JP2017039624A - Method for producing transition metal hydroxide - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a neutralization crystallization method capable of obtaining a transition metal composite hydroxide improving productivity without changing a grain size distribution.SOLUTION: There is provided a method for producing a transition metal hydroxide where, when a reaction solution 3 is continuously made to overflow from a reaction container 1, simultaneously, only a solvent 9 is exhausted from a part of the reaction solution 3 in a solid-liquid separation apparatus 8, and concentrated slurry 10 is re-charged to the inside of the reaction container 1, a transition metal hydroxide having a prescribed grain size distribution is obtained by continuously overflowing the reaction solution 3 without concentrating the transition metal hydroxide slurry in the reaction container 1, provided that the addition speed of a metal salt-containing mixed aqueous solution and a caustic alkali aqueous solution and/or an ammonium ions feeder-containing aqueous solution and the concentration of the transition metal hydroxide slurry, set at this time, are defined as standard conditions, the addition speed is set in such a manner that the ratio between the magnification of the addition speed and the magnification of the transition metal hydroxide slurry concentration, to the standard conditions, reaches the range of 0.8 to 1.2, and also, the solvent in the reaction container 1 is continuously removed.SELECTED DRAWING: Figure 1

Description

  The present invention relates to a method for producing a transition metal hydroxide.

  Transition metals, particularly transition metal hydroxides containing Group 7 to Group 11 transition metals or zinc are widely used as functional powders or precursors for various applications.

  In particular, a positive electrode active material made of a lithium transition metal composite oxide is used as a positive electrode material of a lithium ion secondary battery for power supply applications such as portable electronic devices and electric vehicles, and a precursor of this lithium transition metal composite oxide As a transition metal composite hydroxide is used. Secondary batteries for power supplies such as portable electronic devices and electric vehicles are required to have various battery characteristics such as high energy density, high output, excellent initial capacity characteristics, and cycle characteristics at a high level.

  As a general method for producing a positive electrode active material, a transition metal composite hydroxide as a precursor is prepared by a neutralization crystallization method, and the obtained transition metal composite hydroxide is mixed with a lithium compound and fired. A method for obtaining a lithium transition metal composite oxide is employed. The battery characteristics of the lithium ion secondary battery are greatly influenced by the powder characteristics of the positive electrode active material, but the powder characteristics of the positive electrode active material are greatly influenced by the powder characteristics of the transition metal composite hydroxide as a precursor. Receive. In particular, since the particle size distribution, which is the most basic powder characteristic of the positive electrode active material, almost reflects the particle size distribution of the precursor, in order to obtain a positive electrode active material having excellent powder characteristics, the precursor is used. Control of neutralization crystallization for obtaining is extremely important.

  As a neutralization crystallization method for obtaining a transition metal hydroxide containing a transition metal hydroxide as a precursor of a positive electrode active material, a continuous crystallization method excellent in productivity is widely used. As a means for further improving productivity in the continuous crystallization method, the rate at which the raw material is added is increased, that is, the time during which particles generated in the reaction tank stay in the reaction tank (hereinafter referred to as “particle retention time”). ”) Can be considered. However, shortening the particle residence time, in principle, causes the particle size distribution to become lower and narrower, so this method has limitations in improving productivity while maintaining the conventional particle size distribution. is there.

  As a means for maintaining the particle residence time while increasing the rate at which the raw material is added, a method of concentrating the slurry concentration in the reaction vessel is conceivable. That is, the particle residence time is extended by conducting solid-liquid separation and discharging only the liquid while performing the crystallization reaction.

  As such a method, for example, in Japanese Translation of PCT International Publication No. 2010-536697, a cleaning element or a filter element is used to control the concentration of the reaction solution in the reaction tank to be 150 g / L or more. A method for obtaining a transition metal hydroxide composed of high density particles is disclosed. Japanese Patent Application Laid-Open No. 2013-18705 also discloses a method of obtaining particles having a high tap density by concentrating a reaction solution in a reaction tank using an inclined plate settling device.

  However, by these methods, even when trying to obtain a transition metal hydroxide having the same powder characteristics as before, the particle residence time is extended by concentrating the reaction solution. In principle, the particle size distribution of the obtained particles changes and the particle size distribution of the obtained particles changes, and the transition metal is composed of particles having a particle size distribution equivalent to that of conventional products. It is difficult to obtain hydroxide.

JP 2010-536697 A JP 2013-18705 A

  In view of such a problem, an object of the present invention is to provide a method for producing a transition metal hydroxide capable of greatly improving productivity without changing the particle size distribution of a conventional product. .

  In particular, the present invention provides a transition metal composite as a precursor that can significantly improve the productivity without changing the particle size distribution of a conventional positive electrode active material that exhibits excellent battery characteristics. It is in providing the manufacturing method of a hydroxide.

The method for producing a transition metal hydroxide containing a transition metal of group 7 to group 11 or zinc of the present invention,
In the reaction vessel, while stirring the reaction solution, a mixed aqueous solution containing a metal salt and an aqueous solution containing a caustic aqueous solution and / or an ammonium ion supplier are supplied and reacted, and the crystallized particles are separated into solid and liquid. In the neutralization crystallization step of obtaining a transition metal hydroxide by washing with water and drying,
While continuously overflowing the reaction solution containing the transition metal hydroxide from the reaction vessel, removing the solvent in the reaction vessel continuously and concentrating the transition metal hydroxide slurry in the reaction vessel , Continuing crystallization of transition metal hydroxides, and
It is composed of particles having predetermined powder characteristics, that is, predetermined D10, D50, and D90 values or a value of [(D90−D10) / MV] that is an index indicating the spread of a predetermined particle size distribution. A mixed aqueous solution containing the metal salt, which is set when the transition metal hydroxide is obtained by continuously overflowing the reaction solution without concentrating the transition metal hydroxide slurry in the reaction vessel; The addition rate of the aqueous solution containing the caustic aqueous solution and / or the ammonium ion supplier, and the concentration of the transition metal hydroxide slurry as a reference condition, the magnification of the addition rate with respect to the reference condition, Ratio of magnification of transition metal hydroxide slurry concentration: (magnification of raw material addition rate) / (double of transition metal hydroxide slurry concentration in reaction vessel) ) It is to be in the range of 0.8 to 1.2, setting the addition rate, and, and removing the solvent in the reaction vessel continuously.

  Further, the ratio of the addition rate to the reference condition and the ratio of the transition metal hydroxide slurry concentration: (the ratio of the raw material addition rate) / (the ratio of the transition metal hydroxide slurry concentration in the reaction vessel) Is preferably in the range of 0.9 to 1.1.

  In order to continuously remove the solvent in the reaction vessel, it is preferable to use a wet cyclone.

  The transition metal is preferably at least one selected from Ni, Co, Mn, Fe, and Zn.

  The present invention is not limited to transition metal hydroxides containing only a single transition metal except for inevitable impurities, and in particular, a plurality of transition metals used as a precursor of a positive electrode active material for a non-aqueous electrolyte secondary battery. It is also suitably applied to transition metal composite hydroxides containing other metal elements.

Table with _{Ni 1-x-y Co x} Al y (OH) 2 + α (0 ≦ x ≦ 0.3,0.005 ≦ y ≦ 0.15,0 ≦ α ≦ 0.5): In one aspect, the general formula The present invention can be applied to a method for producing a nickel composite hydroxide.

As another embodiment, the general formula: Ni _x Co _y Mn _z M _t (OH) _{2 + α} (x + y + z + t = 1, 0.1 ≦ x ≦ 0.7, 0.1 ≦ y ≦ 0.5, 0. 1 ≦ z ≦ 0.8, 0 ≦ t ≦ 0.02, 0 ≦ α ≦ 0.5, M is selected from Ti, V, Cr, Zr, Nb, Mo, Hf, Ta, and W The present invention can also be applied to a method for producing a nickel-cobalt-manganese composite hydroxide represented by an additive element of more than one species.

  In any embodiment, it is preferable to use a sodium hydroxide aqueous solution as the caustic aqueous solution, and it is preferable to use aqueous ammonia as the aqueous solution containing the ammonium ion supplier.

  According to the present invention, the productivity of a transition metal hydroxide containing a Group 7 to Group 11 transition metal or zinc can be greatly improved without changing the particle size distribution. In particular, the present invention relates to the productivity of nickel composite hydroxides and nickel cobalt manganese composite hydroxides, which are precursors of positive electrode active materials for non-aqueous electrolyte secondary batteries, and positive electrode actives obtained using these as precursors. While maintaining the powder characteristics of the substance, that is, the battery characteristics of the lithium ion secondary battery using this positive electrode active material as the positive electrode material, it is possible to greatly improve. Therefore, it can be said that the industrial value of the present invention is extremely high.

FIG. 1 is a schematic explanatory diagram of an apparatus for producing a transition metal hydroxide according to the present invention.

  The present inventor becomes a precursor of a transition metal, in particular, a transition metal hydroxide containing a transition metal of group 7 to 11 or zinc, particularly a positive electrode active material for a non-aqueous electrolyte secondary battery. As a result of extensive research on the production method of nickel composite hydroxide and nickel cobalt manganese composite hydroxide, the addition rate of raw materials charged into the reaction vessel and the transition metal hydroxide slurry in the reaction vessel By controlling the concentration so that the ratio of the rate of addition of the raw material to the conventional conditions and the magnification of the transition metal hydroxide slurry concentration in the reaction vessel is within a predetermined range, productivity is higher than in the past. In addition, the inventors have obtained knowledge that transition metal hydroxides having an equivalent particle size distribution can be obtained, and have completed the present invention. Hereafter, the manufacturing method of the transition metal hydroxide of this invention is demonstrated in detail.

  In FIG. 1, the schematic explanatory drawing of the apparatus for manufacturing the transition metal hydroxide of this invention is shown. Also in the method for producing a transition metal hydroxide of the present invention, in the same manner as in the conventional continuous crystallization method, the reaction solution 3 is stirred in the reaction vessel 1 by using the stirring blade 2 from the raw material inlet 4. The mixed aqueous solution containing the metal salt and the aqueous solution containing the caustic aqueous solution and / or the ammonium ion supplier are supplied and reacted to overflow the reaction solution 3 containing the transition metal hydroxide from the reaction vessel 1. A neutralization crystallization step is provided in which a transition metal hydroxide is obtained by continuously overflowing from the mouth 5 and then solid-liquid separating the crystallized particles, washing with water and drying.

  In particular, in the production method of the present invention, the reaction solution 3 is continuously overflowed from the reaction vessel 1, and at the same time, a part of the reaction solution 3 is withdrawn from the reaction vessel 1 by the pump 7. A part of the reaction solution 3 is sent to the solid-liquid separator 8. The solid-liquid separator 8 is characterized in that only the solvent 9 is discharged as a drain from a part of the reaction solution 3 and the concentrated slurry 10 is reintroduced into the reaction vessel 1. By adding such a process, the reaction solution 3 in the reaction vessel 1 is concentrated, that is, the transition metal hydroxide slurry in the reaction vessel 1 is concentrated.

  In the production method of the present invention, a mixed aqueous solution containing a metal salt of a transition metal consisting of a Group 7 to Group 11 transition metal or zinc and, if necessary, a metal salt of an additional element other than the transition metal is a transition solution. It is a supply source of the metal constituting the metal hydroxide. In the present invention, Group 12 zinc is also included in the transition metal.

  Further, the caustic aqueous solution is a pH adjuster for the neutralization reaction. As the caustic alkaline aqueous solution, an aqueous sodium hydroxide solution, an aqueous potassium hydroxide solution, or the like can be used. In general, an aqueous sodium hydroxide solution that is easy to handle and easily available is used.

  On the other hand, the aqueous solution containing an ammonium ion supplier plays a role of controlling the particle size and shape of the particles constituting the transition metal hydroxide to be produced as a complexing agent, and ammonium ions are produced. Since it is not incorporated into the oxide, it functions as a preferable complexing agent in order to obtain a transition metal hydroxide free from impurities. Examples of the aqueous solution containing an ammonium ion supplier include ammonia water, ammonium sulfate aqueous solution, and ammonium chloride aqueous solution. In general, ammonia is easy to handle and easily available. Water is used.

  In the present invention, the specification of the reaction vessel 1 to be used and the method for adjusting the supply amount of each solution are not particularly limited. As described above, the reaction vessel 1 is composed of the stirring blade 2, the overflow port, and the like. 5 and a temperature control means (not shown), supplying a mixed aqueous solution containing a metal salt and an aqueous solution containing an ammonium ion supplier quantitatively and continuously, and supplying a caustic aqueous solution with an added amount adjusted thereto By doing so, a continuous crystallization reaction is performed while maintaining the reaction solution 3 in the reaction vessel 1 at a predetermined pH to generate a transition metal hydroxide, and the generated transition metal hydroxide is passed through the overflow port 5. And can be discharged continuously.

  In such a continuous crystallization reaction, the particle size distribution and crystal structure of the resulting transition metal hydroxide are generally controlled by controlling the pH of the reaction solution during the reaction. In the continuous crystallization reaction, when the concentration of the metal contained in the aqueous solution containing the supplied metal salt exceeds the solubility of the metal in the reaction system, the amount of metal exceeding the solubility is precipitated. The desired transition metal hydroxide can be obtained. In addition, the difference in the solubility of metals in the reaction system relative to the concentration of the metal salt in the supplied raw material solution determines the crystal nucleus generation rate, the generation density per volume, the growth rate of the generated crystal nucleus, the crystal shape, etc. Therefore, it is possible to obtain transition metal hydroxides having various crystal shapes and powder properties by changing the solubility of the metal in the reaction system.

  However, in the present invention, since the setting of these conditions is not directly related to the gist thereof, the above conditions may be appropriately set according to the intended use, and the description thereof is omitted.

  In the method for producing a transition metal hydroxide of the present invention, a part of the reaction solution 3 is simply extracted, subjected to solid-liquid separation, and the concentrated slurry 10 is returned to the reaction vessel 1, whereby the solvent in the reaction vessel 1 is changed. In addition to continuously removing and concentrating the transition metal hydroxide slurry in the reaction vessel 1, a raw material charged from the raw material inlet 4, that is, a mixed aqueous solution containing a metal salt, a caustic alkaline aqueous solution, and / or It is characterized in that the crystallization of the transition metal hydroxide is continued while adjusting the total addition rate with the aqueous solution containing the ammonium ion supplier.

  That is, in the present invention, as a premise, it is a particle having a predetermined powder characteristic, that is, a particle having a predetermined value of D10, D50, and D90, or an index indicating a spread of a predetermined particle size distribution [(D90-D10). / MV] is set when obtaining transition metal hydroxide constituted by continuously overflowing the reaction solution 3 without concentrating the transition metal hydroxide slurry in the reaction vessel 1. The total addition rate of the raw material, that is, the mixed aqueous solution containing the metal salt, and the aqueous solution containing the caustic aqueous solution and / or the ammonium ion supplier, and the concentration of the transition metal hydroxide slurry are used as reference conditions. Set.

  The ratio of the raw material addition rate to the transition metal hydroxide slurry concentration ratio, ie, (raw material addition rate magnification) / (transition metal hydroxide slurry concentration in the reaction vessel) with respect to this reference condition. The addition rate of the raw material and the continuous removal amount of the solvent in the reaction vessel are set so that the magnification) is in the range of 0.8 to 1.2. That is, the concentration of the transition metal hydroxide slurry in the reaction vessel 1 is controlled within a predetermined range.

  Transition metal hydroxides, especially transition metal composite hydroxides as precursors of positive electrode active materials for non-aqueous electrolyte secondary batteries, have transition metal hydroxides or transition metal composite hydroxides as their powder properties. It is an index indicating the value of D10, D50, and D90 of the constituting particles, or the spread of the particle size distribution of the particles constituting the transition metal hydroxide or transition metal composite hydroxide [(D90-D10) / MV] Is required to be controlled within a predetermined range.

  Here, D10 is the number of particles in each particle size accumulated from the smaller particle size side, and the accumulated volume is 10% of the total volume of all particles. D50 is the number of particles in each particle size. Accumulated from the smaller particle size side, the particle size at which the accumulated volume is 50% of the total volume of all particles, D90 similarly accumulates the number of particles at each particle size, and the accumulated volume is the sum of all particles The particle diameter which becomes 90% of a volume is each meant. MV means volume average particle diameter. In addition, D10, D50, D90, and a volume average particle diameter (MV) are calculated | required from the volume integrated value measured with the laser beam diffraction scattering type particle size analyzer, for example.

  In particular, the particle size distribution of the positive electrode active material is strongly influenced by the particle size distribution, which is a basic powder characteristic of the transition metal composite hydroxide that is the precursor. For this reason, the lithium ion secondary battery is required by controlling [(D90-D10) / MV], which is an index indicating the spread of the particle size distribution of the particles constituting the transition metal composite hydroxide, within a predetermined range. Thus, a positive electrode active material having a predetermined particle size distribution according to battery characteristics such as output characteristics and cycle characteristics is obtained.

  The present invention makes it possible to obtain a transition metal hydroxide having a particle size distribution equivalent to the conventional one with high productivity by controlling the rate of addition of raw materials and the rate of slurry concentration within the above ranges. Specifically, the change rate of D10, D50, and D90 of the particles constituting the metal hydroxide obtained by the present invention relative to the particles constituting the metal hydroxide obtained under the conventional conditions (reference conditions) is 20 % Or less.

  When (raw material addition rate magnification) / (slurry concentration magnification) exceeds 1.2, the particle residence time is significantly shorter than conventional, so the particle size distribution of the obtained particles is reduced and It is not preferable because the rate of change of any one of D10, D50, and D90 becomes 20% or more.

  On the other hand, if (raw material addition rate magnification) / (slurry concentration magnification) is less than 0.8, the particle residence time will be significantly longer than before, so the particle size distribution of the resulting particles will be larger. Since the rate of change of any one of D10, D50, and D90 is 20% or more, it is not preferable.

  In particular, the ratio of D10, D50, and D90 with respect to particles obtained under the conventional conditions is 10% by adjusting the ratio of (raw material addition rate) / (slurry concentration) in the range of 0.9 to 1.1. The following can be suppressed.

  When the present invention is applied to a method for producing a transition metal hydroxide containing only a single transition metal, excluding inevitable impurities, the transition metal includes a group 12 zinc, a group 7 to Group 11 transition metals are to be interpreted broadly. However, among the transition metals of Group 7 to Group 11, in particular, Ni, Co, Mn, and Fe, and Zn are highly versatile. Therefore, the present invention provides a method for producing a transition metal hydroxide containing these. It is industrially very useful to improve the productivity by applying.

  In addition, as a method for removing the solvent in the reaction vessel, a wet cyclone is preferable. Although it is possible to use general solid-liquid separation devices and concentrating devices such as crossflow filtration devices and centrifugal filtration devices, crossflow filtration devices are prone to clogging, and centrifugal filtration devices are devices. However, there is a drawback that it is expensive and tends to be large. By using a wet cyclone, clogging does not occur even in a long-time reaction, and stable particle production can be achieved at low cost.

  In addition to transition metal hydroxides containing only a single transition metal except for inevitable impurities, the present invention includes a group 7 to group 11 transition metal or a plurality of transition metals consisting of zinc, If necessary, mainly used as a precursor of a transition metal composite hydroxide containing an additional element (metal element) other than a transition metal, in particular, a positive electrode active material for a non-aqueous electrolyte secondary battery, mainly nickel hydroxide Nickel composite hydroxide, mainly composed of cobalt hydroxide, including other transition metals and optional additional elements, and cobalt composite hydroxide, mainly including manganese water, including other transition metals and optional additional elements A manganese composite hydroxide comprising an oxide, including other transition metals and optional additional elements, and mainly comprising a hydroxide of nickel, cobalt, and manganese, Transition metals and any additional element to be nickel-cobalt-manganese composite hydroxide, is preferably applied. In addition, the additive element is not limited to a transition element of Group 7 to Group 11, but a transition element of Group 3 to Group 11 or a metal element such as aluminum other than the transition element is selected depending on the application. In such a case, the present invention can be applied. In each transition metal composite hydroxide, the composition of main components such as nickel, cobalt, manganese, etc., the kind of additive element and the amount of addition, etc., as described above, the function of these metal elements and the positive electrode It is appropriately set according to the characteristics according to the use of the final product such as the active material. However, since these are not directly related to the gist of the present invention, the description thereof is omitted.

Specifically, the manufacturing method of the transition metal hydroxide of the present invention have the general _{formula: Ni 1-x-y Co} x Al y (OH) 2 + α (0 ≦ x ≦ 0.3,0.005 ≦ y ≦ 0.15, 0 ≦ α ≦ 0.5), and is applicable to a method for producing a nickel composite hydroxide.

  In this method for producing a nickel composite hydroxide, basically, the nickel composite hydroxide is obtained by neutralization crystallization by the continuous crystallization method described above. Also in this case, as a premise, the nickel composite hydroxide composed of particles having [(D90-D10) / MV] which is an index indicating the spread of a predetermined particle size distribution is converted into nickel composite hydroxide in the reaction vessel. The raw material, that is, a mixed aqueous solution containing a metal salt, an aqueous solution containing the caustic alkali aqueous solution, and an ammonium ion supplier, which is set when the reaction solution is continuously overflowed without concentrating the product slurry. The total addition rate and the concentration of the nickel composite hydroxide slurry are set as reference conditions.

  The ratio of the raw material addition rate and the nickel composite hydroxide slurry concentration ratio, ie, (raw material addition rate magnification) / (nickel composite hydroxide slurry concentration in the reaction vessel) with respect to this reference condition. The addition rate of the raw material and the continuous removal amount of the solvent in the reaction vessel are set so that the magnification) is in the range of 0.8 to 1.2. That is, the concentration of the nickel composite hydroxide slurry in the reaction vessel is controlled within a predetermined range.

  When the method for producing transition metal composite oxide particles of the present invention is applied to the method for producing nickel composite hydroxide having the above composition, (magnification rate of raw material addition) / (magnification of slurry concentration in reaction vessel) By setting it as the range of 0.8-1.2, the change rate of [(D90-D10) / MV] with respect to the particle | grains obtained on conventional conditions can be suppressed to 10% or less. Preferably, by setting (raw material addition rate magnification) / (slurry concentration magnification) in the range of 0.9 to 1.1, [(D90-D10) / MV] of particles obtained under conventional conditions. The rate of change can be suppressed to 5% or less.

A method of manufacturing a transition metal hydroxide of the present invention have the general _{formula: Ni x Co y Mn z M} t (OH) 2 + α (x + y + z + t = 1,0.1 ≦ x ≦ 0.7,0.1 ≦ y ≦ 0.5, 0.1 ≦ z ≦ 0.8, 0 ≦ t ≦ 0.02, 0 ≦ α ≦ 0.5, M is Ti, V, Cr, Zr, Nb, Mo, Hf, Ta, And one or more additive elements selected from W) and a method for producing a nickel cobalt manganese composite hydroxide.

  In the nickel-cobalt-manganese composite hydroxide of this embodiment, nickel contributes to an improvement in battery capacity, cobalt contributes to an improvement in cycle characteristics, and manganese (Mn) contributes to an improvement in thermal stability. If these addition amounts are not within an appropriate range, the function is not sufficiently exhibited, or other battery characteristics are impaired. Further, the additive element (M) is appropriately selected according to the use and required performance of the secondary battery in which the positive electrode active material obtained using the nickel cobalt manganese composite hydroxide as a precursor is used.

  Also in this method for producing a nickel cobalt manganese composite hydroxide, basically, the nickel cobalt manganese composite hydroxide is obtained by neutralization crystallization by the continuous crystallization method described above. Also in this case, as a premise, nickel cobalt manganese composite hydroxide composed of particles having [(D90-D10) / MV] which is an index indicating a predetermined particle size distribution is converted into nickel cobalt in the reaction vessel. Supply of raw materials, that is, a mixed aqueous solution containing a metal salt, the caustic aqueous solution, and ammonium ion supply, which are set when the reaction solution is continuously overflowed without concentrating the manganese composite hydroxide slurry. The total addition rate with the aqueous solution containing the body and the concentration of the nickel cobalt manganese composite hydroxide slurry are set as reference conditions.

  The ratio of the raw material addition rate to the nickel cobalt manganese composite hydroxide slurry concentration ratio, that is, (the raw material addition rate multiple) / (nickel cobalt manganese composite hydroxide in the reaction vessel). The addition rate of the raw material and the continuous removal amount of the solvent in the reaction vessel are set so that the product slurry concentration ratio) is in the range of 0.8 to 1.2. That is, the concentration of the nickel cobalt manganese composite hydroxide slurry in the reaction vessel is controlled within a predetermined range.

  When the method for producing transition metal composite oxide particles of the present invention is applied to the method for producing nickel cobalt manganese composite hydroxide having the above composition, (magnification of addition rate of raw materials) / (magnification of slurry concentration in reaction vessel) ) In the range of 0.8 to 1.2, the rate of change of [(D90-D10) / MV] with respect to particles obtained under conventional conditions can be suppressed to 10% or less. Preferably, by setting (raw material addition rate magnification) / (slurry concentration magnification) in the range of 0.9 to 1.1, [(D90-D10) / MV] of particles obtained under conventional conditions. The rate of change can be suppressed to 5% or less.

  The present invention will be described in more detail with reference to examples and comparative examples, but the present invention is not limited to these examples.

  In the following examples and comparative examples, the measurement of particle size distribution was evaluated from the measurement results of a laser diffraction particle size distribution meter (manufactured by Nikkiso Co., Ltd., Microtrack).

  In this example, each sample of a reagent grade manufactured by Wako Pure Chemical Industries, Ltd. was used for the production of transition metal hydroxide or transition metal composite hydroxide.

Example 1
First, as a reference condition, 5 L of industrial water and a 24% caustic soda solution were added to an overflow crystallization reaction tank having a tank volume of 10 L equipped with four baffle plates to make the pH in the tank 10.0. While stirring the reaction vessel maintained at 40 ° C. using a three-blade propeller blade having a diameter of 10 cm (an inclination angle of 30 degrees) at a rotation speed of 800 rpm, a nickel molar concentration of 1.0 mol / L was used using a metering pump. An aqueous nickel sulfate solution (hereinafter referred to as a raw material solution) was supplied at 40 ml / min, and a 24% caustic soda solution was intermittently added, and the pH at 25 ° C. was controlled to be 9.9 to 10.1. . The average value of the total addition flow rate of the raw material solution and the 24% caustic soda solution was 50 ml / min, and the average particle residence time determined by the tank volume / total addition flow rate (slurry discharge flow rate) was 200 min.

  The produced nickel hydroxide was continuously taken out by overflow, and the nickel hydroxide taken out over 48 to 72 hours from the start of the reaction was washed with water and dried to obtain powdered nickel hydroxide particles. The nickel hydroxide slurry concentration in the reaction vessel in the same time zone was 47 g / L. The particle size distribution of the obtained nickel hydroxide was measured and found to be D10: 3.9 μm, D50: 8.6 μm, and D90: 15.9 μm.

  With respect to the above-mentioned standard conditions, the production rate per unit time is doubled, assuming that the addition rate of the raw material solution is 80 ml / min, the average value of the total addition flow rate of the raw material solution and the 24% caustic soda solution is 100 ml / min, It concentrated so that the nickel hydroxide slurry density | concentration in a reaction tank might be 90 g / L with a wet cyclone. As a result, (magnification of raw material addition rate) / (magnification of slurry concentration in the reaction vessel) was 1.04. Other than that, the particle size distribution of the obtained nickel hydroxide was D10: 3.7 μm, D50: 8.0 μm, D90: 14.9 μm as a result of testing under the same conditions as the above-mentioned standard conditions, and D10, D50 , D90 had a change rate with respect to the reference condition of 10% or less.

(Example 2)
A similar test was performed except that nickel in Example 1 was changed to cobalt. The particle size distribution of the cobalt hydroxide particles obtained under the standard conditions was measured and found to be D10: 5.8 μm, D50: 10.6 μm, and D90: 17.3 μm. The particle size distribution of the cobalt hydroxide particles obtained in this example is D10: 5.6 μm, D50: 10.0 μm, D90: 16.8 μm, and all of D10, D50, and D90 have a change rate of 10 with respect to the reference condition. It was less than%.

(Example 3)
A similar test was performed except that nickel in Example 1 was changed to manganese. The particle size distribution of the manganese hydroxide particles obtained under the standard conditions was measured and found to be D10: 4.3 μm, D50: 9.6 μm, and D90: 16.0 μm. The particle size distribution of the manganese hydroxide particles obtained in this example is D10: 3.9 μm, D50: 8.9 μm, and D90: 15.0 μm, and all of D10, D50, and D90 have a change rate of 10 with respect to the reference condition. It was less than%.

Example 4
A similar test was conducted except that nickel in Example 1 was changed to iron. When the particle size distribution of the iron hydroxide particles obtained under the standard conditions was measured, they were D10: 2.8 μm, D50: 5.7 μm, and D90: 9.9 μm. The particle size distribution of the iron hydroxide particles obtained in this example is D10: 2.6 μm, D50: 5.4 μm, D90: 9.5 μm, and all of D10, D50, and D90 have a rate of change of 10 with respect to the reference condition. It was less than%.

(Example 5)
A similar test was performed except that nickel in Example 1 was changed to zinc. When the particle size distribution of the zinc hydroxide particles obtained under the standard conditions was measured, they were D10: 3.8 μm, D50: 8.4 μm, and D90: 14.4 μm. The particle size distribution of the zinc hydroxide particles obtained in this example is D10: 3.6 μm, D50: 8.1 μm, D90: 13.9 μm, and all of D10, D50, and D90 have a change rate of 10% with respect to the reference condition. It was below.

(Example 6)
The addition rate of the raw material solution is 120 ml / min, the average value of the total addition flow rate of the raw material solution and the 24% caustic soda solution is 150 ml / min, and the production volume per unit time is increased three times. Concentration was performed so that the nickel hydroxide slurry concentration was 123 g / L. As a result, (magnification of raw material addition rate) / (magnification of slurry concentration in the reaction vessel) was 1.15. Except for this, the same test as in Example 1 was performed. The particle size distribution of the nickel hydroxide particles obtained in this example is D10: 3.9 μm, D50: 8.6 μm, and D90: 15.9 μm, which are the particle size distributions of nickel hydroxide obtained under the standard conditions. D10: 3.4 μm, D50: 7.5 μm, D90: 13.6 μm, and all of D10, D50, and D90 had a change rate of 20% or less with respect to the reference condition.

(Example 7)
The addition rate of the raw material solution is 160 ml / min, the average value of the total addition flow rate of the raw material solution and the 24% caustic soda solution is 200 ml / min, and the production volume per unit time is increased four times. Concentration was performed so that the nickel hydroxide slurry concentration of 221 g / L. As a result, (magnification of raw material addition rate) / (magnification of slurry concentration in the reaction vessel) was 0.85. Except for this, the same test as in Example 1 was performed. The particle size distribution of the nickel hydroxide particles obtained according to this example with respect to the particle size distribution of the nickel hydroxide particles obtained under the standard conditions, D10: 3.9 μm, D50: 8.6 μm, D90: 15.9 μm D10: 4.5 μm, D50: 10.0 μm, D90: 18.9 μm, and all of D10, D50, and D90 had a change rate of 20% or less with respect to the reference condition.

(Comparative Example 1)
The addition rate of the raw material solution is 80 ml / min, the average value of the total addition flow rate of the raw material solution and the 24% caustic soda solution is 100 ml / min, and the production volume per unit time is doubled. Concentration was carried out so that the concentration of the nickel hydroxide slurry was 72 g / L. As a result, (magnification of raw material addition rate) / (magnification of slurry concentration in the reaction vessel) was 1.31. Except for this, the same test as in Example 1 was performed. The particle size distribution of the nickel hydroxide particles obtained according to this example with respect to the particle size distribution of the nickel hydroxide particles obtained under the standard conditions, D10: 3.9 μm, D50: 8.6 μm, D90: 15.9 μm D10: 3.2 μm, D50: 6.4 μm, D90: 11.4 μm, and the rate of change of D50 and D90 with respect to the reference conditions exceeded 20%.

(Comparative Example 2)
The addition rate of the raw material solution is 80 ml / min, the average value of the total addition flow rate of the raw material solution and the 24% caustic soda solution is 100 ml / min, and the production volume per unit time is doubled. Concentration was carried out so that the concentration of the nickel hydroxide slurry was 134 g / L. As a result, (magnification of raw material addition rate) / (magnification of slurry concentration in the reaction vessel) was 0.70. Except for this, the same test as in Example 1 was performed. The particle size distribution of the nickel hydroxide particles obtained according to this example with respect to the particle size distribution of the nickel hydroxide particles obtained under the standard conditions, D10: 3.9 μm, D50: 8.6 μm, D90: 15.9 μm D10: 5.1 μm, D50: 9.9 μm, D90: 19.6 μm, and the rate of change of D10 and D90 relative to the reference condition exceeded 20%.

  From the above, when the (raw material addition rate magnification) / (slurry concentration magnification in the reaction vessel) with respect to the standard condition is less than 0.8 or greater than 1.2, the particle size distribution of the particles obtained is It was confirmed that the change rate of any of D10, D50, and D90 exceeds 20% with respect to the particles obtained in the above, which is not preferable in terms of obtaining particles equivalent to the reference conditions.

(Example 8)
First, as a reference condition, 170 L of pure water, 25% caustic soda solution and 25% ammonia water were added to a 200 L overflow crystallization reaction tank equipped with four baffle plates, and the pH in the tank at 25 ° C. Was adjusted to 12.4 and the ammonia concentration in the tank was adjusted to 12 g / L. While stirring the reaction vessel maintained at 40 ° C. at a rotational speed of 280 rpm using a 6-blade flat turbine blade having a diameter of 25 cm, using a metering pump, the nickel molar concentration was 1.4 mol / L, the cobalt molar concentration was 0.1. A 3 mol / L nickel cobalt sulfate mixed aqueous solution is supplied at 580 ml / min and an aluminum concentration 0.43 mol / L sodium aluminate aqueous solution is supplied at 92 ml / min, and 25% sodium hydroxide solution and 25% aqueous ammonia are added intermittently. Then, the pH at 25 ° C. was controlled to be 12.4 and the ammonia concentration was maintained at 12 g / L.

  The average value of the total addition flow rate of nickel cobalt sulfate mixed aqueous solution, sodium aluminate aqueous solution, 25% caustic soda solution and 25% ammonia water was 960 ml / min, and the average particle residence time was 208 min.

  The produced nickel composite hydroxide was continuously taken out by overflow, and the nickel composite hydroxide taken out for 48 to 72 hours from the start of the reaction was washed with water and dried to obtain a powdered nickel composite hydroxide. . The nickel composite hydroxide slurry concentration in the reaction vessel in the same time zone was 100 g / L. When the particle size distribution of the obtained nickel composite hydroxide was measured, D10: 6.9 μm, D50: 11.8 μm, D90: 19.5 μm, MV: 12.7 μm, (D90-D10) / MV: 0.00. 99.

  With respect to the above-mentioned standard conditions, the addition rate of the nickel cobalt sulfate mixed aqueous solution is 880 ml / min, the average value of the total addition flow rate of 1453 ml / min of the nickel cobalt sulfate mixed aqueous solution, sodium aluminate aqueous solution, 25% caustic soda solution and 25% ammonia water As a result, the production amount per unit time is increased by 1.5 times, and further, the concentration is made so that the nickel composite hydroxide slurry concentration in the reaction vessel becomes 148 g / L by a wet cyclone, (Magnification) / (magnification of slurry concentration in reaction vessel) was set to 1.02. Otherwise, as a result of carrying out the same test as the standard condition, the particle size distribution of the obtained nickel composite hydroxide is D10: 7.0 μm, D50: 12.4 μm, D90: 19.8, MV: 13. 1 μm, (D90-D10) / MV: 1.03, and the rate of change of [(D90-D10) / MV] with respect to the reference condition was 4%.

Example 9
The pH in the tank of Example 8 was 12.38, the addition rate of the nickel cobalt sulfate mixed aqueous solution was 1160 ml / min, the total addition flow rate of nickel cobalt sulfate mixed aqueous solution, sodium aluminate aqueous solution, 25% caustic soda solution, and 25% aqueous ammonia. The average value of 1,200 ml / min, the production volume per unit time is doubled, and further the concentration is performed so that the nickel composite hydroxide slurry concentration in the reaction vessel becomes 174 g / L by a wet cyclone, A similar test was performed except that (raw material addition rate magnification) / (slurry concentration in reaction vessel) was 1.15. D10: 6.9 μm, D50: 11.8 μm, D90: 19.5 μm, MV :, 12.7 μm, (D90-D10) / MV: particle size distribution of nickel composite hydroxide obtained under the standard conditions In contrast, the particle size distribution of the nickel composite hydroxide of this example was D10: 7.3 μm, D50: 11.5 μm, D90: 18.8 μm, MV: 12.6 μm, (D90-D10) / MV. : 0.91, and the rate of change of [(D90-D10) / MV] with respect to the reference condition was 8%.

(Example 10)
The pH in the tank of Example 8 was 12.42, the addition rate of the nickel cobalt sulfate mixed aqueous solution was 1740 ml / min, the total addition flow rate of the nickel cobalt sulfate mixed aqueous solution, the sodium aluminate aqueous solution, the 25% caustic soda solution, and the 25% ammonia water. The average value is 2880 ml / min, the production amount per unit time is increased three times, and further the concentration is performed so that the nickel composite hydroxide slurry concentration in the reaction vessel becomes 353 g / L by a wet cyclone, A similar test was performed except that (raw material addition rate) / (slurry concentration in reaction vessel) was 0.85. D10: 6.9 μm, D50: 11.8 μm, D90: 19.5 μm, MV :, 12.7 μm, (D90-D10) / MV: particle size distribution of nickel composite hydroxide obtained under the standard conditions On the other hand, the particle size distribution of the nickel composite hydroxide of this example is D10: 7.0 μm, D50: 12.2 μm, D90: 20.6 μm, MV: 12.9 μm, (D90-D10) / MV. : 1.05, and the rate of change of [(D90-D10) / MV] with respect to the reference condition was 6%.

(Comparative Example 3)
The pH in the tank of Example 8 was 12.47, the addition rate of the nickel cobalt sulfate mixed aqueous solution was 880 ml / min, the total addition flow rate of nickel cobalt sulfate mixed aqueous solution, sodium aluminate aqueous solution, 25% caustic soda solution, and 25% ammonia water. The average value is 1453 ml / min, the production volume per unit time is increased by a factor of 1.5, and concentration is further performed by a wet cyclone so that the nickel composite hydroxide slurry concentration in the reaction vessel becomes 115 g / L. The same test was performed except that (raw material addition rate magnification) / (slurry concentration magnification in reaction vessel) was set to 1.32. D10: 6.9 μm, D50: 11.8 μm, D90: 19.5 μm, MV: 12.7 μm, (D90-D10) / MV: 0, which is the particle size distribution of the nickel composite hydroxide obtained under the reference conditions. In contrast, the particle size distribution of the nickel composite hydroxide of this example is D10: 7.4 μm, D50: 11.5 μm, D90: 18.4 μm, MV: 12.5 μm, (D90-D10) / MV: It was 0.88, and the rate of change of [(D90-D10) / MV] with respect to the reference condition was 11%.

(Comparative Example 4)
The pH in the tank of Example 8 was 12.35, the addition rate of the nickel cobalt sulfate mixed aqueous solution was 880 ml / min, the total addition flow rate of nickel cobalt sulfate mixed aqueous solution, sodium aluminate aqueous solution, 25% caustic soda solution, and 25% ammonia water. The average production value is 1453 ml / min, the production amount per unit time is increased 1.5 times, and further, the concentration is performed by a wet cyclone so that the nickel composite hydroxide slurry concentration in the reaction vessel becomes 214 g / L. The same test was conducted except that (raw material addition rate magnification) / (slurry concentration magnification in reaction vessel) was 0.71. D10: 6.9 μm, D50: 11.8 μm, D90: 19.5 μm, MV: 12.7 μm, (D90-D10) / MV: 0, which is the particle size distribution of the nickel composite hydroxide obtained under the reference conditions. In contrast, the particle size distribution of the nickel composite hydroxide of this example is D10: 6.4 μm, D50: 12.0 μm, D90: 20.6 μm, MV: 12.9 μm, (D90-D10) / MV: 1. The rate of change of [(D90-D10) / MV] relative to the reference condition was 11%.

  As described above, in the method for producing the nickel composite oxide, the ratio of the ratio of the mixed aqueous solution containing the metal salt, the aqueous caustic aqueous solution, and the total addition rate of the aqueous ammonia to the ratio of the slurry concentration in the reaction vessel is 0. When the value is less than 0.8 or more than 1.2, the change rate of [(D90-D10) / MV], which is an index indicating the spread of the particle size distribution of the obtained particles, exceeds 10%. It was confirmed that it is not preferable in terms of obtaining equivalent particles.

(Example 11)
First, as a reference condition, 170 L of pure water, 25% caustic soda solution and 25% ammonia water were added to a 200 L overflow crystallization reaction tank equipped with four baffle plates, and the pH in the tank at 25 ° C. Was adjusted to 12.4 and the ammonia concentration in the tank was adjusted to 12 g / L. While stirring the inside of the reaction vessel maintained at 40 ° C. at a rotational speed of 280 rpm using a 6-blade flat turbine blade having a diameter of 25 cm, a nickel molar concentration of 0.7 mol / L and a cobalt molar concentration of 0. 7 mol / L, manganese molar concentration 0.7 mol / L of nickel cobalt cobalt manganese mixed aqueous solution was supplied at 580 ml / min, and 25% sodium hydroxide solution and 25% aqueous ammonia were added intermittently, and pH at 25 ° C. Was controlled to be 12.4 and the ammonia concentration was maintained at 12 g / L. During the reaction, nitrogen gas was blown into the tank at 50 L / min, and the atmosphere in the tank was controlled to be an inert atmosphere.

  The average value of the total addition flow rate of the nickel cobalt cobalt manganese sulfate mixed aqueous solution 25% caustic soda and 25% ammonia water was 960 ml / min, and the average particle residence time was 208 min.

  The produced nickel cobalt manganese composite hydroxide is continuously taken out by overflow, and the nickel cobalt manganese composite hydroxide taken over 48 to 72 hours from the start of the reaction is washed with water and dried to form a powdery nickel cobalt manganese composite A hydroxide was obtained. The nickel cobalt manganese composite hydroxide slurry concentration in the reaction tank in the same time zone was 98 g / L. When the particle size distribution of the obtained nickel cobalt manganese composite hydroxide was measured, D10: 5.2 μm, D50: 7.8 μm, D90: 11.8 μm, MV: 8.5 μm, (D90-D10) / MV: It was 0.78.

  With respect to the above reference conditions, the addition rate of the nickel cobalt manganese sulfate mixed aqueous solution is 880 ml / min, the average value of the total addition flow rate of the nickel cobalt cobalt manganese sulfate mixed aqueous solution, 25% caustic soda solution and 25% ammonia water is 1453 ml / min. The production volume per hour was increased by a factor of 1.5, and further concentrated so that the nickel-cobalt-manganese composite hydroxide slurry concentration in the reaction vessel would be 147 g / L using a wet cyclone (multiplier of raw material addition rate) ) / (Magnification of slurry concentration in reaction vessel) was set to 1.01. Other than that, as a result of carrying out the same test as the standard condition, the particle size distribution of the obtained nickel cobalt manganese composite hydroxide was D10: 5.0 μm, D50: 7.5 μm, D90: 11.4, MV: 8.4 μm, (D90-D10) / MV: 0.76, and the rate of change of [(D90-D10) / MV] relative to the reference condition was 2%.

(Example 12)
The tank pH in Example 11 was 12.38, the addition rate of the nickel cobalt manganese sulfate mixed aqueous solution was 1160 ml / min, the average value of the total addition flow rate of the nickel cobalt cobalt manganese mixed aqueous solution, 25% caustic soda solution, and 25% ammonia water. Is increased to 1920 ml / min, the production amount per unit time is doubled, and further, the wet cobalt is concentrated so that the nickel cobalt manganese composite hydroxide slurry concentration in the reaction tank is 174 g / L. The same test was performed except that the ratio of the raw material addition rate) / (the ratio of the slurry concentration in the reaction vessel) was 1.13. D10: 5.2 μm, D50: 7.8 μm, D90: 11.8 μm, MV: 8.5 μm, (D90-D10) / MV, which is the particle size distribution of nickel cobalt manganese composite hydroxide obtained under standard conditions : 0.78, the particle size distribution of the nickel cobalt manganese composite hydroxide of this example is D10: 4.7 μm, D50: 6.8 μm, D90: 10.2 μm, MV: 7.7 μm, (D90-D10 ) / MV: 0.71, and the rate of change of [(D90-D10) / MV] with respect to the reference condition was 9%.

(Example 13)
The pH in the tank of Example 11 was 12.42, the addition rate of the nickel cobalt cobalt manganese mixed aqueous solution was 1740 ml / min, the average value of the total addition flow rate of the nickel cobalt cobalt manganese mixed aqueous solution, 25% caustic soda solution, and 25% ammonia water. Is increased to 2880 ml / min, the production amount per unit time is increased three times, and further, the concentration is carried out by a wet cyclone so that the nickel cobalt manganese composite hydroxide slurry concentration in the reaction tank becomes 353 g / L. A similar test was performed except that the ratio of the raw material addition rate) / (the ratio of the slurry concentration in the reaction vessel) was 0.83. D10: 5.2 μm, D50: 7.8 μm, D90: 11.8 μm, MV: 8.5 μm, (D90-D10) / MV, which is the particle size distribution of nickel cobalt manganese composite hydroxide obtained under standard conditions : 0.78, the particle size distribution of the nickel cobalt manganese composite hydroxide of this example was D10: 5.4 μm, D50: 8.2 μm, D90: 12.5 μm, MV: 8.6 μm, (D90-D10 ) / MV: 0.83, and the rate of change of [(D90-D10) / MV] with respect to the reference condition was 6%.

(Comparative Example 5)
The pH in the tank of Example 11 was 12.47, the addition rate of the nickel cobalt manganese sulfate mixed aqueous solution was 880 ml / min, the average value of the total addition flow rate of the nickel cobalt cobalt manganese mixed aqueous solution, 25% caustic soda solution, and 25% ammonia water. To 1453 ml / min, the production amount per unit time is increased 1.5 times, and further, the wet cobalt is concentrated so that the nickel cobalt manganese composite hydroxide slurry concentration in the reaction tank becomes 115 g / L. The same test was conducted except that (raw material addition rate) / (slurry concentration in reaction vessel) was 1.29. D10: 5.2 μm, D50: 7.8 μm, D90: 11.8 μm, MV: 8.5 μm, (D90-D10) / MV, which is the particle size distribution of nickel cobalt manganese composite hydroxide obtained under standard conditions : 0.78, the particle size distribution of the nickel cobalt manganese composite hydroxide of this example was D10: 4.9 μm, D50: 7.2 μm, D90: 10.3 μm, MV: 7.9 μm, (D90-D10 ) / MV: 0.68, and the rate of change of [(D90-D10) / MV] with respect to the reference condition was 12%.

(Comparative Example 6)
The pH in the tank of Example 11 was 12.35, the addition rate of the nickel cobalt manganese sulfate mixed aqueous solution was 880 ml / min, the average value of the total addition flow rate of the nickel cobalt cobalt manganese mixed aqueous solution, 25% caustic soda solution, and 25% ammonia water. To 1453 ml / min, the production amount per unit time is increased 1.5 times, and further, the wet cobalt is concentrated so that the nickel cobalt manganese composite hydroxide slurry concentration in the reaction tank becomes 214 g / L. The same test was conducted except that (raw material addition rate) / (slurry concentration in reaction vessel) was 0.69. D10: 5.2 μm, D50: 7.8 μm, D90: 11.8 μm, MV: 8.5 μm, (D90-D10) / MV, which is the particle size distribution of nickel cobalt manganese composite hydroxide obtained under standard conditions : 0.78, the particle size distribution of the nickel cobalt manganese composite hydroxide of this example is D10: 4.9 μm, D50: 8.4 μm, D90: 12.6 μm, MV: 8.7 μm, (D90-D10 ) / MV: 0.89, and the rate of change of [(D90-D10) / MV] with respect to the reference condition was 13%.

  From the above, also in the method for producing nickel cobalt manganese composite hydroxide, the ratio of the mixed aqueous solution containing the metal salt, the caustic alkaline aqueous solution, and the ammonia water addition rate relative to the total reference condition and the ratio of the slurry concentration in the reaction vessel When the ratio is less than 0.8 or more than 1.2, the change rate of [(D90-D10) / MV], which is an index indicating the spread of the particle size distribution of the obtained particles, exceeds 10%. It was confirmed that it is not preferable in terms of obtaining particles equivalent to the reference conditions.

DESCRIPTION OF SYMBOLS 1 Reaction container 2 Stirring blade 3 Reaction solution 4 Raw material input port 5 Overflow port 6 Drainage port 7 Pump 8 Solid-liquid separator 9 Solvent (drainage)
10 Concentrated slurry

Claims (8)

A method for producing a transition metal hydroxide containing a transition metal of group 7 to group 11 or zinc,
In the reaction vessel, while stirring the reaction solution, a mixed aqueous solution containing a metal salt and an aqueous solution containing a caustic aqueous solution and / or an ammonium ion supplier are supplied and reacted, and the crystallized particles are separated into solid and liquid. In the neutralization crystallization step of obtaining a transition metal hydroxide by washing with water and drying,
While continuously overflowing the reaction solution containing the transition metal hydroxide from the reaction vessel, removing the solvent in the reaction vessel continuously and concentrating the transition metal hydroxide slurry in the reaction vessel , Continuing crystallization of the transition metal hydroxide, and
Transition metal hydroxide composed of particles having predetermined D10, D50, and D90 values, or particles having a value of [(D90-D10) / MV], which is an index indicating the spread of a predetermined particle size distribution Is obtained by continuously overflowing the reaction solution without concentrating the transition metal hydroxide slurry in the reaction vessel, and a mixed aqueous solution containing the metal salt, and the caustic alkaline aqueous solution. And / or when the addition rate of the aqueous solution containing the ammonium ion supplier and the concentration of the transition metal hydroxide slurry are used as reference conditions,
The addition rate is set so that the ratio of the addition rate to the reference condition and the transition metal hydroxide slurry concentration ratio is in the range of 0.8 to 1.2, and Continuously removing the solvent in the reaction vessel,
The manufacturing method of the transition metal hydroxide characterized by the above-mentioned.   2. The transition metal hydroxide according to claim 1, wherein a ratio of the addition rate magnification to the reference condition and the transition metal hydroxide slurry concentration ratio is in a range of 0.9 to 1.1. Production method.   The method for producing a transition metal hydroxide according to claim 1 or 2, wherein a wet cyclone is used to continuously remove the solvent in the reaction vessel.   The method for producing a transition metal hydroxide according to any one of claims 1 to 3, wherein at least one selected from Ni, Co, Mn, Fe, and Zn is used as the transition metal. It said transition metal hydroxide is represented by the general _{formula: Ni 1-x-y Co} x Al y (OH) 2 + α (0 ≦ x ≦ 0.3,0.005 ≦ y ≦ 0.15,0 ≦ α ≦ 0. The method for producing a transition metal hydroxide according to any one of claims 1 to 3, which is a nickel composite hydroxide represented by 5). The transition metal hydroxide has a general formula: Ni _x Co _y Mn _z M _t (OH) _{2 + α} (x + y + z + t = 1, 0.1 ≦ x ≦ 0.7, 0.1 ≦ y ≦ 0.5, 0. 1 ≦ z ≦ 0.8, 0 ≦ t ≦ 0.02, 0 ≦ α ≦ 0.5, M is selected from Ti, V, Cr, Zr, Nb, Mo, Hf, Ta, and W The manufacturing method of the transition metal complex oxide in any one of Claims 1-3 which is a nickel cobalt manganese complex hydroxide represented by the additive element of a seed | species or more.   The method for producing a transition metal hydroxide according to claim 1, wherein a sodium hydroxide aqueous solution is used as the caustic aqueous solution.   The method for producing a transition metal hydroxide according to claim 1, wherein ammonia water is used as the aqueous solution containing the ammonium ion supplier.

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