JP5614334B2 - Nickel-cobalt composite hydroxide, method for producing the same, and positive electrode active material for non-aqueous electrolyte secondary battery obtained using the composite hydroxide - Google Patents

Description

  The present invention relates to a nickel-cobalt composite hydroxide, a method for producing the same, and a positive electrode active material for a non-aqueous electrolyte secondary battery obtained by using the composite hydroxide, and more specifically, a positive electrode for a non-aqueous electrolyte secondary battery. The present invention relates to a nickel-cobalt composite hydroxide which is used as a precursor of a lithium nickel composite oxide suitable as an active material and has a large particle size and high particle size uniformity and a method for producing the same.

In recent years, with the advancement of electronic technology, electronic devices are rapidly becoming smaller and lighter. In particular, as portable electronic devices such as mobile phones and notebook PCs have become popular and highly functional, the development of small, lightweight batteries with high energy density has become strong as portable power sources used in these devices. It is desired.
Non-aqueous electrolyte secondary batteries are already used as power sources for portable electronic devices because they are small and have high energy. In addition to such applications, research and development aimed at using non-aqueous electrolyte secondary batteries as large-scale power sources such as hybrid vehicles and electric vehicles are being promoted.

As a positive electrode material applicable as a positive electrode active material for a non-aqueous electrolyte secondary battery, particularly a lithium ion secondary battery, lithium cobalt composite oxide (LiCoO ₂ ), which is relatively easy to synthesize, and manganese, which is cheaper than cobalt, are used. Examples thereof include lithium manganese composite oxide (LiMn ₂ O ₄ ) and lithium nickel composite oxide (LiNiO ₂ ) using nickel.
The lithium-nickel composite oxide has the advantage that it has a higher capacity than the current mainstream lithium-cobalt composite oxide, and that nickel as a raw material is cheaper and more stable than cobalt. Therefore, it is expected as a next-generation positive electrode material, and lithium nickel composite oxide is actively researched and developed.
Further, in recent years, as the added value of portable devices has increased, the performance required of batteries has been increasing. As a result, batteries with higher energy density can be obtained by packing as much positive electrode active material as possible in a limited volume. It has come to be required.

Increasing the particle size of the positive electrode active material is one effective method for increasing the packing density when molded as a battery electrode. Like lithium-cobalt composite oxide, one that can increase the particle size (primary particles) by synthesizing at a high firing temperature is easy to increase the packing density. Is as low as 850 ° C. or lower, the primary particles cannot be increased and the packing density is difficult to increase.
Therefore, the packing density is maintained by using an active material in which a large number of fine primary particles are aggregated to form substantially spherical secondary particles (see, for example, Patent Document 1). On the other hand, the powder characteristics of the lithium nickel composite oxide are basically greatly influenced by the powder characteristics of the nickel compound used as the raw material. Therefore, controlling the powder characteristics of the raw material nickel compound, that is, increasing the particle size is important for improving the packing density of the lithium nickel composite oxide.
Further, Patent Document 2, the chemical _{formula: Ni b M1 c M2 d (} О) x (OH) y ( where in the formula, 1 M1 is selected from the group consisting of Fe, Co, Mg, Zn and Cu M2 is one or more selected from the group consisting of Mn, Al, B, Ca and Cr, b ≦ 0.8, c ≦ 0.5, d ≦ 0.5, 0.1 ≦ x ≦ 0.8, 1.2 ≦ y ≦ 1.9, x + y = 2), the average particle diameter is 2 to 30 μm, and (D90−D10) / D50 (where D is a powder) And a compound having a normalized particle size distribution width of less than 1.2 is disclosed, and has a high tap density and can be used for the synthesis of a high-performance lithium mixed metal oxide. .
However, the disclosed production method involves partial oxidation of the compound, and the process of coprecipitation of the compound is not significantly different from the prior art. Therefore, the particle size distribution of the obtained compound is not necessarily narrow.

Patent Document 3 has a particle size distribution composed of spherical particles and having an average particle size of 0.1 to 30 μm, and particles having 80% by weight or more present at 0.7 to 1.3 times the average particle size. Nickel hydroxide powder is disclosed.
However, although the particle size distribution of the obtained nickel hydroxide is relatively narrow, its production method is to dry the gelled emulsion, and the resulting nickel hydroxide crystals are undeveloped and have low crystallinity. The precursor of the lithium nickel composite oxide is not necessarily suitable.

On the other hand, in order to suppress the generation of fine particles and improve the packing density, attempts have been made to examine the production conditions in the neutralization crystallization method. For example, Patent Document 4 discloses a method for producing spherical high-density nickel hydroxide by continuously supplying a nickel salt aqueous solution containing a nickel-ammonium complex and an alkaline aqueous solution to a reaction vessel and reacting them while stirring. It is disclosed that the stirring power of the reaction tank is 0.1 to 0.5 KW per 1 m ³ and that the shear force is reduced and the stirring blade is used so that the reaction liquid circulates uniformly throughout the tank. An axial-flow type inclined paddle two-stage blade as a stirring blade is illustrated.
However, the average particle diameter of the obtained nickel hydroxide is about 12 μm at the maximum, and is not applicable to the production of large particle diameter nickel hydroxide.
As described above, in the conventional synthesis method, it is difficult to obtain suitable nickel hydroxide as a precursor of the lithium nickel composite oxide having an average particle size of 15 μm or more, and the nonaqueous electrolyte secondary It has been difficult to realize further high filling properties of the positive electrode active material for batteries.

JP 2000-30893 A JP 2009-515799 A JP 2006-151895 A JP 2003-2665 A

In view of the problems of the prior art, an object of the present invention is to provide a method for producing a positive electrode active material for a non-aqueous electrolyte secondary battery capable of improving the packing density and further increasing the energy density of the battery. It is in.
Furthermore, another object of the present invention is to provide a highly crystalline and substantially spherical nickel-cobalt composite hydroxide that is suitable as a positive electrode active material precursor, without sacrificing mass productivity. Is to provide a simple manufacturing method.

  In order to achieve the above object, the present inventors have conducted extensive studies on nickel cobalt composite hydroxide used as a precursor of a positive electrode active material for a non-aqueous electrolyte secondary battery. In the neutralization crystallization method for obtaining a product, (i) the reaction solution in the neutralization crystallization is stirred under specific conditions, and (ii) the supply amount of an aqueous solution containing nickel salt and cobalt salt as a raw material is reacted. By controlling to a specific ratio with respect to the solution, it has been found that a nickel-cobalt composite hydroxide suitable as a precursor of the positive electrode active material having a large particle size, a large crystallinity, and a substantially spherical shape can be obtained. It came to complete.

That is, according to the first aspect of the present invention, the general _{formula: Ni 1-x-y Co} x M y (OH) 2 (0.05 ≦ x ≦ 0.95,0 ≦ y ≦ 0.15, x + y ≦ 0.95, M is an additive element, and is one or more elements selected from Mg, Al, Ca, Ti, V, Cr, Mn, Zr, Nb, Mo, or W. A method for producing a nickel cobalt composite hydroxide comprising:
While stirring the reaction solution, while supplying a mixed aqueous solution (a) containing a nickel salt and a cobalt salt and an aqueous solution (b) containing an ammonium ion supplier, a caustic aqueous solution (c) is supplied and reacted. When obtaining the nickel cobalt composite hydroxide by solid-liquid separation of the crystallized nickel cobalt composite hydroxide particles, washing with water and drying,
While stirring the reaction solution using a stirring blade having an inclination of 15 to 45 degrees with respect to the horizontal plane, the ratio of the supply amount to the reaction solution amount per supply port of the mixed aqueous solution (a) is 0.04 vol% / min. There is provided a method for producing a nickel-cobalt composite hydroxide characterized by the following.

Further, according to the second invention of the present invention, in the first invention, when the reaction solution is stirred using the stirring blade, the blade peripheral speed obtained by the following formula 1 is in the range of 1 to 5 m / second. A method for producing a nickel-cobalt composite hydroxide is provided.
Formula 1: Blade peripheral speed (m / sec) = π × blade diameter (m) × rotational speed (rpm) ÷ 60
Furthermore, according to the third invention of the present invention, in the first or second invention, the mixed aqueous solution (a) and the caustic alkaline aqueous solution (c) are supplied from a supply port provided in the reaction solution. A method for producing a nickel cobalt composite hydroxide is provided.

According to a fourth invention of the present invention, in any one of the first to third inventions, the mixed aqueous solution (a) is supplied from a supply port branched into three or more locations. A method for producing a cobalt composite hydroxide is provided.
Furthermore, according to the fifth aspect of the present invention, in any one of the first to fourth aspects, the pH of the reaction solution is 11.0 to 13.0, the temperature is 20 to 70 ° C., and the ammonium ion concentration is A method for producing a nickel-cobalt composite hydroxide is provided, which is held in a range of 5 to 20 g / L.

According to a sixth invention of the present invention, in any one of the first to fifth inventions, the mixed aqueous solution (a) and the aqueous solution (b) containing an ammonium ion supplier are continuously supplied, respectively, and a reaction vessel The reaction solution containing nickel cobalt composite hydroxide particles is continuously overflowed to recover the nickel cobalt composite hydroxide particles, thereby providing a method for producing nickel cobalt composite hydroxide.
According to a seventh invention of the present invention, in any one of the first to fifth inventions, the mixed aqueous solution (a) and the aqueous solution (b) containing an ammonium ion supplier are respectively supplied continuously. The grown nickel-cobalt composite hydroxide particles are allowed to settle by setting the upward flow in the vicinity of the overflow in the reaction tank to 50 mm / second or less, and the nickel-cobalt composite hydroxide particles are recovered from the bottom of the reaction tank. A method for producing a nickel cobalt composite hydroxide is provided.
Furthermore, according to an eighth aspect of the present invention, there is provided the method for producing a nickel-cobalt composite hydroxide according to the seventh aspect, wherein the blade peripheral speed is 1 to 3 m / sec.

According to a ninth aspect of the present invention, in any one of the first to eighth aspects, the nickel cobalt composite hydroxide particles are coated with a hydroxide of the additive element M. A method for producing a cobalt composite hydroxide is provided.
According to a tenth aspect of the present invention, in any one of the first to ninth aspects, the nickel salt and the cobalt salt are at least one selected from sulfate, nitrate or chloride. A method for producing a nickel cobalt composite hydroxide is provided.
Furthermore, according to an eleventh aspect of the present invention, in any one of the first to tenth aspects, the ammonium ion supplier is at least one selected from ammonia, ammonium sulfate, or ammonium chloride. A method for producing a nickel cobalt composite hydroxide is provided.

On the other hand, according to the twelfth aspect of the present invention, obtained from the manufacturing method according to any one of aspects 1 to 11, the general _{formula: Ni 1-x-y Co} x M y (OH) 2 (0. 05 ≦ x ≦ 0.95, 0 ≦ y ≦ 0.15, x + y ≦ 0.95, M is an additive element, and Mg, Al, Ca, Ti, V, Cr, Mn, Zr, Nb, Mo or at least one element selected from W. consists particles represented by), Ri average particle size 15~50μm der particles are substantially spherical, an indicator of the particle size distribution width [(d90-d10) / average particle size] is 1.2 or less, nickel-cobalt composite hydroxide half width of (101) plane obtained by X-ray diffraction and wherein 0.3 to 0.7 ° der Rukoto Is provided.
Furthermore, according to a thirteenth aspect of the present invention, there is provided the nickel cobalt composite hydroxide according to the twelfth aspect, wherein the average particle size is 25 to 45 μm .

Moreover, according to the fourteenth aspect of the present invention, the nickel cobalt composite hydroxide according to the twelfth or thirteenth aspect of the present invention is obtained by mixing and baking a lithium compound, and has the general formula: LiNi _{1-x- y} Co _x M _y O ₂ (0.05 ≦ x ≦ 0.95, 0 ≦ y ≦ 0.15, x + y ≦ 0.95, M is an additive element, and Mg, Al, Ca, Ti, V And at least one element selected from Cr, Mn, Zr, Nb, Mo or W.), and the particles are substantially spherical and have an average particle size of 15 to Ri 50μm der, size indication of the distribution width [(d90-d10) / average particle size] is 1.2 or less, the half width of which is (003) plane measured by X-ray diffraction is 0.05 to 0. non-aqueous electrolyte secondary battery positive electrode according to claim 085 ° der Rukoto Material is provided.
Furthermore, according to a fifteenth aspect of the present invention, there is provided the positive electrode active material for a non-aqueous electrolyte secondary battery according to the fourteenth aspect, wherein the average particle size is 25 to 45 μm .

According to the present invention, it is possible to provide a nickel-cobalt composite hydroxide having a large particle size, a high density and a substantially spherical shape, which is suitable as a precursor of a positive electrode active material for a non-aqueous electrolyte secondary battery. Moreover, the manufacturing method is excellent without sacrificing mass productivity.
Furthermore, the positive electrode active material for a non-aqueous electrolyte secondary battery according to the present invention has a high packing density and can further increase the energy density of the battery, and has an extremely high industrial value.

1. Method for producing a nickel-cobalt composite hydroxide of the production method the present invention a nickel-cobalt composite hydroxide is represented by the general _{formula: Ni 1-x-y Co} x M y (OH) 2 (0.05 ≦ x ≦ 0.95 , 0 ≦ y ≦ 0.15, x + y ≦ 0.95, M is an additive element, and is selected from Mg, Al, Ca, Ti, V, Cr, Mn, Zr, Nb, Mo or W A nickel-cobalt composite hydroxide represented by the following formula:
While stirring the reaction solution, while supplying a mixed aqueous solution (a) containing a nickel salt and a cobalt salt and an aqueous solution (b) containing an ammonium ion supplier, a caustic aqueous solution (c) is supplied and reacted. When obtaining the nickel cobalt composite hydroxide by solid-liquid separation of the crystallized nickel cobalt composite hydroxide particles, washing with water and drying,
While stirring the reaction solution using a stirring blade having an inclination of 45 degrees or less with respect to the horizontal plane, the ratio of the supply amount to the reaction solution amount per supply port of the mixed aqueous solution (a) is 0.04 vol% / min or less. It is characterized by.

  Here, (i) the angle of the stirring blade that stirs the reaction solution and (ii) the ratio of the supply amount of the mixed aqueous solution (a) to the amount of the reaction solution has a large particle size, high crystallinity, and a substantially spherical nickel-cobalt composite It has important significance for obtaining hydroxide.

In order to obtain particles having a large particle size, it is necessary to suppress new nucleation in the reaction system.
That is, in the production of metal hydroxide particles by neutralization crystallization of a metal salt, as a monomer, the supplied metal salt is neutralized to produce nuclei, and subsequently the nuclei grow by the supplied monomer. By doing so, metal hydroxide particles are obtained. However, if diffusion of the mixed aqueous solution (a), which is a monomer supply source, in the reaction solution is insufficient, a region in which the concentration of nickel and cobalt is extremely high is instantaneously formed. Cause. Further, if the diffusion of the caustic aqueous solution (c) is insufficient, a region having an extremely high pH is instantaneously formed and new nucleation is induced. When nuclei are generated, the subsequent growth of particles becomes extremely slow, and it becomes difficult to constantly obtain particles having a large particle size.

  Therefore, in order to grow the generated nucleus and obtain a substantially spherical nickel-cobalt composite hydroxide having a large particle size and excellent crystallinity, a mixed aqueous solution (a) or a caustic alkaline aqueous solution (c) supplied to the reaction solution is used. ) Needs to be diffused as soon as possible.

  In the method for producing the nickel-cobalt composite hydroxide of the present invention, (i) by stirring the reaction solution using a stirring blade having an inclination of 45 degrees or less with respect to the horizontal plane, the discharge flow in the vertical direction by stirring is reduced. The diffusion rate can be increased to increase the diffusion, and in the supply part of the mixed aqueous solution (a) and the caustic aqueous solution (c), the region where the concentration of the metal salt contained in the mixed aqueous solution (a) is extremely high and high Generation of a pH region can be suppressed.

On the other hand, when the inclination of the stirring blade is larger than 45 degrees, the stirring force itself becomes strong, but the shearing force of the stirring blade increases and the flow velocity in the inner wall surface direction (horizontal direction) increases. In the process of growing the particles, in addition to the growth of single particles, particularly in the case of large-sized particles, a plurality of particles are aggregated, and the aggregate becomes one particle and grows into large-sized particles. In the case of this growth process, when a large force is applied to the aggregated particles, the aggregation is loosened and it becomes difficult to grow into particles having a large particle size.
Therefore, when the inclination of the stirring blade is larger than 45 degrees, the aggregated particles are destroyed by the shearing force or the collision of the generated particles with the inner wall surface of the reaction tank, so that the nickel cobalt hydroxide particles do not grow.

From the viewpoint of alleviating the impact applied to the nickel cobalt hydroxide particles, the inclination angle of the stirring blade is preferably small. On the other hand, sufficient stirring force is required for the above reason.
Therefore, the inclination angle of the stirring blade is preferably 15 degrees or more, and more preferably 30 degrees or more. On the other hand, when the inclination angle is less than 15 degrees, a sufficient discharge flow cannot be obtained and diffusion may be insufficient.

Depending on the rotation direction of the stirring blade, the discharge flow is either in the pushing-down direction or the pulling-up direction. In either case, the discharge flow may be in any direction as long as sufficient stirring force is obtained.
Further, when the blade peripheral speed is increased, the shear force at the outer peripheral portion of the stirring blade where the force is most applied to the particles is increased, so that the particle growth is hindered.
Therefore, it is preferable to set the blade peripheral speed obtained by the following formula 1 in the range of 1 to 5 m / sec.
Formula 1: Blade peripheral speed (m / sec) = π × blade diameter (m) × rotational speed (rpm) ÷ 60

  By setting the blade peripheral speed to 1 to 5 m / second, sufficient diffusion of the mixed solution in the reaction solution can be obtained without destroying the aggregation of particles. On the other hand, when the blade peripheral speed is less than 1 m / s, the mixed solution may not be sufficiently diffused. Further, when the blade peripheral speed is higher than 5 m / sec, the shearing force increases as described above, and thus particle growth may be hindered.

(Ii) Regarding the ratio of the supply amount of the mixed aqueous solution (a) to the reaction solution amount, if the supply rate of the mixed aqueous solution (a) is too high, even if a sufficient discharge flow is obtained, Since the relative diffusion capacity is lowered and the dilution rate is lowered, it is difficult to sufficiently suppress the high concentration region and the high pH region of the metal salt.
Therefore, the supply rate of the mixed aqueous solution (a), that is, the ratio of the supply amount with respect to the reaction solution amount per supply port of the mixed aqueous solution (a) is 0.04% / min or less in volume ratio. It is possible to ensure a dilution rate. On the other hand, if the supply rate is higher than this, a sufficient dilution rate cannot be secured and nucleation is induced. In consideration of productivity, the lower limit of the ratio of the supply amount to the reaction solution amount is preferably about 0.01% / min in volume ratio.

  When the ratio of the supply amount is limited, the supply amount is limited and the growth rate of the particles is also limited. Therefore, in order to further increase productivity, the mixed aqueous solution (a It is effective to secure the supply amount of the entire reaction system while controlling the ratio of the supply amount. In this case, it is preferable to supply the mixed aqueous solution (a) from a supply port branched into three or more locations. Thereby, even in the case of the same productivity, it is possible to further increase the diffusion rate and obtain particles having a sufficient particle size. On the other hand, if there are two or less supply ports, sufficient productivity may not be obtained.

Further, in order to increase the diffusion rate of the supplied mixed aqueous solution (a) or caustic alkaline aqueous solution (c) in the reaction solution, it is effective to supply the aqueous solution from a supply port provided in the reaction solution. Yes, it is preferable. When the mixed aqueous solution (a) or the caustic aqueous solution (c) is dropped from the upper part of the liquid surface, the liquid droplets instantaneously form the extreme high concentration region or high pH region, which causes nucleation. There is.
By supplying the aqueous solutions (a) and (c) from a supply port provided in the reaction solution, formation of the region by droplets can be prevented and new nucleation can be suppressed.

Hereafter, the manufacturing method of the nickel cobalt composite hydroxide of this invention is demonstrated in detail.
In the production method of the present invention, the mixed aqueous solution (a) containing a nickel salt and a cobalt salt is a supply source of nickel and cobalt. Moreover, the aqueous solution (b) containing an ammonium ion supply body plays the role which controls the particle size and shape of the nickel cobalt hydroxide particle | grains to produce | generate as a complex formation agent. Moreover, since ammonium ions are not taken into the produced nickel cobalt hydroxide particles, they are a preferable complexing agent for obtaining high-purity nickel cobalt hydroxide particles. The aqueous caustic solution (c) is a pH adjuster for the neutralization reaction.
The concentration of metal salt such as nickel and cobalt in the mixed aqueous solution (a) is not particularly limited, but is preferably 0.5 to 2.2 mol / L. If it is less than 0.5 mol / L, the amount of liquid in each step becomes too large, and the productivity is lowered, which is not preferable. On the other hand, when it exceeds 2.2 mol / L, when the air temperature is lowered, the metal salt may recrystallize in the mixed aqueous solution (a) and clog piping and the like.

  In the said manufacturing method, it is preferable to hold | maintain pH of a reaction solution at 11.0-13.0, and it is more preferable to hold | maintain at 11.5-12.5. When the pH of the reaction solution is lower than 11, the initial nucleation in the reaction system is suppressed, the number of particles becomes too small, and the monomer consumption due to particle growth becomes too small relative to the monomer supply amount. , Most of the supplied monomer is consumed for nucleation. As a result, a nuclear abnormality called a Cycling phenomenon occurs, the particle size of the particles in the tank hardly grows, and there is a possibility that particles having a large particle size cannot be obtained. On the other hand, when the pH exceeds 13, many nuclei are regularly generated, the number of particles in the system increases, and the particle size may not grow greatly.

  Moreover, it is preferable to hold | maintain the temperature of a reaction solution at 20-70 degreeC, and it is more preferable to hold | maintain at 40-70 degreeC. When the temperature of the reaction solution is less than 20 ° C., the solubility of nickel is low, so that fine particles are likely to be generated. Moreover, in order to eliminate the influence by seasonal fluctuation, it is necessary to introduce a chiller or the like, which increases the equipment cost, which is not industrially preferable. On the other hand, when it exceeds 70 ° C., the volatilization of ammonia becomes intense, and it may be difficult to control the ammonium ion concentration in the reaction system.

  Furthermore, the ammonium ion concentration in the reaction solution is preferably maintained at 5 to 20 g / L, more preferably 10 to 15 g / L. When the ammonium ion concentration is less than 5 g / L, since the solubility of nickel is low, fine particles are likely to be generated, and the particle size may be reduced. In addition, when the particles grow, the monomer is not supplied to the inside of the particles and a precipitation reaction occurs on the surface of the particles, so that only low-density hydroxide particles can be obtained. There is a possibility that the energy density per volume is lowered due to low density. On the other hand, when the ammonium ion concentration exceeds 20 g / L, the concentration of nickel remaining in the liquid increases, leading to an increase in cost due to compositional deviation and increased nickel loss.

  The metal salt such as the nickel salt and cobalt salt is preferably at least one of sulfate, nitrate, or chloride, and more preferably sulfate without contamination by halogen. For example, cobalt sulfate and nickel sulfate are preferably used. Further, when adjusting the mixed aqueous solution (a), the metal salt matches the atomic ratio of the metal element in the target composite hydroxide in the atomic ratio of the metal ions present in the mixed aqueous solution. Adjusted.

  The aqueous solution (b) containing the ammonium ion supplier is not particularly limited, but is preferably aqueous ammonia, ammonium sulfate or ammonium chloride, and more preferably aqueous ammonia or ammonium sulfate free from halogen contamination. The concentration of the ammonium ion supplier is not particularly limited, and may be adjusted within a range in which the ammonium ion concentration in each step can be maintained.

  The caustic aqueous solution (c) is not particularly limited, and for example, an alkali metal hydroxide aqueous solution such as sodium hydroxide or potassium hydroxide can be used. In the case of an alkali metal hydroxide, it is preferable to add it as an aqueous solution to the reaction system in each step because of easy control of the pH value.

  In the nickel-cobalt composite hydroxide of the present invention, one or more elements selected from Mg, Al, Ca, Ti, V, Cr, Mn, Zr, Nb, Mo or W are added as the additional element M. can do. M element can be added to the mixed aqueous solution (a) as a compound of M element. The M element compound is not particularly limited. For example, magnesium sulfate, calcium nitrate, barium nitrate, strontium nitrate, titanium sulfate, ammonium peroxotitanate, potassium titanium oxalate, vanadium sulfate, ammonium vanadate, Chromium sulfate, potassium chromate, zirconium sulfate, zirconium nitrate, niobium oxalate, ammonium molybdate, sodium tungstate, ammonium tungstate, and the like can be used.

When the M element compound is added to the mixed aqueous solution (a), the concentration and supply amount of the mixed aqueous solution (a) are maintained at the above-described conditions. Further, the amount of M element added is adjusted so that the atomic ratio of the metal ions present in the mixed aqueous solution (a) matches the atomic ratio of the metal elements in the target composite hydroxide.
On the other hand, it is not always necessary to add M element to the mixed aqueous solution (a) and coprecipitate with nickel cobalt composite hydroxide particles. For example, nickel and cobalt are coprecipitated to form nickel cobalt composite hydroxide particles. Then, a compound such as a hydroxide or oxide of M element may be deposited on the surface of the nickel cobalt composite hydroxide particles by a wet neutralization method. Furthermore, when adding several types of M element, you may obtain the target nickel cobalt composite hydroxide by combining the said addition method.

The above production method is not particularly limited, but the mixed aqueous solution (a) and the aqueous solution (b) containing an ammonium ion supplier are each quantitatively and continuously supplied to obtain a caustic aqueous solution (c ), While adjusting the amount added and supplying the reaction solution while maintaining the reaction solution at a predetermined pH, the reaction solution containing nickel-cobalt composite hydroxide particles is continuously added from the reaction vessel. It is preferable that the nickel cobalt composite hydroxide particles be recovered by overflowing to the above.
Therefore, the reaction vessel used in the above production method is not particularly limited, but it is preferable to use a vessel equipped with a stirrer, an overflow port, and temperature control means.

Further, in the production method of the present invention, as another aspect, the mixed aqueous solution (a) and the aqueous solution (b) containing an ammonium ion supplier are continuously supplied and the vicinity of the overflow in the reaction vessel is increased. The grown nickel cobalt composite hydroxide particles are allowed to settle at a flow of 50 mm / second or less, and the composite hydroxide particles can be recovered from the bottom of the reaction vessel.
By setting the upward flow in the vicinity of the overflow in the reaction tank to 50 mm / second or less, only the liquid component of the reaction solution is discharged by overflow, and the outflow of particles caused by the overflow to the outside of the system is sufficiently suppressed. Particles can be grown and the particles grown to a large particle size can settle to the bottom of the reaction vessel. By extracting particles that have grown and settled out of the reaction tank continuously or intermittently from the bottom of the reaction tank, particles having a large particle size can be recovered. The recovery from the bottom of the reaction tank is preferable because fine particles that are insufficiently grown are not recovered, and the large particle size in which the particles have grown is preferentially recovered.

The upward flow can be controlled by the inclination angle and blade peripheral speed of the stirring blade. As long as sufficient stirring force can be obtained, the angle of inclination may be reduced and the blade peripheral speed may be reduced. The blade peripheral speed is preferably 1 to 3 m / sec.
In the case of recovering the composite hydroxide particles from the bottom of the reaction tank, the same apparatus as in the case of recovering by the overflow can be used, but the particles from the bottom of the reaction tank such as having a discharge hole at the bottom of the reaction tank. An apparatus having a mechanism capable of facilitating recovery is preferable.

  As a precursor of a positive electrode active material for a non-aqueous electrolyte secondary battery free from complexation agents, halogens, etc., by the above manufacturing method, a large particle size, high crystallinity, and a substantially spherical nickel having a suitable composition A cobalt composite hydroxide is obtained.

2. Nickel-cobalt composite hydroxide of nickel-cobalt composite hydroxide present invention are those obtained by the above production method, the general _{formula: Ni 1-x-y Co} x M y (OH) 2 (0.05 ≦ x ≦ 0.95, 0 ≦ y ≦ 0.15, x + y ≦ 0.95, M is an additive element, Mg, Al, Ca, Ti, V, Cr, Mn, Zr, Nb, Mo or W 1 or more elements selected from the above, and the particles are substantially spherical and have an average particle size of 15 to 50 μm, more preferably 25 to 45 μm.

  In the above general formula, x indicating the ratio of nickel and cobalt is 0.05 to 0.95, preferably 0.1 to 0.9, and more preferably 0.1 to 0.3. That is, when x exceeds 0.95, since the ratio of Co is large, the raw material cost increases. On the other hand, when x is less than 0.05, the thermal stability and charge / discharge cycle characteristics of the positive electrode active material using the nickel-cobalt composite hydroxide of the present invention deteriorate.

  In the nickel-cobalt composite hydroxide, one kind selected from Mg, Al, Ca, Ti, V, Cr, Mn, Zr, Nb, Mo or W is used to further improve the thermal stability and output characteristics. M, which is the above additive element, can be added as 0.15 or less as y in the above general formula. When y exceeds 0.15, the amount of M replaced with nickel becomes too large, and the battery capacity of the obtained positive electrode active material decreases.

  The nickel-cobalt composite hydroxide of the present invention is substantially spherical and has an average particle size of 15 to 50 μm, more preferably 25 to 45 μm. Since the nickel-cobalt composite hydroxide is maintained up to the positive electrode active material for the non-aqueous electrolyte secondary battery, the nickel-cobalt composite hydroxide of the present invention can be obtained by making it approximately spherical and having an average particle size of 15 to 50 μm. The packing density of the positive electrode active material for a non-aqueous electrolyte secondary battery obtained by using it can be increased. Here, the term “substantially spherical” includes a true spherical shape having a fine unevenness on the surface, and an elliptical rotating body shape. However, in order to achieve a high packing density, it is preferable to approximate the spherical shape as much as possible.

Furthermore, the nickel cobalt composite hydroxide preferably has a particle size distribution width index [(d90−d10) / average particle size] of 1.2 or less, and more preferably 1.16 or less. Usually, when trying to obtain the above composite hydroxide having a large particle size, nucleation also occurs during particle growth to a large particle size, so that particles (fine particles) having a small particle size are mixed, and therefore 10 μm The width of the particle size distribution is wider than particles having a normal particle size of about. The composite hydroxide of the present invention has a distribution width equal to or greater than that of the composite hydroxide having an average particle size of less than 15 μm, even though the average particle size is 15 μm or more, more preferably 25 μm or more. It is narrow and has a good particle size distribution. When [(d90-d10) / average particle diameter] exceeds 1.2, the number of fine particles in the positive electrode active material obtained using the composite hydroxide may be excessive. The above [(d90-d10) / average particle size] is preferably as small as possible from the viewpoint of having a good particle size distribution, but the lower limit in the composite hydroxide of the present invention is about 0.5. It is.
Further, when fine particles are mixed, since d10 is relatively small, the ratio of d10 to the average particle diameter [d10 / average particle diameter] is small. Therefore, [d10 / average particle diameter] is preferably 0.4 or more, and more preferably 0.45 or more. When [d10 / average particle diameter] is less than 0.4, the fine particles in the positive electrode active material obtained by using the composite hydroxide may be excessive. [D10 / average particle diameter] is preferably as large as possible from the viewpoint of reduction in mixing of fine particles, but the upper limit of the composite hydroxide of the present invention is about 0.7.
As a result, the positive electrode active material for a non-aqueous electrolyte secondary battery obtained using the composite hydroxide can have a small amount of fine particles and a good particle size distribution, and can have good characteristics. .
In addition, in the index [(d90−d10) / average particle size] indicating the spread of the particle size distribution, d10 is the number of particles in each particle size accumulated from the smaller particle size side, and the accumulated volume is the total volume of all particles. Means a particle size of 10%. D90 means the particle diameter in which the number of particles is accumulated in the same manner and the accumulated volume is 90% of the total volume of all particles.
The method for obtaining the average particle diameter and d90 and d10 is not particularly limited, but can be obtained, for example, from the volume integrated value measured with a laser light diffraction / scattering particle size analyzer. When d50 is used as the average particle size, a particle size with an accumulated volume of 50% of the total particle volume may be used as in d90.

  Further, the complex hydroxide preferably has a half width of the (101) plane obtained by X-ray diffraction of 0.8 ° or less, and more preferably 0.3 to 0.7 °. Since the composite hydroxide is obtained by the particle growth, it has high crystallinity, and when the half width is in the above range, the crystallinity of the positive electrode active material obtained by firing in a normal temperature range is high. It will be good.

3. Cathode active material for non-aqueous electrolyte secondary battery The nickel-cobalt composite hydroxide is obtained by a known technique, and the atomic ratio (Li / Me) of the total (Me) of the lithium (Li) compound and the metal elements in the composite hydroxide. Is mixed with a lithium compound so as to be 0.95 to 1.10 and fired at 650 to 800 ° C., the positive electrode active material for a non-aqueous electrolyte secondary battery of the present invention can be obtained. The composite hydroxide may be mixed with a lithium compound after oxidative roasting at 300 to 800 ° C.
The positive electrode active material of the present invention has a substantially spherical shape and an average particle size of 15 to 50 μm, more preferably 25 to 45 μm in order to leave the composite hydroxide, and the general formula: LiNi _1-xy Co _x M _y O ₂ (0.05 ≦ x ≦ 0.95, 0 ≦ y ≦ 0.15, x + y ≦ 0.95, M is an additive element, and Mg, Al, Ca, Ti, V, Cr, Mn And at least one element selected from Zr, Nb, Mo, or W.), which has a high packing density and further increases the energy density of the battery. Therefore, it is suitable for a non-aqueous electrolyte secondary battery.

Furthermore, the positive electrode active material preferably has a particle size distribution width index [(d90-d10) / average particle size] of 1.2 or less, and more preferably 1.15 or less.
Since the fine particles contained in the composite hydroxide are sintered with the large particle size during firing, it is considered that the particle size distribution of the positive electrode active material tends to be improved compared to the composite hydroxide that is the raw material.
When [(d90-d10) / average particle diameter] exceeds 1.2, the fine particles in the positive electrode active material increase, and when the battery is constructed, the fine particles are selectively deteriorated, and cycle characteristics and the like are improved. May get worse. The above [(d90-d10) / average particle size] is preferably as small as possible from the viewpoint of having a good particle size distribution, but the lower limit in the positive electrode active material of the present invention is about 0.4. is there.

Similarly to the above composite hydroxide, when fine particles are mixed, [d10 / average particle diameter] becomes small. Therefore, [d10 / average particle diameter] is preferably 0.45 or more, and more preferably 0.5 or more. When [d10 / average particle diameter] is less than 0.45, the fine particles in the positive electrode active material increase, and the cycle characteristics and the like may deteriorate. [D10 / average particle diameter] is preferably as large as possible from the viewpoint of reduction in mixing of fine particles, but the upper limit of the positive electrode active material of the present invention is about 0.7.
By setting the particle size distribution in the above range, it is possible to further increase the packing density of the positive electrode active material for a non-aqueous electrolyte secondary battery and to prevent deterioration of battery characteristics due to mixing of fine particles.

  The positive electrode active material preferably has a (003) plane half-value width of 0.09 ° or less, more preferably 0.05 to 0.085 °, as determined by X-ray diffraction. When the half width is in the above range, the crystallinity of the positive electrode active material is improved, and a battery configured using the positive electrode active material has excellent characteristics such as charge / discharge capacity and thermal stability. Will be shown.

  Hereinafter, the present invention will be described in more detail by way of examples and comparative examples of the present invention, but the present invention is not limited to these examples. In addition, the evaluation method of the nickel cobalt hydroxide and the positive electrode active material for non-aqueous electrolyte secondary batteries used in Examples and Comparative Examples is as follows.

(1) Analysis of metal components:
Analysis was performed by ICP emission analysis using an ICP emission analyzer (Varian, 725ES).
(2) Analysis of ammonium ion concentration:
It was measured by a distillation method according to JIS standard.
(3) Measurement of average particle diameter and evaluation of particle size distribution width:
Using a laser diffraction particle size distribution meter (manufactured by Nikkiso Co., Ltd., Microtrac HRA), the average particle size was measured and the particle size distribution width was evaluated.
(4) Observational evaluation of morphology:
Using a scanning electron microscope (manufactured by JEOL Ltd., JSM-6360LA, hereinafter referred to as SEM), observation and evaluation of shape and appearance were performed.

[Example 1]
Into an overflow type crystallization reaction tank having a tank volume of 34 liters equipped with four baffle plates, 32 liters of industrial water and 1300 ml of 25% by mass ammonia water were added, and heated to 50 ° C. in a thermostatic bath and a heating jacket. A mass% sodium hydroxide solution was added to adjust the pH of the reaction solution in the tank to 10.9 to 11.1. Since this pH is a pH at 50 ° C., in order to accurately control the pH, the reaction solution is collected, cooled to 25 ° C., the pH is measured, and the pH at 25 ° C. becomes 11.7 to 11.9. Thus, the pH at 50 ° C. was adjusted.
Next, while stirring the reaction solution maintained at 50 ° C., using a metering pump, a mixed aqueous solution of nickel sulfate and cobalt sulfate (metal element molar ratio) with a nickel concentration of 1.69 mol / L and a cobalt concentration of 0.31 mol / L Ni: Co = 0.82: 0.15, hereinafter referred to as a mixed aqueous solution) at 30 ml / min and 25% by mass of aqueous ammonia at 2.5 ml / min. A crystallization reaction was carried out by adding a 24% by mass caustic soda solution and controlling the pH at 25 ° C. to be 11.7 to 11.9 and the ammonium ion concentration to be 5 to 15 g / L.

The stirring at this time was performed by rotating horizontally at a blade peripheral speed of 800 rpm and 4.2 m / s using a three-blade propeller blade having a diameter of 10 cm and an inclination angle of 30 degrees with respect to the horizontal plane. As a method of supplying the mixed aqueous solution into the reaction system, an injection nozzle serving as a supply port was inserted into the reaction solution so that the mixed aqueous solution was directly supplied into the reaction solution. Furthermore, the tip of the injection nozzle was branched into three locations, and the mixed aqueous solution was supplied to different locations in the reaction solution. At this time, the supply amount of the mixed aqueous solution from each injection nozzle is 10 ml / min, and the ratio of the supply amount to the reaction solution amount is 0.029% / min in volume ratio.
The nickel cobalt composite hydroxide particles produced by the crystallization reaction were continuously taken out by overflow. The particles taken out over 48 to 72 hours after the start of the stable reaction were appropriately solid-liquid separated, washed with water and dried to obtain a powdered nickel-cobalt composite hydroxide.
The average particle size of the obtained nickel-cobalt composite hydroxide is 28.6 μm, and the index [(d90−d10) / average particle size] of the particle size distribution width is 0.97, and [d10 / average particle size] Diameter] was 0.55. Further, when the above particles were observed with an SEM, they were substantially spherical particles, and when the cross section was observed in the same manner, it was confirmed that the particles consisted of dense crystals.
Further, when the composite hydroxide was analyzed by powder X-ray diffraction using Cu-Kα rays with an X-ray diffraction measurement apparatus (X'Pert PRO, manufactured by Panalytic Co., Ltd.), the (101) plane was obtained from the X-ray diffraction chart. The half width was 0.44 °, and it was confirmed to have good crystallinity.

[Example 2]
A nickel cobalt composite hydroxide was obtained in the same manner as in Example 1 except that a 6-blade inclined paddle blade having a diameter of 10 cm and an inclination angle of 45 degrees with respect to the horizontal plane was used for stirring.
The average particle diameter of the obtained nickel-cobalt composite hydroxide is 27.3 μm, and the index [(d90−d10) / average particle diameter] of the particle size distribution width is 0.97, and [d10 / average particle diameter] Diameter] was 0.56. When the particles were observed with an SEM, they were substantially spherical particles, and when the cross section was observed in the same manner, it was confirmed that the particles consisted of dense crystals.
Further, when analyzed by powder X-ray diffraction, the (101) plane half-value width obtained from the X-ray diffraction chart was 0.46 °, and it was confirmed that the film had good crystallinity.

[Example 3]
The supply of the mixed aqueous solution is branched at four points at the tip of the injection nozzle, the supply amount of the mixed aqueous solution from each injection nozzle is 7.5 ml / min, and the ratio of the supply amount to the reaction solution amount is 0.022 by volume. A nickel-cobalt composite hydroxide was obtained in the same manner as in Example 1 except that it was changed to% / min.
The average particle diameter of the obtained nickel-cobalt composite hydroxide is 28.5 μm, and the index [(d90−d10) / average particle diameter] of the particle size distribution width is 1.06, and [d10 / average particle diameter] Diameter] was 0.54. Further, when the above particles were observed with an SEM, they were substantially spherical particles, and when the cross section was observed in the same manner, it was confirmed that the particles consisted of dense crystals.

[Example 4]
The supply of the mixed aqueous solution is branched into five locations at the tip of the injection nozzle, the supply amount of the mixed aqueous solution from each injection nozzle is 6 ml / min, and the ratio of the supply amount to the reaction solution amount is 0.018% by volume. Nickel cobalt composite hydroxide was obtained in the same manner as in Example 1 except that it was changed to / min.
The average particle diameter of the obtained nickel-cobalt composite hydroxide is 29.1 μm, and the index [(d90−d10) / average particle diameter] of the particle size distribution width is 1.16, and [d10 / average particle diameter] Diameter] was 0.46. Further, when the above particles were observed with an SEM, they were substantially spherical particles, and when the cross section was observed in the same manner, it was confirmed that the particles consisted of dense crystals.

[Example 5]
Nickel-cobalt composite hydroxide was obtained in the same manner as in Example 1 except that the stirring blade was rotated at 600 rpm and the blade peripheral speed was 3.1 m / sec.
The average particle diameter of the obtained nickel-cobalt composite hydroxide is 35.8 μm, and the index [(d90−d10) / average particle diameter] of the particle size distribution width is 1.13, and [d10 / average particle diameter] The diameter] was 0.47. Further, when the above particles were observed with an SEM, they were substantially spherical particles, and when the cross section was observed in the same manner, it was confirmed that the particles consisted of dense crystals.

[Example 6]
The stirring blade was rotated at 400 rpm and the blade peripheral speed was 2.1 m / second, and the upward flow in the vicinity of the overflow in the reaction vessel was controlled to 40 mm / second, and the reaction solution was intermittently discharged from the discharge port at the bottom of the reaction vessel. A nickel-cobalt composite hydroxide was obtained in the same manner as in Example 1 except that the particles extracted and settled together were collected.
The average particle diameter of the obtained nickel-cobalt composite hydroxide is 42.4 μm, and the index [(d90−d10) / average particle diameter] of the particle size distribution width is 1.12, and [d10 / average particle diameter] Diameter] was 0.56. Further, when the above particles were observed with an SEM, they were substantially spherical particles, and when the cross section was observed in the same manner, it was confirmed that the particles consisted of dense crystals.

[Comparative Example 1]
A nickel cobalt composite hydroxide was obtained in the same manner as in Example 1 except that a 6-blade paddle blade having a diameter of 10 cm and an inclination angle of 90 degrees with respect to the horizontal plane was used for stirring.
The average particle diameter of the obtained nickel cobalt composite hydroxide was 12.4 μm.

[Comparative Example 2]
A nickel cobalt composite hydroxide was obtained in the same manner as in Example 1 except that a 6-blade turbine blade having a diameter of 10 cm and an inclination angle of 90 degrees with respect to the horizontal plane was used for stirring.
The average particle diameter of the obtained nickel cobalt composite hydroxide was 11.7 μm.

[Comparative Example 3]
The supply of the mixed aqueous solution is branched into two locations at the tip of the injection nozzle, the supply amount of the mixed aqueous solution from each injection nozzle is 15 ml / min, and the ratio of the supply amount to the reaction solution amount is 0.044% by volume. Nickel cobalt composite hydroxide was obtained in the same manner as in Example 1 except that it was changed to / min.
The average particle diameter of the obtained nickel cobalt composite hydroxide was 13.4 μm.

[Comparative Example 4]
The supply of the mixed aqueous solution is made one place without branching the tip of the injection nozzle, the supply amount of the mixed aqueous solution from the injection nozzle is 30 ml / min, and the ratio of the supply amount to the reaction solution amount is 0.088% by volume. Nickel cobalt composite hydroxide was obtained in the same manner as in Example 1 except that it was changed to / min.
The average particle diameter of the obtained nickel cobalt composite hydroxide was 10.3 μm.

From Examples 1 to 6, it can be seen that according to the present invention, a nickel-cobalt composite hydroxide having an average particle diameter of 15 to 50 μm and a substantially spherical and high density is obtained.
On the other hand, Comparative Examples 1 and 2 using a stirring blade having an inclination greater than 45 degrees with respect to the horizontal plane, Comparative Examples 3 and 4 in which the ratio of the supply amount to the reaction solution amount exceeded 0.04 vol% / min, In any case, the average particle diameter is less than 15 μm, and it is understood that a nickel cobalt composite hydroxide having a large particle diameter cannot be obtained.

[Example 7]
The nickel-cobalt composite hydroxide obtained in Example 1 was mixed with water to form a slurry, and an aqueous solution of sodium aluminate and sulfuric acid were added to this mixed aqueous solution with stirring, and the pH of the slurry was adjusted to pH = 9.5. Adjusted.
Thereafter, the nickel cobalt composite hydroxide particles were coated with aluminum hydroxide by continuing stirring for 1 hour. At this time, the aqueous solution of sodium aluminate was added such that the molar ratio of metal elements in the slurry was Ni: Co: Al = 0.82: 0.15: 0.03.
The composite hydroxide coated with aluminum hydroxide was heat-treated at 700 ° C. for 6 hours in an air (oxygen concentration: 21 vol%) air stream to obtain a composite oxide.
Lithium hydroxide is weighed and mixed with the composite oxide so that the atomic ratio of the total (Me) of lithium (Li) and the metal elements in the composite oxide is Li / Me = 1.02. A lithium mixture was obtained. Mixing was performed using a shaker mixer apparatus (TURBULA Type T2C manufactured by Willy et Bacofen (WAB)).
The obtained lithium mixture was calcined at 500 ° C. for 4 hours in an oxygen stream (oxygen concentration: 100% by volume), then calcined at 760 ° C. for 12 hours, cooled, and crushed to obtain a positive electrode active material. It was.
The average particle diameter of the obtained positive electrode active material is 24.8 μm, the particle size distribution width index [(d90−d10) / average particle diameter] is 0.97, and [d10 / average particle diameter] is It was 0.64. Moreover, when the particles were observed with an SEM, they were substantially spherical particles.
Further, when the positive electrode active material was analyzed by powder X-ray diffraction using Cu-Kα rays with an X-ray diffractometer (X'Pert Pro, manufactured by Panalical Co., Ltd.), lithium nickel cobalt composite oxidation of hexagonal layered crystals It was a single phase, and the (003) plane half-value width determined from the X-ray diffraction chart was 0.077 °, confirming that it had good crystallinity.

[Example 8]
A positive electrode active material was obtained and evaluated in the same manner as in Example 7 except that the nickel-cobalt composite hydroxide obtained in Example 3 was used.
The average particle diameter of the obtained positive electrode active material is 25.1 μm, the index [(d90−d10) / average particle diameter] of the particle size distribution width is 1.01, and [d10 / average particle diameter] is 0.62. In addition, the particles are substantially spherical, are hexagonal layered crystal lithium nickel cobalt composite oxide single phase, have a (003) plane half-value width of 0.081 °, and have good crystallinity. confirmed.

[Example 9]
A positive electrode active material was obtained and evaluated in the same manner as in Example 7 except that the nickel-cobalt composite hydroxide obtained in Example 5 was used.
The average particle diameter of the obtained positive electrode active material is 30.1 μm, the index [(d90−d10) / average particle diameter] of the particle size distribution width is 1.01, and [d10 / average particle diameter] is 0.55. Further, the particles are substantially spherical, are hexagonal layered crystal lithium nickel cobalt composite oxide single phase, have a (003) plane half-value width of 0.072 °, and have good crystallinity. confirmed.

  The method for producing a nickel-cobalt composite hydroxide of the present invention is suitable for a precursor of a positive electrode active material for a non-aqueous electrolyte secondary battery. The nickel-cobalt composite having a large particle size, high density, high crystallinity, and substantially spherical shape. A hydroxide can be provided and is excellent without sacrificing mass productivity. Therefore, industrial applicability is high and its industrial value is great.

Claims (15)

General _{formula: Ni 1-x-y Co} x M y (OH) 2 (0.05 ≦ x ≦ 0.95,0 ≦ y ≦ 0.15, x + y ≦ 0.95, M is an additive element , Mg, Al, Ca, Ti, V, Cr, Mn, Zr, Nb, Mo, or W.). And
While stirring the reaction solution, while supplying a mixed aqueous solution (a) containing a nickel salt and a cobalt salt and an aqueous solution (b) containing an ammonium ion supplier, a caustic aqueous solution (c) is supplied and reacted. When obtaining the nickel cobalt composite hydroxide by solid-liquid separation of the crystallized nickel cobalt composite hydroxide particles, washing with water and drying,
While stirring the reaction solution using a stirring blade having an inclination of 15 to 45 degrees with respect to the horizontal plane, the ratio of the supply amount to the reaction solution amount per supply port of the mixed aqueous solution (a) is 0.04 vol% / min. The manufacturing method of the nickel cobalt composite hydroxide characterized by the following. 2. The nickel-cobalt composite hydroxide according to claim 1, wherein when the reaction solution is stirred using the stirring blade, the blade peripheral speed obtained by the following formula 1 is in the range of 1 to 5 m / second. Manufacturing method.
Formula 1: Blade peripheral speed (m / sec) = π × blade diameter (m) × rotational speed (rpm) ÷ 60   The method for producing a nickel-cobalt composite hydroxide according to claim 1 or 2, wherein the mixed aqueous solution (a) and the caustic alkaline aqueous solution (c) are supplied from a supply port provided in the reaction solution.   The method for producing a nickel-cobalt composite hydroxide according to any one of claims 1 to 3, wherein the mixed aqueous solution (a) is supplied from a supply port branched into three or more locations.   The pH of the reaction solution is maintained at 11.0 to 13.0, the temperature is 20 to 70 ° C, and the ammonium ion concentration is within a range of 5 to 20 g / L. The manufacturing method of the nickel cobalt composite hydroxide of description.   The mixed aqueous solution (a) and the aqueous solution (b) containing an ammonium ion supplier are continuously supplied, and the reaction solution containing nickel-cobalt composite hydroxide particles is continuously overflowed from the reaction vessel to obtain nickel cobalt. The method for producing a nickel-cobalt composite hydroxide according to any one of claims 1 to 5, wherein composite hydroxide particles are recovered.   The mixed aqueous solution (a) and the aqueous solution (b) containing an ammonium ion supplier are continuously supplied, and the nickel-cobalt composite hydroxide that has been grown is set so that the upward flow near the overflow in the reaction vessel is 50 mm / second or less. The method for producing nickel-cobalt composite hydroxide according to any one of claims 1 to 5, wherein the product particles are settled and nickel-cobalt composite hydroxide particles are recovered from the bottom of the reaction vessel.   The method for producing a nickel-cobalt composite hydroxide according to claim 7, wherein the blade peripheral speed is set to 1 to 3 m / sec.   The method for producing a nickel-cobalt composite hydroxide according to any one of claims 1 to 8, wherein the surface of the nickel-cobalt composite hydroxide particles is coated with a hydroxide of an additive element M.   The said nickel salt and cobalt salt are at least 1 sort (s) chosen from a sulfate, nitrate, or a chloride, The manufacturing method of the nickel cobalt composite hydroxide in any one of Claims 1-9 characterized by the above-mentioned.   The method for producing a nickel-cobalt composite hydroxide according to any one of claims 1 to 10, wherein the ammonium ion supplier is at least one selected from ammonia, ammonium sulfate, and ammonium chloride. Obtained from the manufacturing method according to any one of claims 1 to 11, the general _{formula: Ni 1-x-y Co} x M y (OH) 2 (0.05 ≦ x ≦ 0.95,0 ≦ y ≦ 0 .15, x + y ≦ 0.95, M is an additive element and is at least one element selected from Mg, Al, Ca, Ti, V, Cr, Mn, Zr, Nb, Mo, or W . consists particles represented by), Ri average particle size 15~50μm der particles are substantially spherical, an indicator of the particle size distribution width [(d90-d10) / average particle size] is 1.2 or less, nickel-cobalt composite hydroxide half width of which is determined by X-ray diffraction (101) plane and wherein 0.3 to 0.7 ° der Rukoto. The nickel-cobalt composite hydroxide according to claim 12, wherein the average particle diameter is 25 to 45 μm . Obtained by sintering a mixture of a nickel-cobalt composite hydroxide and the lithium compound of claim 12 or 13, the general _{formula: LiNi 1-x-y Co} x M y O 2 (0.05 ≦ x ≦ 0.95, 0 ≦ y ≦ 0.15, x + y ≦ 0.95, M is an additive element, and includes Mg, Al, Ca, Ti, V, Cr, Mn, Zr, Nb, Mo, or W is one or more elements selected.) a lithium-nickel-cobalt composite oxide particles represented by Ri average particle size 15~50μm der particles are substantially spherical, an indicator of the particle size distribution width [(d90 -d10) / average particle size] is 1.2 or less, the non-aqueous electrolyte half width of which is (003) plane measured by X-ray diffraction and wherein from 0.05 to .085 ° der Rukoto Positive electrode active material for secondary battery. The positive electrode active material for a non-aqueous electrolyte secondary battery according to claim 14, wherein the average particle size is 25 to 45 μm .