TW201219311A - Cobalt hydroxide, method for producing same, cobalt oxide, and method for producing same - Google Patents

Abstract

The purpose of the invention is to obtain cobalt hydroxide and cobalt oxide, each having high aggregability even if a secondary particle size is large. The invention is cobalt hydroxide characterized by being in the form of secondary particles obtained by aggregating primary particles, comprising, as the primary particles constituting the secondary particles, primary particles in the form of a plate, a pillar, or a needle having a major axis length determined by SEM image analysis of 1.5 [mu]m or more, and having a tap density of 0.80 g/mL or more.

Description

201219311 VI. Description of the Invention: [Technical Field] The present invention relates to cobalt hydroxide or cobalt oxide, and particularly to cobalt hydroxide or cobalt oxide suitable for use as a raw material for lithium-cobalt composite oxide production of lithium rechargeable batteries, and manufacture thereof method. [Prior Art] In recent years, with the rapid development of portable and wireless home appliances, rechargeable batteries have become practical as power sources for small electronic devices such as notebook computers, mobile phones, and video cameras. Since Lithium Cobaltate (LiC〇〇〇 can be used as a report on the anode active material of rechargeable batteries, the research progress of lithium transition metal composite oxides has been active, and many research reports have been made so far. Lithium transition metal composite oxides Lithium cobaltate (Lic〇〇2), lithium nickelate (LiNi0〇, lithium manganate (LiMnOO is often used, especially lithium cobalt oxide which is advantageous in safety surface and charge and discharge capacity). In recent years, lithium The demand for high capacity of rechargeable batteries has increased, and the demand for developing lithium cobalt oxide composite oxides for high-capacity lithium rechargeable batteries has also been proposed. The methods for achieving high capacity of lithium rechargeable batteries include: (1) Cobalt of large particles Lithium acid is mixed with small particles of lithium cobalt oxide, and the filling rate of the anode active material is increased, and the capacity per unit volume is increased (for example, Patent Document υ; (2) as LiNie L · 1 5 Q 2 Change the name of the composition of lithium silicate, increase the capacity per unit weight to 'bite the ancient method of 晋 仆 例如 (for example, Patent Document 2). 201219311 However, in the above method (1), small particles for the battery In addition, in the above method (2), the lithium compound alkali ruthenium used in the production of LiNi.8 <0.ls02 remains, in particular, in the case of repeated charge and discharge, the gas generated by the reaction with the non-aqueous electrolyte is increased. For the safety of the battery, in particular, the problem of the increase in the gas caused by the reaction with the non-aqueous electrolyte during the reversal of the charge and discharge is carried out. [Patent Literature] [Patent Document 1] Japanese Patent Laid-Open No. 2004_1 82564 (Patent Document 1) [Patent Document 2] [Patent Document 2] Japanese Patent Laid-Open Publication No. Hei No. 243 (Patent Application Scope) L SUMMARY OF THE INVENTION [Problems to be Solved by the Invention] In view of the above-described lack of the conventional methods, a new lithium rechargeable battery The high-capacity method needs to be developed. Therefore, a method of increasing the cell size per unit volume by adjusting the particle size of lithium cobaltate to 15 to 35 μm and increasing the tap density is considered. The raw material of lithium acid or cobalt oxide has a k-size of 〇·H5 μm. To obtain a particle size of 15 to 35 μm: lithium cobaltate, it is necessary to use a cobalt hydroxide of 15 μm. Or cobalt oxide reacts with the lithiated compound, and it is necessary to increase the amount of the compound to grow the particles during the reaction. Therefore, in the method, the ratio of the obtained acid clock is

4 201219311 About 1.060, lithium compounds must be used to reach more than 15 microns of cobalt acid. However, when the amount of the chain is too large, the amount of the lithium compound which is reacted with cobalt hydroxide or cobalt oxide will not be reduced after the hydrogen hydroxide reduction or the oxidation particle size is large as the raw material for the production. Too much is left, and lithium cobaltate having a particle size of 5 to 35 μm can be obtained. However, the particle size of 15 to 4 〇 micro-particles of cobalt hydroxide or cobalt oxide produced by the conventional manufacturing method is also weak due to its _ / ', and the lower particle strength of the human particles. = the agglomerability of the secondary particles is weak)), and the secondary particles are decomposed with the bell of the bell before the reaction, so the particle size is reduced when the compound is reversed. It is widely known that the object of the present invention is to develop cobalt oxyhydroxide or cobalt oxide which can increase the particle diameter of secondary particles and maintain the particle strength ( ^ ^ 丌 is called agglomeration of primary particles). [Means for Solving the Problem] :: In the above problems, the inventors of the inventors have worked hard to find out the neutralization of the initial aqueous solution (sputum) and the aqueous solution (sputum) of the anti-Luo solution: 'Use of glycine-containing record The aqueous solution (α liquid) is used to maintain the molar ratio of the initial aqueous solution (the attack and the molar acid) to a specific range, and the sputum and sputum are added to the water solution of the glycerol acid. # and reaction, once M. f. y, sub-group and the primary particles constituting the secondary particle are analyzed by a known electron microscopy, which is a plate shape, a column shape, or a needle shape with a length of light of 15 μm or more - The secondary particles of more than 5% of cobalt hydroxide, 4.80 g / pp of the cobalt ruthenium secondary particles not only 201219311 have large particles and strong agglutination, the present invention is completed. That is, the invention (1) provides a hydroxide Cobalt, its special particles are condensed into secondary particles, and the composition::: After electron microscopy analysis, it is found to be long 2 = ::: upper column or needle-like particles, the density of the shake is " Further, the present invention (2) provides a hydrogen peroxide, which is characterized in that The aqueous solution of proline is 'Atom-converted relative to the record! Moer, Gan = the content of O.OIOUO Mo Erzhi aqueous solution (A liquid) and water test liquid) added glycine aqueous solution (C liquid), by The production and reaction of 55 to 75 〇c can be carried out to obtain the hydration and the engineering. Further, the invention (3) provides a method for producing cobalt hydroxide, which is characterized by a solution of glycine containing algium, which is relative to the The content of 1 ...1 is 〇· °1. ~ °· _ Moer's solution (A solution) Lo solution (β solution) is added to the aqueous solution of glycine (C solution), due to the neutralization reaction of 55^75 The process of obtaining a cobalt hydroxide neutralization process is carried out. Further, the invention (4) provides a oxidized crystal, characterized in that a plate-shaped, column: or primary particle of:: is condensed into secondary particles, and the secondary IA particles are composed. After the analysis by scanning electron microscopy, it was found to have an average diameter of 1.5 μm or more. In the invention (5), the method of producing the oxidized diamond of the invention (3). Cobalt, which is characterized by: inclusion of 200~1000 [Effect of Burning Oxidation of Cobalt Oxide] [Effect of Invention] 201219311 The present invention provides a shape of monohydrogen oxide secondary particles, and secondary particles of cobalt and cobalt oxide, which have a characteristic particle size and a strong aggregability. [Embodiment] [Brief Description of the Invention] Hereinafter, preferred embodiments of the present invention will be described. The hydrogenation start of the present invention is characterized by: primary secondary particles, and the composition of the secondary particles - Dan, ', After micro-mirror analysis, it was found to be a long-distance 子 描 电子 电子 电子 显 霄 霄 霄 霄 霄 霄 ° 霄 霄 霄 霄 霄 霄 霄 霄 霄 霄 霄 霄 霄 霄 霄 霄 I I I I I 氢氧化 氢氧化 氢氧化 氢氧化 氢氧化 氢氧化 氢氧化 氢氧化Image analysis such as the state of the particle characteristics of the electron microscope image, the second two: after the projection, the second sub-subject of the second sub-child is obtained. A mode oblique view in which the major axis length m is a secondary particle length and a short diameter is a plate-shaped constituting secondary particles will be described with reference to Fig. 21 . (1) The angular columnar shape of the secondary particle, the oblique view of the equation. (8) is the mode oblique view of the acicular-secondary particle constituting the sub-particle. (C) is the slab-like particle of the second figure 21(A) and &quot ; face 1a and the side surface la6 of the surface, the intersection surface: -: the side surface la of the surface of the human particle can be fully expressed in the under-particle core 23. Among the surface of the secondary particle, however, the surface of the surface is the second The image is inside the second teaching, because 乂: because most of the existence exists - part of the secondary particle sweep 201219311 electron microscope shadow φ. Therefore, in the present invention, the long diameter of the primary particle electron microscope In the surface of the secondary particle appearing in the image, "the major axis X of the side surface u of the surface of the secondary particle. In addition, in the present invention, the minor axis length of the secondary particle is the side of the surface of the secondary particle in the surface of the scanning electron microscope. (4) Short-diameter"--------------------------------------------------------- Side of the surface ^

Table 2, Figure 22 (β) shows only the portion of the frame. The symbol X of Fig. 22 (8) is not, the degree is the length of the major axis of the primary particle, and the sign is the length of the short diameter of -. Furthermore, the surface of the 00 person pulls the non-plate-like primary particles agglomerated into the secondary particles, and the surface scan electrons 3 the human light mirror W image (1), the frame line portion is the secondary particle = the side of the surface u靡 'Figure 23 (8) shows only the line portion. Fig. 2 The length of the long product J Α m represented by the spoon X is the length of the long diameter of the secondary particle, and the symbol y is the length of the diameter of the human particle. The plate-shaped primary particles shown in Fig. 21(A) are of such a shape, and as long as they are half-reciprocal, the limited-convenient plane direction is also one-shape, and the shape is not π, and may be Curved shape. Figure 21 (B) shows the columnar_subgrain 1 hu café 3 - the side of the surface of the human particle and the "intersection of the side lb of the surface _ side lb can be fully expressed in _ a 4-work one - human particles In the surface, however, the surface of the surface is two: the scanning electron microscope image of the human particle is in the secondary particle: the parent surface 2b is because most of the 圹Φ exists because only a part of it appears in the electron microscope image of the secondary particle. Therefore, in the present invention, the length is a scanning electron display, and the long-diameter 1 micro-mirror image of the one-human particle appears in the surface of the secondary particle. The short-length sound of the surface of the secondary particle surface of the 201219311 secondary particle surface is In addition, in the present invention, the sub-length is the surface of the visible electron microscope shadow S Φ - /> I The primary granules of the cadaveric corpse - the short diameter 乂 of the side lb of the surface of the human particle. Figure 2UB The columnar columnar Μ 韭 韭 TM τ τ τ τ 四 四 τ τ τ τ τ τ 四 四 四 四 四 并非 并非 并非 并非 四 四 并非 并非 四 四 四 四 四 四 四 四 四 四 四 四 四 四 四 四 四 四 四 四 四 四For the curved shape, the needle-like one, the middle, and the dry τ shown in Fig. 21(C) Α—Scanning electron microscopy image of human particles ,.,,) (The six sides of the surface of the secondary particle are not... The side 1C of the surface and the surface 2c of the side lc of the surface. In the present invention, —, the puller The length of the long length is the long diameter x of the lc exposed on the side of the surface of the surface of the scanning thunder microscope. In the invention, the short diameter of the primary particle is twice as observed in the scanning electron microscope image. The side surface of the particle surface has a short diameter of 7 ^. In addition, the long diameter length and the short diameter length of the primary particle can be obtained by analyzing the scanning electron microscope image. The long diameter and the short diameter length of the one-human particle are flat. The long-diameter and the short-diameter measured on the surface of the secondary particle according to the shape of the primary particle in the plan view. The hydrogen peroxide of the present invention is a secondary particle obtained by aggregating the secondary particle. Particle-sub-particles, including slab-like, columnar, or acicular primary particles with a long diameter of 1 and only ib micro or less, and other τ, ie, spheres, are analyzed by scanning electron microscopy. , indefinite shape-sub-particles, scanning electron microscope image analysis, plate-shaped, columnar, or needle-like primary particles having a long diameter of less than 1.5 μm, etc., and the secondary particles constituting the cobalt hydroxide secondary particles of the present invention must be a plate-like, columnar, or needle-shaped sub-particle having a long diameter of 1.5 μm or more ^ 201219311 The cobalt hydroxide of the present invention is (1) a plate shape having a scan length of 1 · 5 μm or more, and micromirror image analysis Long-distance heart-shaped, columnar, secondary particles, or (1) Scanning electrons: plate agglomerates with a degree of agglutination of 1.5 μm or more, long diameters and long shapes, indefinite shapes, scanning power + The human pulls, as well as the 1.5-micron plate, column, and the length of the ball under the length of the ball - is also the primary particle secondary particle. Scanning electron microscopy images of two particles of plate, column, or acicular-sub-particle = set: "The shape of the secondary partial primary particle is confirmed. One of the secondary particles is scanned. Electron microscopy image of plate-shaped, columnar, or needle-shaped primary particles above the meter = length U is slightly more than 40% of the total secondary particles, more excellent...: plate, column, or needle above m If the ratio of the presence of the particles-particles is within the above range, the compressive strength of the corrugated cobalt and the image of the weathered micromirror in the shaking x ^, the long scale guide sound 丨ς ◊ 描 电子 电子 电子 电子 电子 ... ... ... ... ...... , columnar, or acicular-human particle presence ratio Τ head-up A Μ 不 不 U U U U U U U U U U U U U U U U U U U U U U U U U U U U U U U U U U U U U U U U U U U U U U U U U U U U U U U U U U U U U U U U U U U U U U U U U U Plate-like, columnar, or needle-like area ratio of under-particles. Regarding the calculation method, - human electron shovel A @, first enter the secondary particle scanning two micro-mirror image analysis 'to carry the secondary particles The quadratic projection, any 100 secondary particles. Next, Pumping the given volume wash Xi -A, 7 Shang a hill - a surface area of the particles person "long path length of less than U m - secondary particles, then it was extracted juice heterologous with respect to the total area of the secondary particles 100 and

10 201219311 Percentage of the total area of the primary particle ancestors of the long diameter of 1.5 μm or more 0 The long diameter average of the plate-like, columnar, and primary particles constituting the cobalt hydroxide secondary particles of the present invention More than 15 microns, more than 2. 0 to 5. 0 microns, especially more preferably 2 5 to 4 4. b micro. The average value of the long diameter of the plate-like, columnar or needle-like sub-particles is within the above range, and the compressive strength and the tap density of the cobalt hydroxide can be improved. 〇 ^ - The method of calculating the average value of the minor particle diameter, the analysis of the electron microscope image, the owing position ^ Ding - human puller knowing nine kinds of one - human particle for the second element projection thinking out of 100 primary particles. Then, the 6Α 者 疋 疋 疋 疋 疋 疋 一次 一次 一次 一次 一次 一次 一次 一次 一次 i i i i i i i i i i i i i i i i i i i i i i i i i i i i i i i i i i i The long-term flatness of the heart and human particles According to the inventors' group, the wind emulsion containing #复人巧颜介物& 3 is a complex with nickel and nickel. The shape of the rolled metal is slab-like or sturdy ^, and the particles of the pill are integrated into a female object (Japanese special Kaiping 1〇_29 becomes a human grain worker ★ E newspaper) 4 long composite oxide The diameter of the maximum is less than 〇.5 One-piece particle secondary aggregation: secondary particles, and the hydroxide of the invention is recorded in a plate shape or column shape of one micron or more, and: human: sub: contains a long diameter of 15 ., A Needle-like primary particles. -+ Private craftsmanship plate, columnar, or needle-shaped _ a —- human particles in the material spoon _ human particles have a long-axis average value of preferably i 5 micro or less, more preferably 2 衩 good for 1.5 Meter. .. 〇 micron, especially more preferably 2.5 to 4.5 micro Å 本 7 7 7 — — — — 次 次 次 次 次 次 次 次 次 次 次 次 次 次 次 次 次 次 次 次 次 次 次 次 次 次 次 次 次 次 次 次 次 次Better

II 201219311 Two Γ · 2 microns. When the average value of the minor diameter of the secondary particles is within the above range, the initial strength and the tap density of the ammoxidation can be increased. In addition, the method of calculating the average value of the short diameter of the particle is determined by measuring the long diameter of the human B ^ m m ^ ^ field-human particle. The short diameter length of human particles 〆Ύ L has the same effect as the average of the primary particle length. Ding Chang, the secondary particles of cobalt hydroxide of the present invention, 1 η Λη , .. , j, the tenth particle diameter is preferably 10 to 40 μm, more preferably 15 to 4 〇 ^ τ When the average particle diameter of the secondary particles is within the above-mentioned μ micro water dry circumference, the cobalt oxide obtained by the reaction of the cobalt hydroxide/lithium compound] has a ten-average particle diameter of 15 to 35 micro water, and a high unit can be obtained. ... The acid clock in the early volume. In addition, the single particle of the secondary particle of the present invention is oxidized and the thousand particles of the secondary particle are controlled.

Μτ# can be obtained by laser differential scattering method using MICR〇mCK MT330G EX II manufactured by Nikkiso Co., Ltd. The turbidity of the cobalt hydroxide of the present invention is 0.80 g/ml or more, preferably 1.00 to 2.50 g/ml, more preferably A 50 h.摇 虱 录 的 W W W W W W W W W W W Μ Μ 10 10 10 10 10 10 10 10 10 10 10 10 10 10 10 10 10 10 10 10 10 10 10 10 10 10 10 10 10 10 10 10 10 10 10 The primary diameter of the plate, the columnar or the needle-shaped primary particle on the ν!_.m is a compressive strength of the secondary particles of the cobalt oxyhydroxide of the present invention of 5, MPa, preferably 8 ~30 dead par. In the range of the second granules of the initial stage of hydration, it is possible to prevent μ e 7 and prevent the formation of bismuth hydroxide and bismuth-human particles when the reaction between bismuth cobalt and lithium compounds is prevented. Secondary particles of small particle size. The lithium hydroxide of the present invention has a lithium hydroxide of an average particle diameter of 15 to 35 μm by using a large particle having an average particle diameter of 15 to 40 μm 12 201219311. Further, the compressive strength of the secondary particles of the present invention was measured by MTC-W. In particular, by appropriately using large-sized particles having an average particle diameter of the cobalt hydroxide of the present invention having a compressive strength within the above range of 15 to 4 μm, an average acid particle of 15 to 35 μm can be obtained.俾 Increase the unit volume capacity of the rechargeable battery. The cobalt hydroxide of the present invention can pulverize the shearing force of 1, π f π, and the particle size distribution of the secondary particles before and after the pulverization treatment is less/preferably the secondary particles after the pulverization treatment. The average particle diameter is low at .〇 microns at τ. Therefore, when the gasification ring and the raccoon compound of the present invention are mixed in the production of the start acid clock, the secondary particles from the gas oxidation are not easily decomposed, and thus lithium cobalt oxide having a large average particle diameter can be obtained. The hydroxide # of the present invention is preferably produced by the following method of the present invention. The method for producing a hydroxide of the present invention is characterized in that the content of glycine in the cobalt-containing aqueous solution containing glycine is 0010 to 〇3 以 in terms of atomic conversion of cobalt 1 mol. Moore's cobalt solution (sputum). The aqueous solution (sputum) is cut, added to an aqueous solution of glycine (c liquid), and subjected to a neutralization reaction to obtain a method for producing cobalt-containing cobalt.之中; The method and method for producing cobalt ruthenium oxide according to the present invention is to add A y & Α ', the cobalt ruthenium in the sputum and the alkali sputum in the sputum by adding the liquid C and the β solution. In the / text 1Ρ to carry out the project of neutralization. 13 201219311 Liquid A is an aqueous solution containing glycine (10) 2CH2C_). The acid is prepared by dissolving it in water. Nowadays, there is no sputum in the sputum in the liquid A; e笪, the system of the right, can be the vapor of cobalt 'nitric acid ^ barium sulfate. This is better than the use of gas to avoid the incorporation of impurities into the sulfuric acid I. In addition, you can also coexist with a small amount of other metal mites. Metal ruthenium that can coexist, such as metal ruthenium such as snail manganese, magnesium, aluminum, or titanium. The ion channel in the liquid A is not particularly limited, and is preferably 1.0 to 2.2 mol/liter after atomic conversion, more preferably, .^ ^ is preferably 1.5 to 2.0 mol/liter. The concentration of cobalt ion in the liquid A is in the above range - the tongue can be produced in a good manner, and the car is not prone to occur in the case of the sputum. On the other hand, if the cobalt ion concentration in the liquid A does not reach the dry circumference, the productivity is liable to be lowered, and if it exceeds the above range, the image is contained. The raw n n precipitated from the A liquid relative to the beginning of the A liquid, the glycine content is converted to Mohr by atom, preferably q q5 (four) 2q

In the liquid, the content of glycine is in the range of the above, and even if the particle size of the particle is large, it can be made of lithium, ▲ ^ e is strong, and therefore in cobalt. Lithium acid I is mixed with a lithium compound to maintain the particle size, and one person does not decompose the 'Ding Ba』 Fantasy + average particle size of 15 to 35 micro-particles of lithium cobalt oxide. On the other hand, if the content of the cobalt in the liquid A is less than the above range, the agglutination of the cobalt-cobalt-based 0 0-夂 particles is 4, and the right is beyond the above range. There will be +8 + = _ 庑^ & Yes. The unreacted cobalt ruthenium remains in the reaction solution, which deteriorates the productivity. The reverse B solution is an aqueous alkali solution, and the B liquid is the test spoon. The solution is prepared in water and 201219311 * into. The alkali hydrazine used for the liquid B is not particularly limited, and may be a metal hydroxide such as hydrogen hydride or potassium hydroxide, and further preferably: hydroxide. The concentration of the sputum sputum and the total amount of alkali strontium added to the liquid C can be appropriately selected depending on the concentration of the sputum cobalt ion and the total amount. The concentration of the liquid B is preferably 5 to 15 m/l, especially the ear. J. C liquid is an aqueous solution of glycine, and c liquid is prepared by modulating glycine. In the liver, middle and middle engineering, the sputum and the 6 liquid are added. The reaction liquid in the liquid (the glycine concentration in the liquid is preferably 0.010~0.25. Moule/L, ::~°.17° Moule/L. That is, 'for the neutralization project, before the reaction The concentration of glycine and the concentration of glycine in the reaction solution (c liquid) in the reaction are preferably 0.010 to 0.250 m/l 'more preferably 〇〇3〇~〇17〇m/liter". The concentration of glycine in the liquid and the concentration of glycine in the liquid A. When the glycine concentration of the reaction liquid (liquid C) when the liquid A and the liquid B are added to the liquid c are within the above range, it is easier to obtain a larger average particle diameter. If the concentration of glycine in the reaction solution α liquid in the case where the liquid is mixed with the liquid b and the solution c is not in the above range, it is easy to pass to the secondary particles having a smaller average particle diameter, or the cohesive force. reduce. If the range is the same as above, the unreacted (4) part will remain in the reaction solution. The amount of sputum and sputum added to c liquid 'after atomic conversion, relative to the total molar number of drill ions in a 15 201219311 liquid, the total molar ratio of hydrogen and oxygen ions in liquid B to the total 0H ion in liquid The molar number of the total c〇 atom in the molar number/A liquid is preferably 1.8 to 2", more preferably mo. Compared with the total number of moles of the ionic ions in the eight liquids, B; in the case where the total number of hydrogen ions in the night is within the above range, the unreacted cobalt ions in the reaction liquid (liquid C) do not remain, and it is easy. Obtain the argon oxidation of the target. In the neutralization process, a glycine aqueous solution (C solution) was previously added to the reaction vessel, and then a liquid and a liquid b were added. The reaction temperature of the neutralization process is 55 to 75 t, preferably 6 (one) generation, more preferably 65 to 75 t. That is, in the neutralization process, when the sputum and the β liquid are added to the c liquid, the temperature of the reaction liquid (liquid C), that is, the temperature of the liquid c before the reaction and the temperature of the reaction liquid (liquid C) in the neutralization reaction are 75t, preferably 6〇~75, more preferably 5~7m liquid and B liquid plus W liquid, the reaction liquid liquid) if the degree of the liquid is within the above range, a larger average particle diameter bismuth oxide drill can be obtained. Secondary particles. Another second, thousands of other aspects 'When the liquid A and the β liquid are added to the liquid c, the temperature of the liquid (the liquid C) is less than the above range, and it is easy to obtain the secondary particles, or the cohesive force. reduce. Further, when the temperature of the reaction liquid (sputum) in the case where the mash is introduced into the liquid C is out of the above range, it is easy to obtain the primary primary particles of the hydroxide having a smaller average particle diameter. ::In the project, when the liquid A and the liquid B are added to the liquid c, the reaction liquid (liquid C) = value Η before the reaction. The enthalpy of the liquid and the reaction in the neutralization reaction are 9. 〇 11 11 , preferably 9.8 〜 10.2. When the liquid A and the W 0 are in the above range, the cobalt hydroxide secondary particles having an average particle diameter of 2 = liquid (C liquid) and having a strong aggregability 201219311 can be obtained. . In addition, in the case of the ancient mouth. In the aspect, the liquid A and the β liquid are added to the liquid c, and the enthalpy of the reaction liquid (C liquid) is not lowered, and the chlorine oxidation obtained is easy to be y', the productivity is easy, and... There are steroidal impurities such as sulfate. When the liquid A and the liquid B are added to the liquid C, the pH of the liquid (the liquid C) is excessively exceeded, and the pH of the liquid (the liquid C) exceeds the above-mentioned consumption. Furthermore, in the neutralization project, when the wrong secondary particles, liquid and sputum are added to the C solution, the ambiguous value of the reaction can be obtained by, for example, the concentration of hydrogen and oxygen ions in the sputum is two for the sputum The concentration ratio of R ^ _ D produced by the product, the concentration ratio of the liquid oxygen ion of the liquid phase β, and the addition rate of the liquid C added to the liquid solution of the liquid, are selected and adjusted according to the special conditions. In the neutralization project, when the sputum and sputum are added to the c solution, the relative rate of cobalt ion addition, the oxyhydrogen in the 8 liquids;

The ratio of the addition rate of the galvanic ion is preferably 1.8 to 2. 1 ' is more preferably WD 9 9 of the 丨 9 〜 2 ion. Further, with respect to the cobalt velocity of the liquid A, the ratio of the addition rate of the chlorine oxygen ions of the liquid B is relative to the addition rate of the ions of the two =: ... (mole ~ ear / minute; the ratio to the hydrogen of the beta liquid in the reaction W) The rate of addition of oxygen ions (no special restrictions from the beginning, more preferably 1~5 in the neutralization project) when adding sputum and sputum to the C solution, the liquid and sputum to the C solution, until the addition time is added It is not preferable from the viewpoint of favorable industry. 'It is preferably 0.5 to 10 hours, hour. Τ In the neutralization project, the speed, that is, the stirring speed of the liquid before the reaction (c liquid), the amount of the reaction liquid, etc. When mixing, the stirring speed of the reaction liquid (c liquid) and the reaction liquid in the neutralization reaction are the size of the reaction vessel, and the diameter of the (four) wing is selected. The rotation speed of the stirring blade is preferably 〇. 5~4 〇公17 201219311 ft / sec, more preferably 0.5 ~ 2 · 0 m / s. In addition, in the 'neutralization project, the addition time of liquid A and liquid B added to C liquid, at the beginning 'better The stirring speed between the start and the one hour is slower. Then the stirring speed is accelerated, and it is easier to obtain the hydroxide with a large average particle diameter. The secondary particles, J, also have a high degree of filling. The method for producing cobalt hydroxide of the present invention can obtain the initial (secondary particles) of hydrogenation by the above neutralization process. After the neutralization process, the hydroxide formed in the reaction liquid Cobalt (secondary particle) is subjected to a pressure reduction transition and centrifugal separation to separate the gas oxidation from the reaction liquid, and if necessary, to be washed and dried. The cobalt hydroxide obtained by the method for producing cobalt argon according to the present invention is The oxidized drill of the invention is a secondary particle obtained by agglomerating primary particles, and has a plate-shaped, columnar, or needle-like primary particle having a long diameter of L 5 μm or more. The shaking density is 〇·8 gram/ml. The above 'has a special particle shape, and the secondary particles have an average particle diameter of 15 to 4 μm, which is larger than the conventional = particles and has a strong cohesive force. The chlorine obtained by the method of the present invention Oxidation Ming, that is, the invention of the hydroxide in the manufacture of the acid clock, when mixed with the bell compound, the average particle size of the secondary particles even if the large secondary particles of 15~40 microns are not easy to decompose' because Inconsistent with the bell compound: a large particle size of 15' micron. With the cobalt hydroxide of the present invention: the initial oxidation of the gas, that is, the nitrogen oxide of the present invention, the shearing force of the grinder is pulverized. The treatment and the secondary particles 4 are not so small, and it is preferable that the secondary particles of the secondary particles 18 after the pulverization treatment have a diameter of less than 7.0 μm, and the particle size distribution before and after the pulverization mixing is changed by using the cobalt hydroxide of the present invention. The oxidized hydroxide obtained by the production method also utilizes the hydrolytic oxidization of the present invention, and the secondary particles averaged = 4 〇 micrometers of the oxidized hydroxide of the present invention, and the compound is reversed with the compound: Particle growth does not require the use of a large number of clock compounds, so you can get to the average ring of 15 ~ 35 microns, and the relative Ming of the original: (four): Mo Erbi (经经/幻化. Hui 1 Hui compares the large particle size of the past, and can get (four) clocks when the amount of the clock is too small. The chlorine oxidation prepared by the method for producing a ruthenium oxide drill of the present invention also produces a positive electrode active material for a lithium rechargeable battery having a high capacity per unit volume and a high capacity retention. In addition, the oxime drill of the present invention is characterized by using the above-described hydrogen oxyhydroxide production method of the present invention and the hydrogen hydride of the invention obtained by the invention. - Moer, its glycine content after atomic conversion is 0. 10~. 30. The aqueous cobalt solution (4 liquids) and the aqueous alkali solution (8 liquids) were added to the liquid C, and the neutralization reaction was carried out at 5 °C and the initial oxidation of the obtained product was carried out. The method for producing Oxidation of the present invention, characterized in that the hydroxide drill obtained by the method for producing a hydroxide of the present invention comprises oxidizing and sintering by oxidation at 2Q (M〇〇『c) to obtain cobalt oxide. The preparation of the cobalt oxide of the present invention has a firing temperature of 200 to 1 000 ° C and a time of 2 to 20 hours, preferably a oxidative firing process of the method, and the cobalt hydroxide ruthenium is preferably 300 to 900 ° C. In addition, the firing may be carried out for 2 to 10 hours, and the firing environment may be 19 201219311 air or oxygen. The oxidized cobalt production method of the present invention is pulverized, pulverized, and classified. The cobalt oxide is a secondary particle of the interest M, and the secondary particle of the human branch is composed of the same particle. The first particle of the human particle is a small particle, and the small particle is analyzed by an electron scanning microscope. The length is 1 > 5 micrometers; „ from a plate, column or needle-like puller' and the tap density is 0.80 square ^fb ^ it f} 4- + or more. Forming the oxidation of the present invention One of the columnar or needle-shaped ones. The value of 1.5 μm is preferably 2. 〇~5. 〇 micron, ^, and the cooker is more preferably 2. 5 to 4. 5 μm. Further, the cobalt oxide of the present invention is preferably two micrometers, and preferably: The average particle diameter of = is 1 〇, preferably 8 to 30 MPa. -: The compressive strength of human particles is 5, dead pat'. The cobalt oxide of the present invention can force 彳f # π # » 咖啡 with coffee grinding The cutting degree of the machine is cut into the smashing and smashing treatment, and the pulverizing treatment is less. The car's particle size distribution changes in the micro-particles: the average particle diameter of the secondary particles after the lower is 7_. As a series "" 虱 虱 虱 虱 檨 & & & _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ Cobalt production: The obtained cobalt hydroxide is obtained by oxidative firing at 2 Torr, 〇t, preferably 3 Torr. 'Next, the cobalt hydroxide of the present invention or the oxidation of the present invention will be described. Ming made the method of drilling acid.

20 201219311 A method for producing lithium cobalt oxide using the cobalt hydroxide of the present invention or the cobalt oxide of the present invention comprises mixing a hydroxide of the present invention or a particle of the present invention with a lithium compound, and a mixing plant for particles The obtained particle mixture is subjected to a firing reaction process of 80 (Ml5 (rc is calcined to obtain lithium cobaltate). The particle mixing process is a process of mixing the cobalt hydroxide of the present invention or the cobalt oxide of the present invention with a lithium compound. The compound of the bell used by the Guardian Spear King is not particularly limited as long as it is a raw material for the manufacture of a general acid clock. (4) Oxides, hydroxides, cesium carbonate, cerium nitrate, and organic acid cesium may be considered. From the viewpoint of industrial economy, it is preferred to use carbonic acid. The average particle diameter of the compound is 0. H00 μm, preferably 2 to 50 μm, and the reactivity is good, so it is suitable. When the cobalt hydroxide or the oxidation start of the present invention is mixed with the chain compound, the molar ratio of the aquarium to the clock after the atom conversion (mixed molar ratio (4) $ Q 9g (m plan, .95〇~more preferably, after the atomic conversion, the molar ratio of the atomic ratio can be increased by the above-mentioned range (4). The capacity retention rate of the fourth is not included in the above range, so the meaning of lithium is caused by the unit weight. Discharge = 22 has the remaining days] 孜 奋 里 有 有 有 : : : : : : : : : : : : : : : : : : : : 显 显 显 显 显 显 显 显 显 显 显 显 显 显 显 显 显 显 显 显 显The mixing method of the compound ' can be, for example, a spiral agitator, 21 201219311 agitator, a super agitator, a Notta agitator, etc. The firing reaction process is a hydrogenation chain of the present invention obtained by mixing the particles. Or the particle mixture of the oxidation start and the bell compound of the present invention is obtained by heating the hydroxide of the present invention or the particle mixture of the oxide and the complex of the present invention to obtain a lithium cobaltate. When the cobalt hydroxide of the present invention or the particle mixture of the oxidized guar and the bell compound of the present invention is subjected to a calcination reaction, the temperature thereof is preferably _] 15 generations, more preferably the bubbling reaction time is hour 'more preferably 5 〜 20 hours ° The additional firing reaction environment may be air or oxygen oxidation environment. After the firing reaction process, the generated lithium cobaltate may be pulverized or classified as needed to obtain lithium cobaltate. The cobalt oxide or the cobalt oxide obtained by the cobalt oxide of the present invention preferably has an average particle diameter of 15 to 35 μm, more preferably 18 to 3 μm, so that high filling can be performed. Thus, the hydrogen of the present invention is used. The lithium cobalt oxide obtained by the cobalt oxide or the cobalt oxide of the present invention can obtain a lithium rechargeable battery having a high capacity per unit volume. Further, the average particle diameter of the lithium cobalt oxide of the present invention can be obtained by using MICROTRACK MT3300 manufactured by Nippon Machine Co., Ltd. ΐ τ &quot; + ^ la u is determined by laser differential scattering method. Dan Kao's use of lithium cobalt oxide, atomic conversion, lithium cobalt molar ratio (lithium / cobalt) is 〇·9 〇(Μ.040' is less than the conventional large-diameter lithium cobaltate, and the remaining lithium content is small', so that the high capacity retention rate of the lithium rechargeable battery can be maintained. Χ And using the cobalt hydroxide of the present invention or the strip of the present invention to obtain cobalt oxide, the solid density of the acid clock of 22 201219311 is 2.^2 g/ml. Preferably, it is more than 2 gram per liter. More preferably, it is made by the embodiment of the present invention in detail, but is limited by the embodiment. X is not <Preparation of aqueous solution for reaction> (1) Cobalt aqueous solution 1 Solution = Sulfuric acid recorded 7 water and 425.5 g of glycine and 5.7 g of glycine dissolved ^ Add water until the total amount is 1 liter, and prepare into the aqueous solution b At the time of the atomic conversion, the cobalt ion wave in the initial aqueous solution 彳φ# secret is 丨5 mol/liter. The concentration of glycine was 0.075 moles, and after opening the atomic exchange, it was 0.050 moles relative to cobalt 1 molar glycine. (2) Cobalt aqueous solution 2 Industrial sulfuric acid starting water 7 and water 425 5 g and glycine U g were dissolved in water 're-added water until the total amount was 1 liter' to prepare a solution 2. At this time, the concentration of the ion in the aqueous solution 2 was converted to 5 m/L after atomic conversion. The glycine indifference was 0.015 mol/l. After atomic conversion, it is relative to Ming 1 mol glycine. 010 mol. (3) Starting aqueous solution 3 Industrial sulfuric acid starting water 7 and 425. 5 g were dissolved in water, and water was added until the total amount was 1 彳' to prepare a wrong aqueous solution 3. At this time, the cobalt ion concentration in the aqueous solution 3 was 15 mol/liter after atom conversion. (4) Cobalt aqueous solution 4 Industrial sulfuric acid drill 7 water and material 425. 5 grams and Gan (tetra) 〇 · 9 grams dissolved in water, and then add water until the full amount is!升, modulated into a solution of 〇 23 201219311 At this time, the cobalt 龅 in the aqua solution 4, the cobalt ion of the radix / 44_, the atomic conversion of A 1. 5 mol / liter. The concentration of glycine was 〇 〇, horse. 2 4 ears / liter. 008摩尔。 Relative to cobalt 1 molar glycine after the atomic conversion is 0. 008 mole. (5) Aqueous alkali solution 1% sodium hydroxide At this time, sodium hydroxide was dissolved in water to form a 25 mass aqueous solution, and a 0.5 liter aqueous alkali solution having a concentration of 7.9 mol/liter was prepared. (6) Initial addition liquid 1 Further, water was added until the total amount was 〇. 35 liters of glycine in the initial addition liquid 1, acid concentration 1.4 g of glycine was dissolved in water to prepare an initial addition liquid 1. The degree is 0. 054 m / liter. (7) Initial addition liquid 2 0.3 g of glycine was dissolved in water to make an initial addition liquid 2. The acid concentration is 〇·011 mole/liter. (8) In the initial addition liquid 3, 'addition of water to the total amount is 0.35 liters. At this time, the ammonia in the initial addition liquid 2 is 0.35 liters of water as the initial 3 and does not contain glycine. Add liquid 3. That is, the initial addition liquid (9) Initial addition liquid 4 0.2 g of glycine was dissolved in water to prepare an initial addition liquid 4. This additional water is added to the total amount of 〇·35 male acid concentration is 〇. 008 Moer/Leng. The glycine in the initial addition liquid 4 (test examples 1 to 5, comparative examples 1, 4) <Manufacture of cobalt hydroxide 〉

24 201219311 'Into a 2 liter reaction vessel, add 3 liters of the initial addition solution and heat to the reaction temperature as shown in Table 1. Then, the reaction liquid (initial addition liquid) in the reaction cell was mixed while stirring at the stirring rate shown in Table 1, and the cobalt aqueous solution and the aqueous alkali solution were added for neutralization according to the reaction temperature and the dropping time shown in Table 1. The reaction was adjusted to adjust the pH of the reaction liquid to the pH shown in Table 1. After the neutralization reaction, the reaction liquid was cooled, and then the product was filtered and washed with water, and then dried at 70 ° C to obtain cobalt hydroxide. The average particle diameter, compression strength, pulverization characteristics, and tap density of the secondary particles of cobalt hydroxide obtained were measured, and the results are shown in Table 2. (Example 6) <Production of cobalt hydroxide> Other than the reaction conditions shown in Table 1, the reaction was carried out under the same conditions as in Example 5 to obtain cobalt hydroxide. The average particle diameter, compression strength, pulverization characteristics, and tap density of the secondary particles of cobalt hydroxide obtained were measured, and the results are shown in Table 2. (Example 6) <Production of Cobalt Oxide> The cobalt hydroxide obtained in Example 3 was fired at 500 ° C for 5 hours in the air to obtain cobalt oxide (C〇3〇4). The average particle diameter, compression strength, pulverization characteristics, and tap density of the secondary particles of the obtained cobalt oxide were measured, and the results are shown in Table 2. (Experimental Examples 8 to 11 and Comparative Examples 5 to 8) <Production of Lithium Cobaltate> 25 201219311 The above-mentioned cobalt hydroxide and lithium carbonate were mixed according to the lithium/cobalt molar ratio shown in Table 3, and then as shown in Table 3 The firing reaction temperature shown is heated to obtain lithium acid hydride. The average particle size, the tap density, the capacity retention rate, the initial discharge capacity (the masking tongue, the u, the inner weight of the front), the initial discharge capacity (unit volume), and the average operating voltage of the initial acid clock obtained by the measurement. 'The results are shown in Table 3. <Evaluation> (1) The average particle diameter of the secondary particles of the cobalt hydroxide or cobalt oxide and the average particle diameter of the initial acid clock were measured by a laser differential scattering method. The measurement was carried out using a MICROTRACK MT3300 EX u manufactured by 曰 装. (7) The compressive strength of the secondary particles of the present invention was measured by a Shimadzu Miniature Compression Tester MTC_w. (3) The pulverization characteristics were measured by using a household agitator (IFM side, manufactured by Iwatani Co., Ltd.) for 1 sec., nitrous oxide or oxidized secondary particles (4), and the average particle of the treated secondary particles (b) was measured. path. The particle size distribution diagrams before and after the human particle mashing treatment are shown in Figs. 1 to 1B, 24, and 25, respectively. (4) The density of the solid is based on the appearance of the seventh, the paper, the degree of measurement, and the apparent specific volume as described in JIS-K-510, and the § pattern of the A brother is added to the 50 ml measuring cylinder. The DUAIj AUT〇TA &quot; shredded 旦 旦 丄 丄 装置 浅 浅 浅 浅 浅 浅 浅 浅 浅 浅 浅 浅 浅 DU DU DU DU DU DU DU DU DU DU DU DU DU DU DU DU DU DU DU DU DU DU DU DU DU DU DU (5) Determination of long diameter and short diameter of secondary particles

26 201219311 4 thoughts to extract 100 primary particles, into the image solution, ^ ν trace electron microscope into the rod ~ image analysis, measurement scanning electron microscopy

And &quot;Α I have observed 2 U long and short diameters. Next, the average value of the extracted - scorpion is calculated; 5 - 4 long diameter J value U and short diameter average of the primary particles. Further, only the comparative examples, the nitrogen oxide surface of the household, the actual example 5, and the sixth embodiment are shown in Figs. 11 to 20, 26 and 27. The field electron microscope image (6) measures the presence of primary particles on a ratio of 1.5 micrometers in length and length, and randomly extracts 100 secondary particles, and extracts the _A i / the one-person of the electron microscope image 4 The total area of the particles is calculated as the total area of the sub-particles relative to the _-like shape in terms of _ U micron with μ and the length of the primary particle, and the plate-like, columnar, and acicular enthalpy on the raft. The ratio of the total area of the plate-like, columnar-like primary particles of the total area of the secondary particles to the R of the 1st particle and the needle makeup. The battery performance test was performed as described below. Examples 8 to 11 and Comparative Examples Percent + ^ ^ b 8 Lithium cobaltate served as 91 J J "Graphite powder 6 wt% b" than the rod -, the person from the 1 rat ethylene 3 weight The core s is divided into a positive electrode. The pottery eight gentleman, Japanese, and the knife are scattered in N-methyl-2-pyrrolidone, and the mixture is mixed with the paste. , flattening, _ 15 mm diameter disc positive plate. C plate, isolation device, negative electrode, positive electrode, collector plate, charged battery H to solve each piece, to make a round bell charge m ^ ^ 5 j using lithium metal foil, electrolyte using ethylene carbonate $ yoghurt yin yin (LipP + .1 lysate 1 liter dissolved in lithium hexafluorophosphate 6 mole solution. 2Ί 201219311 <Battery performance evaluation And the test conditions for the charging cycle characteristics are the first, at 0. 5C for the above-mentioned test conditions. Charged to 2.5 volts for 2 hours, and then held at a voltage of 4.5 volts for 3 hours to charge at a constant current (cccv charge). Discharge at a constant current of 0.2C to 27 volts ((::: discharge) for charge and discharge, thus as a human cycle. The mother's cycle measures its discharge capacity. This repeats 20 cycles. (2) Initial discharge capacity (per unit weight) The discharge capacity of the first cycle of the charging cycle is the initial discharge capacity. ^ (3) Initial discharge capacity (per unit volume) The electrode density and initial discharge capacity measured when the positive plate is made ( (4) The capacity retention rate of the sub-cycle and the 20th cycle are calculated according to the following formula: The discharge capacity of the cycle / the first cycle of the first cycle charge cycle characteristic evaluation Discharge capacity (per unit of weight), capacity retention rate U) = (20th discharge capacity) * 丨〇〇 (5) Average operating voltage of the average operating voltage charging cycle characteristics evaluation. Average operating voltage when 28 201219311 Table 1 Cobalt 7 solution initial solution in the initial addition of droplets (hours) pH stirring speed (meters / sec) reaction temperature (. 〇 species amount (liter) species amount (liter) species Amount (liter) Example 1 1 1 1 0.5 1 0.35 5 10.1 2 70 Example 2 1 1 1 0.5 1 0.35 5 10 2 70 Example 3 1 1 1 0.5 1 0.35 5 10 1.0-2.0° 70 Example 4 1 1 1 0.5 1 0.35 5 9.9 1.0-2.0° 70 Example 5 2 1 1 0.5 2 0.35 5 10 2 60 Example 6 1 1 1 0.5 1 0.35 5 9.9 1.5 70 Comparative Example 1 3 1 1 0.5 3 0.35 10 10 2 60 Comparative Example 2 4 1 1 0.5 4 0.35 5 10 2 70 Comparative Example 3 1 1 1 0.5 1 0.35 5 10 2 50 Comparative Example 4 1 1 1 0.5 1 0.35 5 10 2 80 1) Stirring speed "1.0 to 2.0" is 1 hour after the start of mixing, 1.0 m/s, followed by agitation at 2.0 m/s. Table 2 1 Average particle diameter of i-cobalt oxide or cobalt oxide secondary particles (a) Compressive strength Secondary particle (6) Average particle size Shake density Primary particle shape Micron megapascal μg/ml Long diameter (μm) Short diameter (μm) Existence ratio (8) Example 1 15.3 9.6 15 1.53 2.7 0.5 100 Plate-shaped primary particles to form spherical secondary particles Example 2 21.2 10.9 20.8 1.71 3.3 0.7 100 Plate-like primary particles to form spherical secondary particles Example 3 25.8 18.2 24.5 1.73 3.1 0.8 100 plate-like primary particles to form spherical secondary particles Example 4 32.2 23.1 30.4 1.81 3.0 0.6 100 Plate-shaped primary particles to form spherical secondary particles Example 5 20.8 8.3 15.1 0.88 2.7 0.3 83 Plate-shaped primary particles Formation of spherical secondary particles Example 6 32.4 6.7 28.0 0.85 1.7 0.2 53 Plate-shaped primary particles to form spherical or unshaped secondary particles Example 7 25.0 8.4 19.8 2.10 2.9 0.8 100 Plate-like primary particles form spherical secondary Particles 29 201219311 Comparative Example 1 7.7 0.8 0.4 0.4 0.1 or less 0.1 or less 0 Fine primary particles form non-specific shape secondary particles Comparative Example 2 15.9 2.2 11.2 0.79 1.4 0.2 37 Plate-shaped primary particles forming non-specific shape secondary particles Comparative Example 3 15.7 0.7 7.3 0.48 0.1 or less 0.1 or less 0 Fine primary particles forming elliptical shape secondary particles Comparative Example 4 6.9 3.2 2.6 0.65 0.9 0.2 8 Plate-shaped primary particles form spherical secondary particles * In Table 2, the average particle diameter of the secondary particles (a) refers to the average particle diameter before the pulverization treatment of the household agitator, and the average particle diameter of the secondary particles (b) Refers to the average particle size of secondary particles after pulverization of household agitator. ** In Table 2, there is a ratio of the total area of primary particles with a relative diameter of 1.5 μm or more relative to the total area of the secondary particles. Table 3 Types of Cobalt Hydroxide Manufacturing Conditions of Lithium Cobaltate Properties of Cobalt Acid of Lithium Cobalt (Battery Characteristics) Lithium/Cobalt Mohr Ratio Reaction Temperature (°C) Average Particle Size (μm) Initial Discharge Capacity (weight unit) (milliampere/gram) Initial discharge capacity (volume unit) (milliampere/ml) Capacity retention rate (%) Average operating voltage (volt) Example 8 Example 1 1.02 1050 16.5 185.5 506.5 97.5 3.8 Example 9 Example 2 1.02 1050 19.8 186.1 508.1 96.9 3.82 Example 10 Example 3 1.02 1050 24.4 187.4 514.4 95.5 3. 82 Example 11 Example 6 1.02 1050 22.1 189.2 505.2 95.0 3.82 Comparative Example 5 Comparative Example 1 1.02 1100 9.8 188.2 483.6 93.4 3.81 Comparative Example 6 Comparative Example 1 1.06 1100 21.3 188.6 516.3 89.8 3. 54 Comparative Example 7 Comparative Example 2 1.02 1050 12.1 187.2 483.8 97.6 3. 85 Comparative Example 8 Comparative Example 2 1.06 1100 18.9 186.9 508.9 90.2 3. 66 INDUSTRIAL APPLICABILITY According to the present invention, lithium cobalt oxide having a large average particle diameter and a small amount of remaining lithium can be obtained, and thus can be used for producing a high unit volume capacity and a high capacity dimension. Rate of lithium rechargeable batteries. 30 201219311 BRIEF DESCRIPTION OF THE DRAWINGS Fig. 1 is a particle size distribution diagram of cobalt hydroxide particles (secondary particles (a)) obtained in Example 1 of the present invention. Fig. 2 is a graph showing the particle size distribution of cobalt hydroxide particles (secondary particles (b)) after the pulverization treatment of the cobalt hydroxide particles (secondary particles (a)) obtained in Example 1 of the present invention. Fig. 3 is a graph showing the particle size distribution of cobalt hydroxide particles (secondary particles (a)) obtained in Example 5 of the present invention. Fig. 4 is a graph showing the particle size distribution of cobalt hydroxide particles (secondary particles (b)) after the pulverization treatment of the cobalt hydroxide particles (secondary particles (a)) obtained in Example 5 of the present invention. Fig. 5 is a graph showing the particle size distribution of cobalt hydroxide particles (secondary particles (a)) obtained in Comparative Example of the present invention. Fig. 6 is a view showing the particle size distribution of the cobalt hydroxide particles (secondary particles) after the pulverization treatment of the cobalt hydroxide particles (secondary particles (a)) obtained in the comparative example of the present invention. Fig. 7 is a comparison example 2 of the present invention. The particle size distribution map of the obtained cobalt hydroxide particles (secondary particles (a)). Fig. 8 is a hydrogen after the red mashing treatment of the cobalt hydroxide particles (secondary particles (a)) obtained in Comparative Example 2 of the present invention. Particle size distribution map of cobalt oxide particles (secondary particle enthalpy). Fig. 9 is a particle size distribution diagram of cobalt hydroxide particles (secondary particles (a)) obtained in Comparative Example 3 of the present invention. Fig. 10 is a graph showing the particle size distribution of the cobalt oxychloride particles (secondary particles (b)) after the pulverization treatment of the cobalt hydroxide particles (secondary 31 201219311 particles (a)) obtained in the fourth column. Fig. 11 is a scanning electron micrograph (3000 magnifications) of the cobalt ruthenium oxide particles obtained in Example 1 of the present invention. Fig. 12 is a scanning electron micrograph (10,000 times) of the hydroxide flap particles obtained in Example 1 of the present invention. Fig. 13 is a scanning electron micrograph (3000 magnifications) of cobalt hydroxide particles obtained in Example 5 of the present invention. Fig. 14 is a scanning electron micrograph (10000 times) of the hydroxide (IV) particles obtained in Example 5 of the present invention. Fig. 15 is a scanning electron micrograph (3000 magnifications) of the cobalt hydroxide particles obtained in Comparative Example 1 of the present invention. Figure 16 is a comparative example of the present invention! Scanning electron micrograph (10,000 times) of the obtained cobalt hydroxide particles. Fig. 17 is a scanning electron micrograph (300 times) of the cobalt oxychloride particles obtained in Comparative Example 2 of the present invention. Fig. 18 is a scanning electron micrograph (1 〇 〇 〇 )) of cobalt oxyhydroxide particles which were evaluated by Φ ^ θ in Comparative Example 2 of the present invention. Fig. 19 is a scanning electron micrograph (3000 magnifications) of Φ 7 bismuth cobalt oxide particles of Comparative Example 3 of the present invention. Scanning electron micrograph (10000 times) of the hydroxide (tetra) obtained in Comparative Example 3. Fig. 21 (A) to (C) are mode squints of secondary particles constituting the second teaching 32 201219311 Fig. 22 (A) and (B) are explanatory diagrams of the primary particle long diameter and the short diameter. 23(A) and (B) are explanatory diagrams of the primary particle long diameter and the short diameter. Fig. 24 is a graph showing the particle size distribution of cobalt hydroxide particles (secondary particles (a)) obtained in Example 6 of the present invention. Fig. 25 is a particle size distribution diagram of cobalt hydroxide particles (secondary particles (b)) after the pulverization treatment of the cobalt hydroxide particles (secondary particles U) obtained in Example 6 of the present invention. Fig. 26 is a scanning electron micrograph (3000 magnifications) of the hydroxide drill particles obtained in Example 6 of the present invention. Figure 27 is a scanning electron micrograph (10,000 times) of the gas oxidized drill particles obtained in Example 6 of the present invention. [Main component symbol description] 33

Claims (1)

201219311 VII. Scope of application for patents: 1. A type of hydrazine, characterized in that primary particles are condensed into primary particles, and primary particles constituting the secondary particles are analyzed by scanning electron microscopy, and plates having a long diameter of 1.5 μm or more The primary particles of the shape, columnar shape or needle shape have a shake density of 〇80 g/ml or more. 2. A type of hydrogen peroxide, characterized in that in the scanning electron microscope image analysis, the presence ratio of the plate-like, columnar, or needle-like primary particles having a long diameter of 1 to 5 μm or more is 40% or more. 3. The cobalt hydroxide according to claim 1 or 2, wherein the secondary particles have an average particle diameter of from 1 to 4 μm and a compressive strength of from 5 to 50 MPa. 4. A cobalt hydroxide solution, characterized in that: a cobalt aqueous solution containing glycine is used, and the content of glycine is 0. 010~0·300 mol of cobalt aqueous solution (liquid A) and alkali relative to cobalt oxime. The aqueous solution (solution B) is added to the aqueous solution of glycine (solution C), and the neutralization reaction is carried out by 55 to 75 〇c, whereby the hydrogenation process can be obtained. A method for producing cobalt sulfate according to the invention, characterized in that a cobalt aqueous solution containing glycine is used, and in an atomic conversion, the amount of the glycine is 0.010 to 0.300 mol of the cobalt aqueous solution (liquid A) and the alkali relative to the cobalt 1 molar. An aqueous solution (6 liquids) was added to the aqueous glycine solution (liquid c), and a neutralization reaction was carried out at 55 to 75 t to obtain a cobalt hydroxide neutralization process. 6. The method for producing cobalt hydroxide according to claim 5, wherein the neutralization process is carried out in a pH 9 to u environment for neutralization. 34 201219311 7·The manufacturer of the cobalt hydroxide described in the fifth or the seventh paragraph of the patent application is characterized in that: in the above neutralization project, the sputum and sputum are added to the liquid C, and the glycine in the liquid C is The concentration is 〇. 01〇~〇. 250mol/L. 8 _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ Or needle-like sub-particles, the density of shaking is 〇·80 g/ml or more. 9. The cobalt oxide according to item 8 of the patent application is characterized in that the average particle diameter of the secondary particles is 10 10 to 40 μm, and the compression thereof is 5 to 50 MPa. &amp; '1 0 · A method for producing cobalt oxide, which is characterized in that the cobalt hydroxide obtained by the method for producing the hydroxide 33 according to any one of claims 5 to 7 is used in the art of 200 to 1,000. Oxidation and firing of cobalt oxide by firing and oxidation. The method for producing cobalt oxide according to claim 10, wherein the firing temperature in the oxidizing firing process is 200 to 700 〇C. &amp; 35