JP2020205205A - Method for manufacturing transition metal composite hydroxide - Google Patents

Abstract

To provide a manufacturing method which makes it possible to obtain a nickel cobalt manganese composite hydroxide having a uniform particle size distribution, and a desired particle size, and which enables an industrially stable operation.SOLUTION: A method for manufacturing a transition metal composite hydroxide to be used as a precursor of a positive electrode active material for a lithium ion secondary battery comprises neutralization crystallization, including at least: a nucleus-producing step of forming a post-nucleus production liquid produced in such a way that each fine transition metal composite hydroxide particle makes a nucleus while keeping pH of a reaction liquid within a predetermined range by addition of a pH conditioner; and a particle-growing step of growing each nucleus in the post-nucleus production liquid as a particle by precipitation while keeping pH of the post-nucleus production liquid within a predetermined range. In the nucleus-producing step, a reaction liquid is supplied to and mixed with a predetermined amount of the pH conditioner to form the post-nucleus production liquid. When pH of the post-nucleus production liquid is lowered by supply and mixing of the reaction liquid and then reaches a fixed value to be kept in the particle-growing step, the supply of an alkali metal aqueous solution is started. Since that time, the pH is kept at the fixed value until the end of the particle-growing step.SELECTED DRAWING: None

Description

The present invention relates to a method for producing a transition metal composite hydroxide used as a precursor of a positive electrode active material for a lithium ion secondary battery.

In recent years, with the widespread use of small information terminals such as smartphones and tablet PCs, the development of small and lightweight secondary batteries having a high energy density is strongly desired. Further, it is strongly desired to develop a high output secondary battery as a battery for electric vehicles such as hybrid vehicles.
As such a secondary battery, there is a lithium ion secondary battery. The lithium ion secondary battery is composed of a negative electrode, a positive electrode, an electrolytic solution, and the like, and a material capable of desorbing and inserting lithium is used as an active material for the negative electrode and the positive electrode.

This lithium-ion secondary battery is currently being actively researched and developed. Among them, the lithium-ion secondary battery using a layered or spinel-type lithium metal composite oxide as a positive electrode material is 4V. Since a high-grade voltage can be obtained, it is being put into practical use as a battery having a high energy density.

The materials that have been mainly proposed so far are lithium cobalt composite oxide (LiCoO ₂ ), which is relatively easy to synthesize, lithium nickel composite oxide (LiNiO ₂ ), which uses nickel, which is cheaper than cobalt, and lithium nickel. Examples thereof include a cobalt manganese composite oxide (LiNi _1/3 Co _1/3 Mn _1/3 O ₂ ) and a lithium manganese composite oxide using manganese (LiMn ₂ O ₄ ).
Of these, lithium nickel-cobalt-manganese composite oxide is attracting attention as a material that has good cycle characteristics and can take out high output with low resistance.

By the way, in order to obtain the above-mentioned good performance, a composite oxide having a uniform particle size is suitable. This is because when a composite oxide having a wide particle size distribution is used, the voltage applied to each particle in the electrode becomes non-uniform, which causes problems such as cycle deterioration. Therefore, it is necessary to produce a composite oxide having a uniform particle size distribution, and for that purpose, it is important to use a composite hydroxide having a uniform particle size distribution and optimize the production conditions.
Further, since the specific surface area of the particles has a great influence on the output, it is important to control the particle size in order to obtain the desired specific surface area.

For example, in Patent Document 1, in the production stage of composite hydroxide particles, there is a method of clearly separating a step in which a nucleation reaction mainly occurs (nucleation step) and a step in which a particle growth reaction mainly occurs (particle growth step). Have been described. According to such a method, it is possible to prevent the generation of fine particles and coarse particles, so that nickel cobalt-manganese composite hydroxide particles having an appropriate particle size and a narrow particle size distribution can be obtained. It is disclosed.

However, as shown in Patent Document 1, when the steps are separated, the alkali salt solution that has flowed back into the supply pipe reacts with the nickel-cobalt-manganese mixed aqueous solution to precipitate a hydroxide in the supply pipe, and the pH is precipitated in the supply pipe. If there is a problem that the tip of the pH is clogged and the operation is stopped, or if the concentration of sulfuric acid added to lower the pH is high, it can be lowered in a short time, but too much sulfuric acid enters and the pH is higher than the specified pH. There is a problem that it becomes low and some nuclei are redissolved, and the reaction temperature rises due to the heat of neutralization, which makes it difficult to control the physical properties such as the target pH fluctuates. On the other hand, it is neutralized by using dilute sulfuric acid. Although heat can be suppressed, it takes time to lower the pH, the amount of liquid increases, the concentration of ammonia is lowered, and a dilution facility is required, which causes a problem of high cost.

Furthermore, if NaOH is added to maintain a predetermined pH in the nucleation step, it will be in excess of the amount of NaOH required for the neutralization reaction, so if the pH is lowered to the particle growth step with a stock solution instead of sulfuric acid, the excess will be used. There is also a problem that nucleation occurs and the amount of nucleation exceeds the desired amount, which makes it difficult to control the particle size.

Japanese Unexamined Patent Publication No. 2011-116580

In view of the problems involved, the present invention provides a production method capable of industrially stable operation to obtain a nickel-cobalt-manganese composite hydroxide having a uniform particle size distribution and a desired particle size.

The aspect of the method for producing a transition metal composite hydroxide according to the present invention is characterized in that the particle size distribution is narrow and monodisperse, the average particle size is 3 to 7 μm, and it is an index showing the spread of the particle size distribution [((). D90-D10) / D50] is 0.55 or less. In order to obtain nickel-cobalt-manganese composite hydroxide particles, a mixed aqueous solution of nickel, cobalt, and manganese (hereinafter referred to as undiluted solution) added to the crystallization reaction tank in the nucleation step. ), The NaOH necessary for neutralization calculated from the liquid volume was added in advance, and the undiluted solution and aqueous ammonia were added until the specified pH in the particle growth process was reached, and then the addition of NaOH was restarted. By continuously performing the nucleation step and the particle growth step by reacting to a predetermined amount of liquid which is the total of the growth steps, excess nucleation when adjusting the pH with the undiluted solution is prevented, and the nozzle is clogged due to the suspension of the undiluted solution supply. It is characterized by eliminating the remelting of nuclei due to the addition of or sulfuric acid and the temperature rise due to heat of neutralization, enabling simple and stable operation.

The first invention of the present invention is a method for producing a transition metal composite hydroxide used as a precursor of a positive electrode active material for a lithium ion secondary battery, wherein a pH adjuster is added to adjust the pH at a liquid temperature of 25 ° C. A compound solution of a transition metal and a compound solution forming a complex ion with the transition metal are continuously supplied and mixed in a reaction vessel while maintaining a constant value of 12.0 or more and 14.0 or less. By forming the reaction solution, a nucleation step of forming a post-nuclearization solution in which fine transition metal composite hydroxide particles are formed in the solution as nuclei, and the post-nuclearization solution are formed. While maintaining the pH at a liquid temperature of 25 ° C. as a reference at a constant value in the range of 9.0 or more and 12.0 or less, the transition metal compound solution and the compound solution forming a complex ion with the transition metal are produced. Neutralization crystallization, which includes at least a particle growth step of continuously supplying the after-liquid to grow particles formed by precipitating a composite hydroxide of the transition metal around the nucleus, is the nuclear formation step. The amount of each transition metal ion contained in the compound solution of the transition metal supplied in the above is X (M ₁ ), X (M ₂ ), X (M ₃ ), ..., X (M _K ) ( When k = 1, 2, ... N), the valences when the transition metal ion becomes a transition metal hydroxide are Z (M ₁ ), Z (M ₂ ), Z (M ₃ ), ...・ ・ When Z (M _K ) is set, X (M ₁ ) × Z (M ₁ ) + X (M ₂ ) × Z (M ₂ ) + X (M ₃ ) × Z (M ₃ ) + ・ ・ ・ X ( An alkali metal hydroxide having a substance amount corresponding to M _K ) × Z (M _K ) (K = 1, 2, ... N) forms a complex ion with the transition metal compound solution and the transition metal. When a compound solution is continuously supplied and mixed to form a reaction solution, a compound that is previously charged into a reaction vessel as the pH adjuster to form a compound ion with the transition metal compound solution and the transition metal. The pH of the post-nuclear liquid is lowered by continuous supply and mixing of the solution, and the pH of the post-nuclear liquid reaches the constant value to be maintained in the particle growth step. A positive electrode active material for a lithium ion secondary battery, characterized in that the supply of an aqueous alkali metal solution is started and the pH is maintained at a constant value in the range of 9.0 or more and 12.0 or less until the end of the nuclear growth step thereafter. It is a method for producing a transition metal composite hydroxide used as a precursor of.

A second aspect of the present invention is characterized in that the transition metal compound in the first invention is any one of a transition metal sulfate, a transition metal chloride, a transition metal nitrate, or a mixture of at least two or more kinds. This is a method for producing a transition metal composite hydroxide.

A third invention of the present invention is a method for producing a transition metal composite hydroxide according to the first and second inventions, wherein the compound solution forming a complex ion with the transition metal is aqueous ammonia.

The fourth invention of the present invention is an index showing the spread of the particle size distribution, in which the transition metal composite hydroxide in the first to third inventions has an average particle size of 3 to 7 μm [(D90-D10). ) / D50] is 0.55 or less, which is a method for producing a transition metal composite hydroxide.

In the fifth invention of the present invention, the transition metal composite hydroxide in the first to fourth inventions has an atomic weight ratio of Ni, Co, Mn, and the additive element M in which Ni: Co: Mn: M is 1-xy. −Z: x: y: z (0.1 ≦ x ≦ 0.4, 0.1 ≦ y ≦ 0.5, 0 ≦ z ≦ 0.1, 0.3 ≦ 1-x−y−z ≦ 0 .7, M is Al, Mg, Ca, Ti, V, Cr, Zr, Nb, Mo, Hf, Ta, represented by the general formula 1 or more selected from _{W) Ni x Co y Mn z} (OH ) _{2 + α} (0.3 ≦ x ≦ 0.7, 0.1 ≦ y ≦ 0.4, 0.1 ≦ z ≦ 0.5, x + y + z = 1, 0 ≦ α ≦ 0.5) nickel cobalt It is a method for producing a transition metal composite hydroxide, which is characterized by being a manganese composite hydroxide.

According to the present invention, a nickel-cobalt-manganese composite hydroxide having a desired particle size, which has a narrow particle size distribution and is monodisperse, can be obtained by industrially stable operation.
In addition, the secondary battery using the positive electrode active material for a non-aqueous secondary battery derived from the nickel-cobalt-manganese composite hydroxide according to the present invention has excellent electrical characteristics with high capacity and high output, and is therefore recently portable. It has become possible to meet the demands of high output and good cycle characteristics for portable electronic devices such as telephones and laptop computers, power tools, and small secondary batteries installed in power supplies such as hybrid vehicles or electric vehicles. It has an extremely useful effect in industry.

The present inventor has studied in detail a method for stably obtaining composite hydroxide particles having a narrow particle size distribution, and as a result, crystals are crystallized in the nucleation step in order to obtain the desired nickel-cobalt-manganese composite hydroxide particles. The amount of NaOH required for neutralization calculated from the amount of undiluted solution added to the analysis reaction tank is added to the reaction tank in advance, the undiluted solution and ammonia water are added, the nucleation process is performed, and then the undiluted solution. And ammonia water were added as they were until the pH reached the predetermined pH in the particle growth step, then the addition of the pH adjuster NaOH was restarted, and the reaction was carried out to the total predetermined liquid volume of the nucleation step and the particle growth step. By continuously performing the nucleation step and the particle growth step, the crystallization step can be simplified, and the target pH shift due to the formation of nuclei by excess NaOH when adjusting the pH with the undiluted solution, the re-dissolution of nuclei by sulfuric acid, and the heat of neutralization We have found that it is possible to prevent nozzle clogging due to suspension of supply of undiluted solution and enable stable operation, and completed the present invention.
Hereinafter, the present invention will be described in detail.

Transition metal composite hydroxide of the present invention have the general formula _{Ni x Co y Mn z (OH} ) 2 + α (0.3 ≦ x ≦ 0.7,0.1 ≦ y ≦ 0.4, 0.1 ≦ A nickel-cobalt-manganese composite hydroxide represented by z ≦ 0.5, x + y + z = 1, 0 ≦ α ≦ 0.5), which has an average particle size of 3 to 7 μm and is an index showing the spread of the particle size distribution. [(D90-D10) / D50] is 0.55 or less, and the particle size distribution is narrow and monodisperse.
The present invention has been completed based on the above findings.
Hereinafter, the method for producing a transition metal composite hydroxide according to the present invention will be described in more detail.

(First step: Nucleation step)
First, a nickel salt, a cobalt salt, and a manganese salt (sulfates are preferably sulfates) are dissolved in water at a predetermined ratio as easily water-soluble transition metal salts to prepare a stock solution of a mixed aqueous solution of nickel, cobalt, and manganese.
After charging the stock solution into a crystallization reaction tank with a predetermined amount of pure water and an aqueous solution of sodium hydroxide as a pH adjuster in an amount required for neutralization calculated from the amount of the stock solution used for nucleation, An aqueous solution containing an ammonium ion feeder such as aqueous ammonia is added to a predetermined concentration, and the mixture is stirred and mixed to prepare a reaction solution having a predetermined pH.

By the way, the amount of the pH adjuster required for neutralization is calculated and obtained as follows.
First, the amount of substance of each transition metal ion contained in the compound solution of the transition metal supplied in the nucleation step is X (M ₁ ), X (M ₂ ), X (M ₃ ), ... Let X (M _K ) (k = 1, 2, ... N).
Next, the valences of the transition metal ions when they become transition metal hydroxides are Z (M ₁ ), Z (M ₂ ), Z (M ₃ ), ... Z (M _K ), respectively. To do.
The amount F of the pH adjuster to be obtained is calculated by the following formula (1). That is, the amount of substance corresponding to F is the required amount of alkali metal hydroxide.

Next, nucleation of the transition metal composite hydroxide is generated in the reaction solution to form a post-nucleation solution. At that time, without supplying the pH adjuster aqueous sodium hydroxide solution, only the undiluted solution and aqueous ammonia are quantitatively and continuously supplied into the crystallization reaction tank until the pH value reaches the set pH value in the particle growth step of the next step. Then, the aqueous sodium hydroxide solution is supplied from the time when the pH is reached, the pH is maintained at a predetermined pH, and the process proceeds to the particle growth step.

Here, the pH in the reaction vessel becomes 12.0 or more as the pH value measured based on the liquid temperature of 25 ° C. in the initial state of the reaction, nucleation occurs until the undiluted solution is consumed in the neutralization reaction, and then nucleation occurs. The pH begins to drop, the pH value of the particle growth step is reached, and the particle growth step is started. That is, there is a continuous transition from the nucleation process to the particle growth process.

Further, the concentration of ammonia in the liquid in the reaction vessel is maintained at a constant value within the range of 3 to 25 g / L.
Unless the ammonia concentration is above a certain level, the solubility of metal ions cannot be kept constant, and gel-like nuclei are generated. However, at a concentration of 25 g / L or more, the solubility increases too much, the amount of metal ions remaining in the solution increases, and the composition shifts.

It is desirable to set the temperature in the reaction vessel to 35 ° C or higher and 60 ° C or lower.
If the temperature is lower than 35 ° C, the temperature is too low to obtain sufficient solubility of the supplied metal ions, and if the temperature exceeds 60 ° C, the volatilization of ammonia is promoted, resulting in a shortage of ammonia for complex formation, and the solubility of the metal ions. Decreases.

It is desirable to control the oxygen concentration in the reaction vessel space to an air atmosphere of 18% or more by blowing air or the like, and to carry out the crystallization reaction at a dissolved oxygen concentration of 4 mg / L or more in the reaction vessel solution.
The pH value and control time of this first step can be arbitrarily set according to the average particle size of the target composite hydroxide.

(Second step)
The main feature of this step is that the inside of the reaction vessel is controlled to 10.5 to 12.0 as the pH value measured based on the liquid temperature of 25 ° C. as the particle growth step after the first step. By setting this pH value during nucleation, the pH will drop when the NaOH required for nucleation is consumed in the first step, so new nuclei can be obtained by continuously supplying undiluted solution and ammonia water. It is possible to shift to the particle growth process while suppressing the formation.

When the pH value is higher than 12.0, nucleation occurs and the particles do not become uniform.
Further, if the pH value is less than 10.5, the amount of S (sulfur) remaining in the particles when the metal sulfate is used as a raw material increases, which is not desirable.
When changing the pH value, what is normally done with sulfuric acid is performed by continuing to supply the undiluted solution, and the steps from the first step to the second step are continuously performed.

In addition, after growing arbitrarily in an air atmosphere for about 0 to 30 minutes at the beginning of the second step according to the desired characteristics of the hydroxide particles, the growth reaction is continued by switching to a nitrogen atmosphere. Since it is necessary to stop the feeding of the undiluted solution when switching the atmosphere, the piping and the tip nozzle are washed with water by passing pure water to prevent nozzle clogging.

When a predetermined amount of undiluted solution is finally passed to complete the growth reaction, pure water is passed to wash the pipe and the tip nozzle with water to prevent nozzle clogging.

Hereinafter, the present invention will be described in detail with reference to Examples.

(Crystalization process)
-First step First, put up to 140 liters of water in the reaction tank (600 liters), and while stirring at 260 rpm using a turbine-type stirring blade, set the temperature control to the temperature rise side and inside the tank. The temperature was set to 40 ° C. and controlled. In addition, air is blown at 20 to 40 L / min, a predetermined amount of 25% ammonia water is added while maintaining the air atmosphere, and the pH of the liquid is measured as a pH value of 12.6 based on the liquid temperature of 25 ° C. The concentration of ammonia in the liquid was adjusted to 10 g / L.

Here, 2 liters of a 2 mol / L aqueous solution (hereinafter referred to as a stock solution) obtained by dissolving nickel sulfate, cobalt sulfate, manganese sulfate (Ni: Co: Mn = 38: 32: 30 in molar ratio of metal elements) in water. Is used for nucleation, and the required amount obtained by calculating the 25% sodium hydroxide aqueous solution required for neutralization is added and mixed with 1.28 liters to carry out the nucleation step to obtain a post-nuclear solution. It was.

-Second step Add the stock solution and 25% aqueous ammonia to the post-nucleation liquid obtained in the first step at a constant addition rate, and the pH is 11.6 (pH value measured based on the liquid temperature of 25 ° C.). The control pH is set so as to reach (particle growth pH), and when the pH reaches 11.6, NaOH is supplied, and while the pH value is controlled to 11.6, 22 liters of undiluted solution is passed through to perform nucleation. did.

Then, in order to wash the stock solution remaining in the pipe, about 5 liters of pure water was passed through the pipe, and then the supply of NaOH and ammonia was stopped. There was no change in the temperature inside the tank on the way, and it was kept at 40 ° C.
Then, after flowing nitrogen gas to reduce the oxygen concentration in the reaction tank space to 1% or less and the dissolved oxygen concentration in the reaction tank solution to 0.5 mg / L or less, the supply of the stock solution, ammonia, and NaOH was restarted. In order to wash the undiluted solution remaining in the pipe after passing 270 liters of undiluted solution for about 4 hours with the pH value controlled to 11.6, about 5 liters of pure water was passed through and then ammonia. The supply was stopped, and the pH value was further increased by 1.2 to 12.8, and almost all of Ni contained in the slurry solution was precipitated. The resulting product was washed with water, filtered and dried.

By the method described above, a composite hydroxide represented by Ni _0.38 Co _0.32 Mn _0.30 (OH) _{2 + α} (0 ≦ α ≦ 0.5) was obtained.
The average particle size of the obtained composite hydroxide was 5.2 μm, and the tap density was 1.22 g / cc.

(Comparative Example 1)
After performing the nucleation step of the first step in the same manner as in Example 1, about 1 liter of pure water was passed to extrude the liquid in the undiluted solution pipe. After that, as a result of adding 64% sulfuric acid in order to adjust the pH to 11.6 controlled in the particle growth step of the second step, the pH was lowered to 11.4 by overshoot and the temperature in the tank was raised by about 5 ° C. Crystallization was restarted from there, and although it decreased by about 2 ° C while passing 20 liters of the undiluted solution, it did not decrease to the set temperature of 40 ° C, and apparently the controlled pH was constant but the actual pH fluctuated by about 0.1. .. After the substitution with a nitrogen atmosphere, the temperature was lowered to the set temperature, crystallization was restarted, and a hydroxide was obtained by the same operation as in Example 1.
The average particle size of the obtained hydroxide was 5.6 μm, and the tap density was 1.26 g / cc.

(Comparative Example 2)
As a result of adding 64% sulfuric acid in order to adjust the pH to be controlled in the particle growth step of the second step in the same manner as in Comparative Example 1, the temperature in the tank increased by about 5 ° C. Therefore, in order to lower the temperature inside the tank, the temperature control control of the reaction tank was switched to the cooling side, and as a result of passing water through the jacket until the set temperature was reached, the temperature was lowered by about 3 ° C. from the set temperature due to overshoot. The temperature control was switched to the temperature rising side again, and the temperature was adjusted while taking the overshoot into consideration, and it took about 20 minutes to reach the set temperature of 40 ° C. If the inside of the undiluted solution pipe was not cleaned, it would cause the nozzle to become clogged. Crystallization was resumed from there, and 20 liters of the undiluted solution was passed. Then, after substitution with a nitrogen atmosphere, crystallization was restarted, and a hydroxide was obtained by the same operation as in Example 1.
The average particle size of the obtained hydroxide was 5.3 μm, and the tap density was 1.20 g / cc.

Claims (5)

A method for producing a transition metal composite hydroxide used as a precursor of a positive electrode active material for a lithium ion secondary battery.
By adding a pH adjuster, a compound solution of a transition metal and a compound solution forming a complex ion with the transition metal are prepared while maintaining the pH at a liquid temperature of 25 ° C. at a constant value of 12.0 or more and 14.0 or less. By continuously supplying and mixing in the reaction vessel to form a reaction solution, a post-nuclear solution is formed in which fine transition metal composite hydroxide particles are used as nuclei in the reaction solution. Nuclear generation process and
The post-nuclear solution forms a compound solution of the transition metal and a complex ion with the transition metal while maintaining the pH at a liquid temperature of 25 ° C. at a constant value in the range of 9.0 or more and 12.0 or less. Neutralization crystallization including at least a particle growth step of continuously supplying a compound solution to the post-nuclear liquid to grow particles formed by precipitating a composite hydroxide of the transition metal around the nucleus. And
The amount of each transition metal ion contained in the compound solution of the transition metal supplied in the nucleation step is X (M ₁ ), X (M ₂ ), X (M ₃ ), ..., X ( M _K ) (k = 1, 2, ... N), and the valences when the transition metal ion becomes a transition metal hydroxide are Z (M ₁ ), Z (M ₂ ), Z (M). ₃ ), ... When Z (M _K ) is set, X (M ₁ ) x Z (M ₁ ) + X (M ₂ ) x Z (M ₂ ) + X (M ₃ ) x Z (M ₃ ) + ... An alkali metal hydroxide having a substance amount corresponding to X (M _K ) × Z (M _K ) (K = 1, 2, ... N) is mixed with the transition metal compound solution and the transition metal. When a compound solution that forms ions is continuously supplied and mixed to form a reaction solution, the pH adjuster is previously charged into the reaction vessel.
The pH of the post-nuclear liquid is lowered by continuous supply and mixing of the transition metal compound solution and the compound solution forming a complex ion with the transition metal, and the pH of the post-nuclear liquid is adjusted in the particle growth step. When the constant value to be maintained is reached, the supply of the alkali metal aqueous solution of the pH adjuster is started, and the pH is kept constant in the range of 9.0 or more and 12.0 or less until the end of the nuclear growth step thereafter. A method for producing a transition metal composite hydroxide used as a precursor of a positive electrode active material for a lithium ion secondary battery, which is characterized by being maintained. The transition metal composite hydroxide according to claim 1, wherein the transition metal compound is any one of a transition metal sulfate, a transition metal chloride, and a transition metal nitrate, or a mixture of at least two or more kinds. Manufacturing method. The method for producing a transition metal composite hydroxide according to claim 1 or 2, wherein the compound solution forming a complex ion with the transition metal is aqueous ammonia. Claims 1 to 3 in which the transition metal composite hydroxide has an average particle size of 3 to 7 μm and [(D90-D10) / D50], which is an index indicating the spread of the particle size distribution, is 0.55 or less. The method for producing a transition metal composite hydroxide according to any one of the above items. The transition metal composite hydroxide has an atomic weight ratio of Ni, Co, Mn, and the additive element M. Ni: Co: Mn: M is 1-x−y−z: x: y: z (0.1 ≦ x ≦ 0). .4, 0.1 ≤ y ≤ 0.5, 0 ≤ z ≤ 0.1, 0.3 ≤ 1-x-y-z ≤ 0.7, M is Al, Mg, Ca, Ti, V, Cr , Zr, Nb, Mo, Hf , Ta, represented by the general formula 1 or more selected from _{W) Ni x Co y Mn z} (OH) 2 + α (0.3 ≦ x ≦ 0.7,0 .1 ≦ y ≦ 0.4, 0.1 ≦ z ≦ 0.5, x + y + z = 1, 0 ≦ α ≦ 0.5), which is a nickel-cobalt-manganese composite hydroxide. The method for producing a transition metal composite hydroxide according to any one of Items to 4.