68) Then mix thoroughly to make Li / (Ni + Mn) into a state of 1.02. This mixture was filled in an aluminum bowl, and the temperature was raised to 1000 ° C at a rate of 1000 t / hour using an electric furnace, and maintained at 1000 t: 15 hours at 1000 ° C. Cool down to 600 ° C per hour and let cool. The obtained sintered body was pulverized and classified using a 7 5 // m sieve to obtain D 5. = 9 · 5 // m of lithium-nickel-manganese composite oxide (composite oxide A 6). The specific surface area is 1.8 m2 / g. Full pore volume is 0.006423ml / g. As a result of X-ray diffraction measurement of this powder using CuKα rays, the diffraction peaks were the same as those of the composite oxide A1, and it was found that a single phase having a high crystallinity having a layered structure belonging to the space group R 3 / m was synthesized. The lattice constant a is 2 · 8 9 1, the lattice constant is c = 1 · 4 · 30, and the crystal lattice volume is V = · 1035 n m3. 2Θ = 4 4 · 12 ° peak pair 20 = 18. 56. The relative intensity ratio of the peaks is 0 · 7 7 and the half-widths of the peaks are 0 · 188 ° and 0.259 °, respectively. As a result of elemental analysis, this powder became Li i.osMno.sN i0.52. (Composite oxide A 7; conventional powder mixing method) The electrolytic manganese dioxide powder (r-M η02, purity 92%) was pulverized with a wet pulverizer to an average particle diameter of 2.0 m. The nickel hydroxide powder was pulverized with a wet pulverizer to an average particle diameter of 2. 0 // m. Mix the manganese dioxide powder and nickel hydroxide powder with the ratio of nickel to manganese to 1: 1. The paper size is applicable to China National Standard (CNS) A4 specification (210X 297 mm) (Please read the note on the back first) Please fill in this page again) Order% -71-Lion Co., Ltd. Printed on the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs. 5. Description of the Invention (Μ) 〇〇 Use the heater intermittently to fix the temperature of the solution in the reaction tank to 50 t. Five hours after the start of the feeding of the raw material solution, a slurry of nickel-manganese composite co-precipitate, which may cover the surface with a hydroxide precipitate or a cobalt precipitate of an oxide, was taken. The collected slurry was washed with water and filtered. It was then dried at 100 ° C. for 20 hours to obtain D 5 of a nickel-manganese composite co-precipitate whose surface was covered by a cobalt precipitate. = 1 1 · 2 # m of dry powder. The specific surface area of this powder was measured on the nitrogen release side using 4 S U-8 U 2 manufactured by YUASAIONIX. The result was 1 5 · 6 m 2 / g. Ping take the mirror of the mirror-Meng Yiguo 0 coprecipitate powder and nitrogen oxide bond monohydrate salt powder, and then thoroughly mixed to make Li / (N i + Μη + C) to 1 · 02. This mixture was poured into an aluminum bowl, and the temperature was raised to 100 ° C at a rate of 100 ° C / hour using an electric furnace. (: Hold at 1000 ° C for 15 hours, cool to 600 t at 100 ° C / hour, and leave to cool. After crushing the sintered body, use 7 5 # The sieve classification of m yields D 5 ◦ = 1 2 · 6 / zm of lithium-nickel monolithic composite oxide (complex oxide C 7). The specific surface area is 0 · 3 m 2 / g. The total pore volume is 〇 · 00 1285 ml / g. The results of X-ray diffraction measurement of Cu powder with Cu κ α were the same as those of the complex oxide A 1, and it was found that a layered structure belonging to the space group R 3 / m was synthesized. Single phase with high crystallinity. Lattice constant a 2 · 8 7 7; Lattice constant c · = 1 4 · 2 8; Crystal lattice volume v = 0 · 1 ◦ 2 3 nm 3. 2Θ = 44 · The peak pair at 20 ° is 20 = 18.60. A7 B7 (please read the notes on the back before filling this page) ·· The size of the paper is applicable to the Chinese National Standard (CNS) A4 specification (21〇X: 297) (Centimeters) -86- A7 B7 (revised) Page V. Description of the Invention (Q / l) The relative intensity ratio of 84 peaks is 0 · 6 6 and the half-widths of each peak are 0.059 ° and 0.1 18 ° respectively. As a result, the The final composition is L i 1.02Mni / 3N i 1 / 3C 〇2 / 12〇2. (Composite oxide C 8) The high-density nickel-manganese composite coprecipitate obtained by (complex oxide C 1) 5 0 g is added to 1 liter of a sodium hydroxide aqueous solution of 3 2% sodium hydroxide aqueous solution so that P Η = 1 1 · 6. Using a mixer equipped with a 70 mm0 blade type stirring blade, stir at 1 350 0 pm, Use a heater to maintain the temperature of the solution in the reaction tank at 50 ° C. The 1.5 mol / liter aqueous solution of cobalt sulfate and the 6 mol / liter aqueous solution of ammonium sulfate were used in a volume ratio of 5 · 0: 1 · 4 0 (liters), respectively. As a raw material solution for coating co-precipitation. For a high-density nickel-manganese composite co-precipitate at 50 g, the raw material solution for coating co-precipitation is weighed so that (N i + Mn) / Co 2 2 0 / 1 (Molar ratio). This raw material solution was dropped into the reaction tank. In addition, a 3 2% sodium hydroxide aqueous solution was intermittently injected to fix the solution P Η in the reaction tank to 1 1 · 3. It was heated intermittently. The temperature of the solution in the reaction tank is fixed to 50 ° C. Five hours after the start of the feedstock solution, a hydroxide or The nickel-manganese composite co-precipitate slurry covered by the cobalt precipitate on the surface of the compound. The collected slurry was washed with water, filtered, and then dried at 100 ° C for 20 hours to obtain the nickel-coated nickel-manganese coated surface.锸 Dso II 1 1 · 〇 # m dry powder of composite coprecipitate The paper size is applicable to Chinese National Standard (CNS) Α4 specification (210X297 mm) (Please read the precautions on the back before filling this page)

Printed by 1T Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs -87- 541745,

95 Body 1! Month 13 LV_ Sudden) Tochi Ombe I 5. Description of the invention (87) C 0) becomes 1 · 02. This mixture was filled in an aluminum bowl. 'The temperature was raised to 100 ° C using an electric furnace at a rate of 100 ° C / hour.' The temperature was maintained at 1,000 ° C for 15 hours at 100 t. : Cool down to 600 ° C per hour, then leave to cool. The sintered body thus obtained was pulverized and classified using a sieve of 75 V m to obtain a lithium-nickel-manganese-cobalt composite oxide (composite oxide C 9) having D 5 G = 1 0 · 6 // m. The specific surface area is 0 · 6 m 2 / g. The total pore volume was 0.0000 1979 ml / g. As a result of X-ray diffraction measurement of this powder using Cu κ α rays, the diffraction peaks were the same as those of the composite oxide A 1, and it was found that a single phase having a high crystallinity having a layered structure belonging to the space group R 3 / m was synthesized. 2 ^ = 44 · 40 peak pair 26 = 18. 60. The relative intensity ratio of the peaks is 0. 8 5 ′, and the half-widths of the peaks are 0.172 ° and 0.142 °, respectively. The composite oxide C 9 is a result of X-ray diffraction measurement using Cu κ α rays, at 20 = 1 8 · 5 8 °, 3 5. 5 6. , 37.72 °, 38.20 °, 44.28. , 48.44 °, 58.40 °, 64.12 °, 6 3.7 6 °, 68.02. It was found that the diffraction peak, an α-N a F e〇2 layered structure composed of a single phase of a highly crystalline hexagonal crystal, has a lattice constant of 3 = 2 · 881 and a lattice constant of C = Ο η. d J, $ 口 said lattice volume V = ◦ · 1 0 3 0 Π m 3. Elemental analysis results, the composition of the powder is Li i.uMno.esNici.HCo n This paper size is applicable to China National Standard (CNS) A4 specification (210X 297 mm) (Please read the precautions on the back before filling this page ) Order printed by the Intellectual Property Bureau's Consumer Cooperatives of the Ministry of Economic Affairs-90- V. Description of the invention (id (please read the precautions on the back before filling out this page) is 1 · 3 M m. The measurement of powder distribution uses Japan Horiba Laser diffraction / scattering type particle size distribution measuring device (HORIBA LA ~ 9 1 〇). At this time, the specific surface area of BE but is 0.8 m 2 / g. (Composite oxide C 1 8) In addition to the powder obtained by screening The powder was made to have D 5 0% of 7 # m and d 1 〇% to 3.4 · zm, and the rest was the same as (composite oxide c 1 7) to obtain a powder (composite oxide C 18). The BET ratio at this time The surface area is \ 0 · 9 m 2 / g. (Composite oxide C 1 9) Except for the powder obtained by screening, D5 0% is 1 0 // m, D 1 〇% is 6 // m, the rest is the same as (Composite oxide C 1 7) The same powder was obtained (composite oxide C 19). At this time, the specific surface area of BE butane was 1.2 m 2 / g. (Composite oxide C 2〇 ) Printed by the Consumer Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs, except that the powder obtained was screened so that D 50% was 0.8 // m and D 1 0% was 0.4 · m. C 1 7) The same powder was obtained (composite oxide C 2 0). The BET specific surface area at this time was 9 · 0m2 / g. (Composite oxide C 2 1) j, V ^ 1 ^ 0 J \ £ .IKJ Λ. 1.7 / -104-B7 In each year, the jealousy of the jealousy (officials) is guaranteed to be bought by V. V. Description of the invention (1 (^ Except for the powder obtained by screening, D 5 0% is 2 // m, D 1 〇% (Please read the precautions on the back before filling this page) Except for 0 · 4 // m, the rest is the same as (composite oxide c 1 7) to obtain a powder (composite oxide C 2 1). The BET ratio at this time The surface area is 7.0 m 2 / g. (Composite oxide C22) Except for the powder obtained by screening so that D 50 0% is 1 2 · 5 # m and D 1 〇% is 7 // m, the rest are the same as ( The composite oxide C 1 7) was obtained in the same manner (composite oxide C 2 2). At this time, the BET specific surface area was 0 · 3 m 2 / g. For the powders of the composite oxide C 1 7 to C 2 2 The important part of the measured particle size distribution curve is shown in Figure 18. (Composite oxide C 2 3) A reaction tank 1 1 used in (Composite oxide A 1) was used. This reaction tank 11 was filled with 13 liters of water. Add 3 2% aqueous sodium hydroxide solution to make P Η = 1 1 · 6. Use a blender with a blade type of 70 mm 0 to print the blender blades 1 2 a of the Ministry of Economic Affairs Intellectual Property Bureau's Consumer Cooperatives, and stir at 1 350 rpm. Use a heater to keep the temperature of the solution in the reaction tank 5 0 ° C (refer to Figure 1) ° 0. 701 mol / liter of nickel sulfate aqueous solution, 0.7 mol / liter of manganese sulfate aqueous solution, 0 · 351 1 mol / liter of cobalt sulfate solution, 1 · 〇Mole / liter ammonium sulfate solution and 0. 0 1 0 mol / liter hydrazine aqueous solution were mixed at a volume ratio of 1: 1: 1: 1.1: 1 (liter), respectively, as Ni / Mn / C. = 〇 · 4/0. 4 / This paper size applies to China National Standard (CNS) Α4 specification (21〇 × 29 * 7mm) -105-

V. Description of the Invention (12g Printed by the Consumer Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs, Z0 Crystal structure, crystal lattice f-% ε c &gt; S5 0.1033 0.1039 0.1034 0.1036 0.1034 0.1035 0.1029 Thai 0.1030 0.1029 Lattice constant O 14.29 14.33 14.30 14.28 14.30 14.30 14.30 1 14.29 14.27 CC 2.889 2.894 2.889 2.895 2.889 2.891 2.883 1 2.885 2.886 Half width 44.1 ± 10.41 0.141 0.141 | 0.176 0.282 0.259 Flat 0.094 0.090 Half width 18.6 + 1 ° 0.141 0.188 0.118 oo, one o 0.212 -1 0.188 0.188 1 0.141 0.107 Peak intensity ratio 0.86 0.98 0.72 0.63 i Ή wn o -1 0.60 0.76 0.70 0.88 ir-H space group R3 / m R3 / m R3 / m R3 / m R3 / m R3 / m R 3 / m R3 / m + C2 / m R3 / m R3 / m composite oxide »4 &lt; cs &lt; cn &lt; inch &lt; &lt; &lt; r- &lt; oo &lt; ON &lt; A 1 0 G« ^ s ^ 4 &lt; liAeco ~ CNI, e 拗 • Pan Zhao Itf 戥 _Leading (菡 日 G) Λ »Parrot Wax Waves: 〇, towels are dumb (please read the precautions on the back before filling this page) Order Line ▲ This paper size applies to China National Standard (CNS) A4 (210X297 mm) -123- Repair (more) Replace the poor 1, --- = V. Description of the invention (12i Printed by the Consumer Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs 9 sintered composite oxide / ^ S? Q ^ un ο r—Η i 10.9 On 9.4 9.9 10.4 All Pore volume (m 1 / g) 0.001945 0.002285 0.001945 0.001605 0.001945 0.001605 Specific surface area (m2 / g) 0.6 ov〇〇υη 〇o 0.5 Pre-sintering precursor coating and co-precipitation 鹿 Deer soil £ 10.8 inch r m &lt; r 1 Ί ON On 9.6 inches of Ή production · Η specific surface area (nr / o) cn CNJ cn H vn CO 1 28.8 m cn 26.9 Composition L ΐ Μ n 〇. 4 9 5 N 1 〇 4 9 5 M g 〇 〇1 0 2 L Μ n 〇. S 9 4 N 1 〇 3 9 6 M g 〇. 〇! 0 2 1 LL Μ n 〇 3 9 6 N 1 〇 5 9 4 M g 〇. 〇1 0 2 LiMn〇495Ni〇49 5 Al〇.〇i 〇2 LiMn〇.5 94Ni〇.396Al〇.〇i〇2 LiMn〇.396Ni〇. 5 94Al〇.〇i〇2 composite oxide r-i CN Q cn Q CN va cn (Please read the notes on the back before filling in this page) Order k ··. This paper size applies to China National Standard (CNS) A4 (21〇X 297 mm) -127- A7 B7 (more) Page 5 is being replaced Description of the invention (the size of crystals in the dnm and c-axis directions (L c) 5 5 nm) and the polyvinylidene fluoride (P d F) of the adhesive, N-methyl-2 ~ pyrrolidone (NM P ) To obtain a negative electrode paste after thorough kneading °. The foregoing negative electrode paste was coated on one side of a copper foil current collector with a thickness of 15 // m and was' pressed and cut into a disc shape of 1 cm 2. (Preparation of non-aqueous electrolyte) Li P F 6 containing a fluorine-containing electrolyte salt was dissolved in a mixed solvent of a volume ratio of 1: 1 of ethylene carbonate and diethyl carbonate of 1: 1 at a ratio of 1 m ο to prepare a non-aqueous electrolyte. The amount of water in the non-aqueous electrolyte is 20 P P m or less. (Manufacturing of coin-type batteries) Using the above-mentioned components, in a dry atmosphere with a dew point of -50 ° C or lower, the same as coin-type batteries (type I) was used to produce coin-type batteries (type ΙΙ) ° (Charge-discharge cycle performance test ) ^ Two coin-type batteries (type ΙΠ) were produced, and initial charge and discharge were performed for 5 cycles. The charging and discharging conditions at this time are the current 0 · 1 I t A (10 hr rate), 4 · 2 V constant current and constant voltage charging, and the discharge conditions are current 0.1 I t A (10 hr rate), Discharge at a constant current with a termination voltage of 3.0V. The charging current for the subsequent charge-discharge cycle test is 0 · 5 I t A, 4.2 λ / 'constant current and constant voltage for 3 hours, and the paper is discharged according to the Chinese National Standard (CNS) A4 specification (21〇X29: 7mm) (Please read the precautions on the back before filling out this page) Order Printed by the Intellectual Property Bureau Staff Consumer Cooperatives of the Ministry of Economy -132-

3: ¾ potential: more) positive replacement I: A7 B7 5. Description of the invention (13l lithium-manganese-nickel composite oxide manufactured by sintering time, etc., but the above-mentioned one is a high-density lithium-manganese-nickel composite oxide (Please read the notes on the back before filling this page) (Relationship between specific surface area and total pore volume) Calculated from the release side of the nitrogen adsorption isotherm based on the lithium-manganese-nickel composite oxide based on the previous method and basis The full pore volume and specific surface area of the high-density active material (lithium-manganese-nickel composite oxide) of the co-precipitation method defined in the manufacturing method of the present invention. The results are due to PΗ, sintering time or The sintering temperature and the addition of different elements change the total pore volume and specific surface area of the prepared composite oxide. (Relationship between the total pore volume and specific surface area for sintering conditions) The composite oxide with a sintering temperature of 8 50 ° C A 4, with a specific surface area of 3.5 m 2 / g. The total pore volume is 0.5% of the particle volume (0.222 ml / g). Consumption cooperation between employees of the Property Bureau, printing compound with sintering temperature of 1 0 3 0 t Compound A 1 has a specific surface area of 0.89 m 2 / g and a total pore volume of 0.003 3 m 1 / g, which can be reduced to a volume of particles (0 · 2 2 0 m 1 / g). 1 · 5% 〇 (Relationship between specific surface area for sintering temperature and charge-discharge cycle performance) For example, the relationship between specific surface area and charge-discharge cycle performance versus sintering temperature when producing L 1 Μ η 〇 0.5 N i 〇 0.52 (Refer to Figure 8) As shown in the figure, to increase the size of this paper, the Chinese National Standard (CNS) A4 specification (210 X 29 * 7 mm) -138- A7 B7 V. Description of the invention (13 &amp; (Please read the precautions on the back first) Fill out this page again) When 1% solid solution substitution with Mg, the same layered structure as the unsubstituted body can be maintained to obtain high-density particles. The solid solution substitution of Mg shows a tendency to increase the charge-discharge cycle performance. As shown in Comparative Example 3-1, when the amount of 'M η is much larger than the amount of Ni, the discharge capacity is reduced due to the formation of impurities of L 1 2 Μ η03 with the structure of the space group C 2 / m. Another example is the comparative example. As shown in 3-2, when the amount of Ni is much larger than the amount of Mη, although the initial discharge capacity is higher than that of the non-solid-solution substitute, the charge and discharge Instead, the ring performance is reduced. As shown in Example 4-1, when 1% solid solution substitution is performed for Li i η 0.5 0.5 N i 0.52 with A 1, it is also shown to be the same as in Example 3-1. Tendency. The substitution effect of these elements is to promote the crystallization by the substituted elements, which can suppress the change in the crystalline structure of the charge and discharge. (Relationship between the discharge capacity and the relative intensity ratio of the charge and discharge cycle performance to the X-ray diffraction pattern) The table shows the powder X-ray diffraction pattern of Li i Μη〇 · 5Ν i 〇0.52 using the CuK α line. 203 4 4.1 Relation diagram of the relative intensity ratio of the diffraction peaks to the diffraction peaks of 2 β = 1 8 · 6 ± 1 ° and the discharge capacity. As shown in Figure 10, when the relative intensity ratio exceeds 1.05, the amount of discharge capacity decreases significantly. This is based on the use of a powder X-ray diffraction pattern. * When analyzing, the former @relative intensity ratio is replaced by the element "_" in the face occupied by each constituent element. High sintering temperature, long sintering time, etc., such as nickel, manganese or cobalt elements and the paper size in accordance with Chinese National Standard (CNS) A4 specifications (210X 297 mm) -141-

Α7 Β7 V. Description of the invention (the relationship between the half-width of 14g) Figure 12 shows the powder X-ray diffraction pattern of L iMn0.5.5Ni2. 50 using CuK α. 2 0 = 18 · 6 Soil 1. Relationship between half width and discharge capacity. 18 · 6 soil 1. The half-width is in the range of 0.050 to 0 · 200, regardless of the discharge capacity. Fig. 13 shows the powder X-ray diffraction pattern of L iMn0.5Ni0.5〇2 using CuK α rays, 2 0 = 18 · 6 11. Relationship between half width and charge-discharge cycle performance. In the battery of this example, the half width of 20 = 1 8 · 6 ± 1 ° has nothing to do with the charge-discharge cycle performance. However, 1 ^ 1] ^ 11〇.5] ^ 10.5.02 manufactured according to the conventional neutralization method or powder mixing method, which has 2 (9 = 18 · 6 ± 1. The half width is about 0. · Near 2000, the charge-discharge cycle performance tends to decrease. This is because according to the conventional neutralization method and the powder mixing method, the sintered L iMn〇.5N i 〇0.52, whose N i and Mη The reason why the uniform sentence is mixed and the half width is widened. Because there is a part of the composition ratio with more M η materials or more Ni materials, it can be found that the low charge and discharge cycle performance of Li M η〇2 is low and L 1 Ν 1〇2 has low thermal stability during charging. (Relationship between discharge capacity and charge-discharge cycle performance for 2 β = 4 4 · 1 ± 1 ° half width) Figure 14 shows L 11 \ / [11〇. 5 ^ 1..5〇2 use (: 1 ^ 1 &lt;: powder X-ray diffraction pattern of α 2 2 β 2 4 4 · 1 soil 1 ° half-width and discharge capacity relationship chart. This paper scale applies China National Standard (CNS) Α4 specification (210 × 297 mm) (Please read the precautions on the back before filling this page}

J1T Φ. Printed by the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs ----- -143- A7 B7 See {History.) Zhengdu page change V. Invention description (14; | L i Μ η 〇 ·· 5 N i 〇 In the battery of the embodiment composed of 502, the discharge capacity is 20 = 44.1. The half-width of 1 ° is about (please read the precautions on the back before filling this page) 〇 · 1 〇0 °, Fig. 15 shows a series of powder X-ray diffraction diagrams using Cu κ α rays, which are shown in Fig. 15 as Li Μ 11 〇 0.5 N Ni 〇 0.5 2 θ = 4 4 · 1 ± 1. The relationship between the half-width and the charge-discharge cycle performance. In the battery of the embodiment consisting of L i Μ η 〇. 5 N i 〇 0.52, the charge-discharge cycle performance is 2 Θ = 4 4 · 1 ± 1. The half width is around 0.170, and there is a tendency to decrease. The battery manufactured according to the conventional neutralization method or powder mixing method, because 20 = 44 · 1 ± 1. The half width exceeds 0 · 2 5 0 As the crystal is not uniform, the charge-discharge cycle performance tends to decrease. From the above, it is known that 20 = 44 · 1 ± 1. When the half-width is 0 · 100 ° or more and 0 · 200 ° or less, excellent charge and discharge can be maintained. Ring performance and high discharge capacity. (Distance from the crystal lattice volume of the relationship between the lattice charge amount) Ci-chi Economic Co-op Property Office employee printed

As shown in FIG. 16, the complex oxide represented by L i aMn 0.5-xN i 0.5-7] // [乂 + 7〇2] is replaced by solid solution of different elements M, and especially ^ 1 is (: 〇 1 ^ 31 ^ .. 51..5 "(: 〇 ^ 〇2 (the composite oxide C1 of the positive electrode active material of the battery of Example 2-1), the a-axis and c-axis crystals before charging The distances between the cells are all smaller than L 1 Μ η 0.5 Ni 0.52, (the composite oxide A 1 of the positive electrode active material of the battery of Examples 1-1), and the crystal lattice volume is reduced. Charge again The state of the c-axis lattice This paper scale applies the Chinese National Standard (CNS) A4 specification (210X297 mm) -144- A7 B7 V. Description of the invention (in terms of distance between 141, the composite oxide c 1 is slightly higher than the composite oxide In the charged state, the inter-lattice distance of the c-axis in the charged state roughly maintains the narrowing gap before charging, as shown in Figure 17, the crystal lattice volume (composite oxide C) when different elements M are solid-solution replaced. 1) It is smaller than the crystal lattice volume (composite oxide A 1) when it is not solid-solution replaced with a different element M. Therefore, even with a small total pore volume, it is easy to use a different element M The reason for ensuring the discharge capacity is not caused by the increase of the crystal lattice volume and the increase of the freedom degree of the Li ion ions, but the influence of the electronic states of the oxygen bound by different elements M and the freedom degree of the Li ion ions. Increasing sake. The high-density lithium-nickel-manganese-cobalt composite oxide produced by the coating co-precipitation method is a sintered single-phase composite oxide. Its charge-discharge cycle performance is slightly better than that of the co-precipitation method. The composite oxide has the effect of reducing the shrinkage and deformation of the surface due to the addition effect of C0.

From the results of the previous examples, it is known that L ia Mn η 5/1 2 N i 5 / 12C 02/12 〇 2 is more than c 0 than L Mn 0.5-xN i 〇 .5-71 \ / 1 '\ + 7〇2 When used as a positive electrode active material, an operating voltage of 4 · 3 V ~ 3 · Ο V with excellent interchangeability with conventional lithium batteries can be obtained and 160 m can be obtained High discharge capacity of A h / g. The same evaluation was performed when a large amount of Li was used as the positive electrode active material, and a composite oxide represented by the composition formula L i a M η 0.5-X N 1 0.5-y M X + y02 was used. When a exceeds 1 · 1, the initial discharge capacity tends to decrease. This is because the unreacted lithium becomes L 1 2 C03. This paper size applies the Chinese National Standard (CNS) A4 specification (210 X 297 mm) (read the precautions on the back before filling in this page). Printed by the Employees ’Cooperatives of the Ministry of Intellectual Property Bureau -145- 5 Printed by the Employees’ Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs and printed by Gu Geng) Replacement page A7 Β 7 V. Description of the invention (14 ^ From the results in Table 1 1 50% of the distribution has a particle size of 0 · 8 // m or more and 10 // m or less, and 10% particle size of 0.4 / m or more and 7 // or less composite oxide is used for the positive electrode active material The battery of Example 5 _ 1 to 5-3 has a high discharge capacity (refer to the discharge capacity at the 50th cycle), and the charge-discharge cycle performance (refer to the capacity maintenance rate) is better than that of Examples 5-4 to 5-6 Battery (Example 6-1) (Production of the positive electrode) The positive electrode active material was a composite oxide C 1 6 and a square nonaqueous electrolyte battery as shown in FIG. 19 was produced as follows. Mix at a weight ratio of 8 5: 1 0 ·· 5 Composite oxide C 1 6, conductive agent acetylene black and adhesive agent polyvinylidene fluoride (p V d F), add solvent N-methylpyrrolidone of the agent is kneaded and dispersed to prepare a positive electrode coating liquid. The polyvinylidene fluoride system uses a solid content to dissolve the dispersed solution, and the solid content is converted by weight. The positive electrode coating liquid is applied to a thickness of 20 // m two sides of the aluminum foil current collector, adjust the overall thickness to 2 3 0 to make a positive electrode plate. The positive electrode plate is cut into a shape with a width of 61 mm and a height of 107 mm, and the thickness at the end of the plate is 2 0 / / m, 10 mm wide guide plate, as the positive plate 7. Change the positive electrode active material] ^ 1〃1 ^ .. 45 化 ..45 (: 〇..102。 2 X-ray winding The measurement of the crystal lattice volume calculated from the obtained crystal sizes of the a-axis and c-axis is shown in Fig. 20. The crystal lattice volume when X 値 is 0.6 is 0 when X 値 is 0. For the crystal lattice volume, about this paper size applies the Chinese National Standard (CNS) A4 specification (210X297 mm) (Please read the precautions on the back before filling this page) -151-

V. Description of the invention (15j particle size L c · is about 60 ~ 100 nm. 'Carbon material with true specific gravity of 2.24g / cc and specific surface area of 1.7m2 / g.' There is no particular restriction on the relationship between the substance and the volume change rate of the crystal lattice within the foregoing range. The foregoing (battery performance evaluation) is described with respect to a square battery, but the characteristics described above are not limited to this structure, and the cylinder The same effect can also be obtained with batteries of the shape, flat type, coin type, etc. (Example 7-1) A non-aqueous electrolyte secondary battery of 800 m Ah as shown in FIG. Weight ratio 4 5: 4 5 ·· 5: 5 mixed lithium-cobalt oxide (called Cellseet C-10 by Ben Chemical Industry Co., Ltd.), composite oxide C9, acetylene black and polyvinylidene fluoride as adhesive (PVdF), adding N-methylpyrrolidone as a solvent, and kneading and dispersing the coating solution. The polyvinylidene fluoride is a solid solution that dissolves and disperses the dissolved solution, and the solid content is converted by weight. The coating solution is coated on Adjust both sides of the aluminum foil current collector with a thickness of 10 # m The thickness is 100 0 // m, and a positive electrode plate having a positive electrode active material of 20 mg / cm 2 is produced. The foregoing positive electrode plate is cut into a shape having a width of 61 mm and a length of 4 4 5 mm, and the positive electrode at the end of the plate is removed. Ultrasonic welding is used to install aluminum positive terminal 3 2 with a thickness of 1 0 // // m and a width of 3 mm as the positive electrode plate. Artificial graphite (particle size 6 // m) is used as the negative electrode carbon material, mixed with an adhesive 2% by weight of styrene butadiene rubber and carboxymethyl of tackifier The paper size is applicable to China National Standard (CNS) A4 (210X 297 mm) (Please read the precautions on the back before filling this page) Order Printed by the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs -157-

ABCD VI. Patent application scope 1 No. 9 1 1 0 8 1 4 8 Chinese patent application scope correction I 1---! -I pv: -1 1 —I i— n (Please read the Note: Please fill in this page again.) Correction on November 13, 1995 1 · A positive electrode active material characterized by the composition formula LiaMn〇.5- xNi〇.5- yMx + y〇2 (〇 &lt; a & lt 1.3, — O.lS X — 0.1, M is a compound oxide represented by elements other than Li, Mn, and Ni). 2. The positive electrode active material according to item 1 of the patent application range, wherein the μ is at least one element selected from the group consisting of Al, Mg, and Co, and the coefficient in the aforementioned composition formula contains a composite oxide satisfying the following relational formula , 0.05S x &lt; 0.3 0.05 ^ y &lt; 0.3 -〇.l ^ x-yg〇〇2 0 &lt; a &lt; 1.3 x + y &lt; 0 · 5 〇3. The positive electrode active material of 2 wherein M is Co. Printed by the Consumer Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs 4. A positive electrode active material, which is characterized by LiwMn &quot; Ni &quot; Co &quot; 〇2 (^, y ,, z 'is in the ternary state diagram, (x', y ', z') exist at point a (0.51, 0.49, 0), point B (0.45, 0'55, 0), point C (0.25, 0.35, 0.4), and point D (0 · 3 1, 0 · 2 9, 0.4) are the numbers on the line or inside of the quadrilateral ABCD with apex, 値 Sw / (x '+, + z') ^ 丨 .30). 5. If applied The paper size of the positive electrode in any one of the patent scope 1, 2, and 4 is applicable to the Chinese National Standard (CNS) A4 specification (210 X 297 male thin)

ABCD 541745 VI. Patent application scope 2 Active substance 'wherein the composite oxide system has a total pore volume of 0.0000 ml / g or more' 0.006 ml / g or less and uses a powder X-ray diffraction pattern of CUK α rays 2Θ: diffraction peak pair of 44 · 1 ± Γ 20: 18.6 ± 1. The relative intensity ratio of the diffraction peaks is 0.6 5 or more and 1.0 5 or less. 6. The positive electrode active material according to any one of the claims 1 '2, 4', wherein the specific surface area of the composite oxide is 0.3 m2 / g or more and i. 6 m2 / g or less, and CuK α wire is used The relative intensity ratio of the diffraction peaks of the powder X-ray diffraction pattern of 2 0 I 44 ″ 11 1 ° to 2 Θ: 18.6 ± Γ is 0.6 5 or more and 1.0 5 or less. 7 · The positive electrode active material according to item 5 of the patent application scope, in which 20: 18.6 ± 1. The half-width of the diffraction peak is 0.05. Above 0.2. Below, and this 2 Θ: 44.1 ± 1. The half-width of the diffraction peak is 0.10 ° or more and 0.20 ° or less. 8 · The positive electrode active material according to any one of claims 1, 2, and 4, wherein the composition of the composite oxide is an a-NaFe0 2 layered structure, and the crystal unit lattice is hexagonal. At the potential of metallic lithium, the lattice constant a, lattice constant c, and crystal lattice volume V of the aforementioned hexagonal crystal in a state of 3.2 V to 3.3 V satisfy the following formula, 2.860 $ 2.89 0 14.20 ^ c ^ 14.33 0.1 0 0 7 n m3 ^ V ^ 0. 1 0 3 4 n m3 where a and c are lattice constants, respectively equal to the length in the a-axis direction and the length in the c-axis direction of the unit crystal lattice, in Angstroms (A) The paper size of the unit applies to the Chinese National Standard (CNS) A4 specification (2IOX297 mm) n I n LI I— LI I nn I (Please read the notes on the back first and fill in this page)-Intellectual Property of Ministry of Sound Economy Printed by Bureau Consumers Cooperative

ABCD 541745 6. Scope of patent application 3 9. If the positive electrode active% of any of the items i, 2, and 4 of the scope of patent application is' wherein the composite oxide is sintered at a temperature of more than 9Q0t and less than 10 ° C Those who earn more than 3 hours. 1 · If the positive electrode active material according to any one of claims 1, 2, and 4, the particle size distribution of the composite oxide is 50%, and the particle size is 0.8 or more; πm or more and 10 μm or less, The 10% particle size is 0.4 μm or more and 7 or less m. 1 1 · The cathode active I biomass according to any one of claims 1, 2, and 4, which further contains lithium cobalt oxide. 1 2 · The positive electrode active material according to any one of claims 1, 2, and 4, which further contains "having a spinel structure with Li 1+ SMη 2 —S" M… t〇4 (but 〇 $ s $ 0.3, 〇StS0.2, M ... are lithium manganese compounds represented by at least one element selected from the group consisting of Mg'A1'Ti, V, Cr, Fe, Co, and Ni "." 1 3 · A method for manufacturing a positive electrode active material, which is characterized by containing LiaMn0.5-xNi〇.5-y] Vrx + y〇2 (but 0.98 $ a &lt; 1.1, ySO "Is a method for producing a positive electrode active material of a composite oxide represented by at least one element selected from Al, Mg and Co) by dissolving a nickel (N i) compound and a manganese (M η) compound in an aqueous solution of water 'Or in an N i compound, M n compound, and M, compound (M, same as above) dissolved in an aqueous solution of water, adding an alkali compound, a reducing agent, and a complexing agent' while controlling the pH of the aforementioned aqueous solution to be 10 to 3 The co-precipitation step of causing the Ni-M η composite co-precipitate or N 丨 -μ n-μ 'composite co-precipitate to precipitate in the aforementioned aqueous solution "to produce the aforementioned composite oxide. This paper size applies Chinese National Standard (CNS) Α4 specification (210X297 male thin) (Please read the precautions on the back before filling this page) ♦ Τ Printed by the Intellectual Property Bureau Staff Consumer Cooperatives of the Ministry of Economic Affairs 541745 Α8 Β8 C8 D8 Scope of patent application 4 (please read the precautions on the back before filling out this page) 1 4. For the method of manufacturing the positive electrode active material in the scope of patent application No. 13 in which the nickel (Ni) compound aqueous solution is used in the co-precipitation step , An aqueous solution of a manganese (Mn) compound, an aqueous solution of an M1 compound (1VT is an element selected from at least one of A1, Mg, and Co), an aqueous solution of a complexing agent, and an aqueous solution of a reducing agent, as the foregoing aqueous solutions, or the foregoing At least two or more mixed mixed aqueous solutions in the aqueous solution are continuously supplied into the reaction tank, while the alkaline compound aqueous solution is continuously supplied into the aforementioned reaction tank, and then the generated Ni-Mn-M 'composite coprecipitate is continuously taken out. 1 5 · The method for manufacturing a positive electrode active material according to item 13 or 14 of the scope of patent application, wherein the reducing agent uses rhenium. Printed by the Consumer Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs 16 · If the method of manufacturing a positive electrode active material in the scope of patent applications No. 13 or 14 is characterized by "N} obtained by the aforementioned co-precipitation step -M η The composite coprecipitate or Ni-Mη-M 'composite coprecipitate is dispersed, and the IVT compound (M' is an element selected from at least one of Al, Mg, and Co) is dissolved in the dispersion to dissolve the water, Add an alkali compound and a complexing agent 'to control the pH of the water-soluble dispersing liquid to be 10 ~ 13, and then make the composite coprecipitate of the same element as above) precipitate on the Ni-Mn composite coprecipitation obtained in the aforementioned co-precipitation step. Co-precipitation step of coating the surface of a compound or the surface of a compound of a Ni-M η-M 'composite co-precipitate "to produce the aforementioned composite oxide. 1 7 · A method for manufacturing a positive electrode active material such as π or I 4 in the scope of patent application, wherein the complexing agent is a compound capable of dissociating ammonium ions in an aqueous solution. 1 8. If the paper size of the positive electrode active material in item 13 or 14 of the scope of patent application is applicable to the Chinese national standard (CNS) A4 specification (210 × 297 mm) -4- 541745 A8 B8 C8 D8 6. Application scope 5 A manufacturing method in which "the compound J capable of dissociating ammonium ions in an aqueous solution is one or more compounds selected from the group consisting of ammonium nitrate, ammonium sulfate, ammonium chloride, and ammonia water. 19. The positive electrode according to item 13 or 14 of the scope of patent application The method for manufacturing an active material, wherein the aforementioned NT is Co. 20. The method for manufacturing a positive electrode active material according to the scope of application patent No. Π or 14, wherein the Ni-Mn obtained through the aforementioned co-precipitation step or the co-precipitation step is applied. The composite coprecipitate or the Ni-Mn-M 'composite coprecipitate is sintered together with the lithium compound at a temperature of 900 ° C or higher and 1100 ° C or lower for more than 3 hours to produce the aforementioned composite oxide. 2 1. A positive electrode for a non-aqueous electrolyte secondary battery, characterized in that it contains a positive electrode active material according to any one of claims 1 to 12 of the scope of patent application. 22. —A positive electrode for a non-aqueous electrolyte secondary battery, characterized in that it contains a positive electrode active material such as any of items 1 to 12 of the scope of application for a patent; and the aforementioned positive electrode active material has a conductivity of 1% by weight or more. Carbon material; Adhesive with ion conductivity due to electrolyte solution. 23. A non-aqueous electrolyte secondary battery, which is characterized by including a positive electrode for a non-aqueous electrolyte secondary battery, a negative electrode for a non-aqueous electrolyte secondary battery, and a non-aqueous electrolyte as described in the patent application No. 21 or 22. 24. If the non-aqueous electrolyte secondary battery of item 23 of the patent application scope, wherein the aforementioned negative electrode for a non-aqueous electrolyte secondary battery is a negative electrode material containing a lithium ion which can be occluded and released. 25. If the non-aqueous electrolyte 2 of the scope of application for the patent No. 23 or 24; battery, the positive electrode active material is with the non-aqueous electrolyte secondary battery &amp; (Please read the precautions on the back before filling this page) Printed by the Consumers' Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs, the paper size is applicable to China National Standards (CNS) A4 specifications (210X297). -5- 745 745 A8 B8 C8 D8 6. Application for patent scope 6 Lithium ions are released upon charging to make crystals For the cell volume shrinkage, the above-mentioned crystalline lattice volume shrinkage ratio is 4% or less of the crystalline lattice volume of the positive electrode active material at the end of the discharge state of the non-aqueous electrolyte secondary battery. The negative electrode material follows the non-aqueous electrolyte. Lithium ions are charged and charged in the secondary battery, which causes the crystalline lattice volume to expand. The crystalline lattice volume expansion rate is less than 6% when the crystalline lattice volume of the negative electrode material in the end state of the non-aqueous electrolyte secondary battery is discharged. Within the general charge and discharge range of non-aqueous electrolyte secondary batteries, the 値 of the aforementioned expansion coefficient of the negative electrode material is greater than or equal to that of the aforementioned positive electrode active material The difference between the aforementioned shrinkage ratio and the shrinkage ratio of the anode active material within the general charge / discharge range of the non-aqueous electrolyte secondary battery is 0% or more and 3% or less. 1 511 I ------ IT---I m ill n (Please read the notes on the back before filling out this page) Order 4 Printed on paper standards of the Ministry of Economic Affairs, Intellectual Property Bureau, Employees' Cooperatives, Chinese paper standards ( CNS) A4 grid (210 X 297 mm) -6-