JP7619978B2 - Nickel-cobalt-aluminum composite hydroxide - Google Patents

Description

The present invention relates to a nickel-cobalt-aluminum composite hydroxide, which is a precursor of a positive electrode active material and is composed of secondary particles formed by agglomeration of primary particles containing nickel, cobalt, and aluminum, or of primary particles and secondary particles.

In recent years, with the widespread use of portable electronic devices such as smartphones, tablet devices, and laptop computers, there has been a growing need to develop high-power secondary batteries, including small, lightweight non-aqueous electrolyte secondary batteries with high energy density, as well as batteries for hybrid and electric vehicles.

Lithium-ion secondary batteries are an example of a secondary battery that can meet these needs. Lithium-ion secondary batteries are composed of a positive electrode, a negative electrode, and an electrolyte, and the active materials used for the positive and negative electrodes are materials that can extract and insert lithium. Lithium-ion secondary batteries are still being actively researched and developed, and among these, lithium-ion secondary batteries that use layered or spinel-type lithium metal composite oxides as the positive electrode active material can obtain a high voltage of about 4V, and are therefore being put into practical use as batteries with high energy density.

Among these, lithium nickel cobalt composite oxide has attracted attention as a material that has good cycle characteristics of battery capacity and can provide high output with low resistance. In recent years, it is also suitable as a power source for electric vehicles and hybrid vehicles, which are constrained by mounting space, and is considered important as an on-board power source. Generally, lithium nickel cobalt composite oxide is produced by mixing the precursor nickel cobalt composite hydroxide with a lithium compound and baking it.

This nickel-cobalt composite hydroxide contains impurities such as sulfate, chlorine, and sodium derived from the raw materials and chemicals used in the manufacturing process. These impurities induce side reactions and worsen the reaction with lithium during the process of mixing the nickel-cobalt composite hydroxide with a lithium compound and firing it, thereby reducing the crystallinity of the lithium-nickel-cobalt composite oxide, which has a layered structure.

When lithium nickel cobalt composite oxide with low crystallinity due to the influence of impurities is used as a positive electrode active material to construct a battery, it inhibits the diffusion of lithium in the solid phase, resulting in a decrease in battery capacity. In addition, since these impurities hardly contribute to the charge/discharge reaction, it is necessary to use extra negative electrode material in the battery to cover the irreversible capacity of the positive electrode material. As a result, the capacity per weight or volume of the entire battery becomes smaller, and excess lithium accumulates in the negative electrode as irreversible capacity, which is a safety issue.

Impurities include sulfate radicals, chlorine radicals, sodium, etc., and techniques for removing these impurities have been disclosed.

For example, Patent Document 1 discloses a method for reducing sulfate and chlorine radicals by performing a crystallization process to obtain a niobium-containing transition metal composite hydroxide and washing the obtained niobium-containing transition metal composite hydroxide with an aqueous solution of a carbonate such as potassium carbonate, sodium carbonate, or ammonium carbonate.

Patent Document 2 also discloses that in the process of producing nickel manganese cobalt composite hydroxide from a crystallization reaction, the alkaline solution used for adjusting the pH is a mixed solution of an alkali metal hydroxide and a carbonate, thereby reducing the impurities of sulfate, chlorine, and carbonate.

Patent Documents 3 and 4 disclose that the nickel-manganese composite hydroxide particles or nickel composite hydroxide particles having a void structure inside the particles obtained in the crystallization process are washed with an aqueous solution of a carbonate such as potassium carbonate, sodium carbonate, potassium hydrogen carbonate, or sodium hydrogen carbonate, thereby reducing the sulfate radicals, chlorine radicals, and sodium.

Patent Document 5 also discloses that a nickel-cobalt-M element-containing aqueous solution or aqueous dispersion obtained by mixing a nickel ammine complex, a cobalt ammine complex, and an M element source is heated to thermally decompose the nickel ammine complex and the cobalt ammine complex, and a nickel-cobalt-M element-containing composite compound with a low content of impurities such as sulfate radicals, chlorine radicals, sodium, and iron is used.

JP 2015-122269 A JP 2016-117625 A International Publication No. 2015/146598 JP 2015-191848 A International Publication No. 2012/020768

However, Patent Documents 1 and 2 make no mention at all of sodium removal. Furthermore, Patent Documents 3 and 4, even in solid precursors with a porosity of about 3%, sodium still remains at 0.001 to 0.015 mass%, and sodium reduction is insufficient. Furthermore, in Patent Document 5, a nickel-cobalt-M element-containing composite compound is obtained by thermal decomposition, and in terms of the spherical shape of the particles, particle size distribution, and specific surface area, it is questionable whether sufficient battery characteristics will be obtained when used as a positive electrode active material. In particular, the focus is not on nickel-cobalt-aluminum composite hydroxides containing aluminum.

Therefore, an object of the present invention is to provide a nickel-cobalt-aluminum composite hydroxide containing nickel, cobalt, and aluminum, which is a precursor of a positive electrode active material for a lithium-ion secondary battery that can reliably reduce the content of impurities, particularly sodium, which hardly contributes to charge/discharge reactions, and enable high capacity.

A nickel-cobalt aluminum composite hydroxide according to one embodiment of the present invention is a nickel-cobalt aluminum composite hydroxide that is a precursor of a positive electrode active material and is composed of secondary particles in which primary particles containing nickel, cobalt, and aluminum are aggregated, or the primary particles and the secondary particles, and is characterized in that the nickel-cobalt aluminum composite hydroxide has a sodium content of less than 0.0005 mass% and a chlorine root content of 0.01 mass% or less .

In this way, it is possible to provide a nickel-cobalt-aluminum composite hydroxide containing nickel, cobalt, and aluminum, which is a precursor of a positive electrode active material for a lithium-ion secondary battery that reliably reduces the contents of sodium and chlorine radicals and enables a high capacity to be achieved.

In this case, in one embodiment of the present invention, the nickel-cobalt-aluminum composite hydroxide may have a specific surface area of 30 to 50 m ² /g.

In this way, it is possible to provide nickel-cobalt-aluminum composite hydroxide, which is a precursor of a positive electrode active material that can be used to obtain a lithium-ion secondary battery with a higher capacity by increasing the specific surface area.

In this case, in one aspect of the present invention, the content of sulfate radicals contained in the nickel-cobalt-aluminum composite hydroxide may be 0.2 mass % or less .

In this manner, it is possible to provide a nickel-cobalt-aluminum composite hydroxide, which is a precursor of a positive electrode active material that can reliably reduce the sulfate group content and obtain a lithium-ion secondary battery with a higher capacity.

In this case, in one embodiment of the present invention, the index showing the spread of the particle size distribution of the nickel-cobalt-aluminum composite hydroxide, [(d90-d10)/average particle size], may be 0.55 or less.

In this way, the proportion of fine particles and large particles is reduced when the positive electrode active material is used, so that a lithium-ion secondary battery using this positive electrode active material in the positive electrode is safe and can achieve good cycle characteristics and battery output.

In this case, in one aspect of the present invention, the nickel-cobalt- _aluminum composite hydroxide may be represented by the general formula: _{Ni1-xyCoxAly (} OH) _2+a (where 0.05≦x≦0.35, 0.01≦y≦0.20, x+y<0.40, and 0≦a≦0.5).

In this way, it is possible to reliably reduce the sodium content of the nickel-cobalt-aluminum composite hydroxide and provide a nickel-cobalt-aluminum composite hydroxide, which is a precursor of a positive electrode active material that can produce a lithium-ion secondary battery with a high capacity.

According to the present invention, it is possible to provide a nickel-cobalt-aluminum composite hydroxide containing nickel, cobalt, and aluminum, which is a precursor of a positive electrode active material for a lithium-ion secondary battery that can reliably reduce the sodium content and increase the capacity.

FIG. 1 is a cross-sectional SEM photograph of a nickel-cobalt-aluminum composite hydroxide according to one embodiment of the present invention, showing that the internal structure is a solid structure. FIG. 2 is a process diagram showing an outline of a method for producing a nickel-cobalt-aluminum composite hydroxide according to one embodiment of the present invention.

The present inventors have conducted extensive research to solve the above problems, and have discovered that, in particular in the production of nickel-cobalt-aluminum composite hydroxides containing aluminum, the reaction atmosphere in the crystallization process can be controlled, the alkaline solution used in the crystallization process is a mixed solution of an alkali metal hydroxide and a carbonate, and the transition metal composite hydroxide obtained in the crystallization process is washed in the washing process with an ammonium hydrogen carbonate solution, which is a washing solution containing hydrogen carbonate (bicarbonate), thereby more efficiently reducing the impurities, sulfate radicals, chlorine radicals, and sodium, and thus completing the present invention. Preferred embodiments of the present invention are described below.

The present embodiment described below does not unduly limit the contents of the present invention described in the claims, and can be modified within the scope of the present invention. Furthermore, not all of the configurations described in the present embodiment are necessarily essential as a means for solving the problems of the present invention. The nickel-cobalt-aluminum composite hydroxide, the method for producing the nickel-cobalt-aluminum composite hydroxide, and the lithium-nickel-cobalt-aluminum composite oxide according to one embodiment of the present invention will be described in the following order.
1. Nickel-cobalt-aluminum composite hydroxide 2. Lithium-nickel-cobalt-aluminum composite oxide 3. Method for producing nickel-cobalt-aluminum composite hydroxide 3-1. Crystallization process 3-1-1. Nucleation process 3-1-2. Particle growth process 3-2. Washing process

<1. Nickel-cobalt-aluminum composite hydroxide>
A nickel-cobalt-aluminum composite hydroxide according to one embodiment of the present invention is a precursor of a positive electrode active material, which is composed of secondary particles in which primary particles containing nickel, cobalt, and aluminum are aggregated, or the primary particles and the secondary particles.

The nickel-cobalt-aluminum composite hydroxide is characterized in that the sodium content is less than 0.0005% by mass. The nickel-cobalt-aluminum composite hydroxide according to one embodiment of the present invention will be specifically described below.

[Particle composition]
The nickel-cobalt- _aluminum composite hydroxide is preferably adjusted so that its composition is expressed by the general formula: _{Ni1-xyCoxAly (} OH) _2+a (where 0.05≦x≦0.35, 0.01≦y≦0.20, x+y<0.40, 0≦a≦0.5).

In the above general formula, x, which indicates the cobalt content, is preferably 0.05≦x≦0.35. By adding an appropriate amount of cobalt, it is possible to improve cycle characteristics and further reduce the expansion and contraction behavior of the crystal lattice due to the desorption and insertion of lithium accompanying charge and discharge. If the cobalt content is too low and x is less than 0.05, it is difficult to obtain the expected effect, which is not preferable. On the other hand, if the cobalt content is too high and x exceeds 0.35, it is not preferable because there is a possibility of a large decrease in the initial discharge capacity and there is also a problem of being disadvantageous in terms of cost. Therefore, x, which indicates the cobalt content, is preferably 0.05≦x≦0.35, and taking into consideration battery characteristics and cost, it is preferably 0.07≦x≦0.25, and in practice, it is more preferable to set it to 0.10≦x≦0.20.

In addition, y, which indicates the aluminum content, is preferably 0.01≦y≦0.2. Adding aluminum within this range can further improve durability and safety when the battery is used as a positive electrode active material. In particular, if aluminum is adjusted so that it is distributed uniformly inside the particles, the above effect can be obtained throughout the entire particle, so there is an advantage that a greater effect can be achieved with the same amount of aluminum added and capacity reduction can be suppressed. If the amount of aluminum added is too small and y is less than 0.01, it is difficult to obtain the expected effect, which is not preferable. On the other hand, if it exceeds 0.2, the amount of aluminum added is too large, which reduces the metal elements that contribute to the Redox reaction and may reduce the battery capacity, which is not preferable.

Other analytical methods for the particle composition are not particularly limited, but can be determined by chemical analysis methods such as acid decomposition-ICP emission spectrometry.

[Particle structure]
The nickel-cobalt-aluminum composite hydroxide is composed of spherical secondary particles formed by agglomeration of a plurality of primary particles. The primary particles constituting the secondary particles may have various shapes such as plate-like, needle-like, rectangular, elliptical, and rhombohedral. In addition, the present invention can be applied to the case where the agglomeration state of a plurality of primary particles is not only agglomerated in random directions, but also agglomerated in the long diameter direction of the particles radially from the center.

As for the agglomeration state, it is preferable that plate-like or needle-like primary particles are agglomerated in random directions to form secondary particles. In the case of such a structure, almost uniform voids are generated between the primary particles, and when mixed with a lithium compound and fired, the molten lithium compound spreads throughout the secondary particles, allowing sufficient diffusion of lithium.

The method for observing the shapes of the primary particles and secondary particles is not particularly limited, but they can be measured by observing the cross section of the nickel-cobalt-aluminum composite hydroxide using a scanning electron microscope (SEM) or the like.

[Particle internal structure]
The nickel-cobalt-aluminum composite hydroxide according to one embodiment of the present invention has a solid structure and does not have a hollow structure or a porous structure inside the secondary particles. Since there are no voids inside the secondary particles, the particle strength is the best. Therefore, the life of the positive electrode active material is extended.

This solid structure can also be confirmed by observing the cross section of nickel-cobalt-aluminum composite hydroxide particles with a scanning electron microscope (SEM).

[Average particle size (MV)]
The nickel-cobalt-aluminum composite hydroxide is preferably adjusted to have an average particle size of 3 to 20 μm. If the average particle size is less than 3 μm, the packing density of the particles decreases when the positive electrode is formed. On the other hand, if the average particle size exceeds 20 μm, the specific surface area of the positive electrode active material decreases, and the interface with the electrolyte of the battery decreases. This is not preferable because it may increase the resistance of the positive electrode and reduce the output characteristics of the battery. Therefore, the nickel-cobalt-aluminum composite hydroxide has an average particle size of 3 to 20 μm, preferably 3 to 15 μm. If the thickness is adjusted to 4 to 12 μm, it is possible to increase the battery capacity per volume in a lithium ion secondary battery using this positive electrode active material as a positive electrode material, and the battery capacity per volume can be increased, and the safety and cycle life can be improved. It has good characteristics.

The method for measuring the average particle size is not particularly limited, but it can be determined, for example, from the volume-based distribution measured using a laser diffraction/scattering method.

[Impurity content]
In general, nickel-cobalt composite hydroxide and nickel-cobalt aluminum composite hydroxide contain sulfate radicals, chlorine radicals, and sodium as impurities. These impurities cause the reaction with lithium to deteriorate and hardly contribute to the charge-discharge reaction, so it is preferable to remove them as much as possible and reduce their content. In addition, although details will be described later, when producing nickel-cobalt aluminum composite hydroxide containing aluminum, it is preferable to use sodium aluminate and sodium hydroxide rather than sulfate, and the sodium concentration during crystallization is higher than when producing nickel-cobalt composite hydroxide not containing aluminum, making it difficult to remove sodium by washing. Conventionally, techniques for removing these impurities have been disclosed, but they are still insufficient.

The nickel-cobalt-aluminum composite hydroxide according to one embodiment of the present invention is characterized in that the sodium content contained therein is less than 0.0005% by mass. In this way, it is possible to reliably reduce the sodium content and provide a nickel-cobalt-aluminum composite hydroxide containing nickel, cobalt, and aluminum, which is a precursor of the positive electrode active material for lithium-ion secondary batteries that can achieve high capacity.

It is also preferable that the sulfate radical content in the nickel-cobalt-aluminum composite hydroxide is 0.2% by mass or less, and the chlorine radical content is 0.01% by mass or less. In this way, it is possible to reliably reduce the sulfate radical, chlorine radical, and sodium content, and provide a nickel-cobalt-aluminum composite hydroxide that is a precursor of a positive electrode active material for a lithium-ion secondary battery that can improve battery characteristics.

The content of each impurity can be determined, for example, by the following analytical methods. Sodium can be determined by acid decomposition-atomic absorption spectrometry, acid decomposition-ICP emission spectrometry, or the like. Sulfate radicals can be determined by analyzing the total sulfur content of the nickel-cobalt-aluminum composite hydroxide by combustion infrared absorption spectrometry, acid decomposition-ICP emission spectrometry, or the like, and converting this total sulfur content into sulfate radicals (SO ₄ ²⁻ ). Chlorine radicals can be determined by analyzing the nickel-cobalt-aluminum composite hydroxide directly, or by separating the chlorine radicals contained in the nickel-cobalt-aluminum composite hydroxide by a distillation operation in the form of silver chloride or the like, and analyzing the separated chlorine radicals by X-ray fluorescence (XRF) analysis.

[Particle size distribution]
The nickel-cobalt-aluminum composite hydroxide is preferably adjusted so that the index showing the spread of the particle size distribution of the particles, [(d90-d10)/average particle size], is 0.55 or less.

If the particle size distribution is wide and the index showing the spread of the particle size distribution, [(d90-d10)/average particle size], exceeds 0.55, there will likely be many fine particles whose particle size is very small compared to the average particle size, and many particles whose particle size is very large compared to the average particle size (large diameter particles).

These characteristics of the particle size distribution at the precursor stage also have a significant effect on the positive electrode active material obtained after the firing process. If a positive electrode is formed using a positive electrode active material containing many fine particles, not only may there be a risk of heat generation due to local reactions of the fine particles, which may reduce safety, but also the fine particles with a large specific surface area may be selectively deteriorated, which may result in poor cycle characteristics, which is undesirable. On the other hand, if a positive electrode is formed using a positive electrode active material containing many large-diameter particles, there may not be enough reaction area between the electrolyte and the positive electrode active material, which may result in a decrease in battery output due to an increase in reaction resistance, which is undesirable.

Therefore, in the particle size distribution of the precursor nickel-cobalt-aluminum composite hydroxide, it is preferable that [(d90-d10)/average particle size] is 0.55 or less, and since the proportion of fine particles and large-diameter particles is reduced when used as a positive electrode active material, lithium-ion secondary batteries using this positive electrode active material in the positive electrode are safer and can achieve good cycle characteristics and battery output.

In the index showing the spread of particle size distribution [(d90-d10)/average particle size], d10 means the particle size at which the cumulative volume of the number of particles at each particle size, when accumulated from the smallest particle size, is 10% of the total volume of all particles. In contrast, d90 means the particle size at which the cumulative volume of the number of particles at each particle size, when accumulated from the smallest particle size, is 90% of the total volume of all particles. There are no particular limitations on the method for determining the average particle size, d90, and d10, but they can be determined, for example, from a volume-based distribution measured using a laser diffraction/scattering method.

[Specific surface area]
The nickel-cobalt-aluminum composite hydroxide is preferably adjusted so that its specific surface area is 15 to 60 m ² /g, because if the specific surface area is in the range of 15 to 60 m ² /g, a more sufficient particle surface area can be obtained that can come into contact with the molten lithium compound when mixed with the lithium compound and fired.

On the other hand, if the specific surface area is less than 15 m ² /g, the contact with the molten lithium compound when mixed with the lithium compound and sintered becomes insufficient, and the crystallinity of the resulting lithium nickel cobalt aluminum composite oxide decreases, and when used as a positive electrode material to form a lithium ion secondary battery, there is a concern that lithium diffusion in the solid phase is hindered and the capacity decreases. Also, if the specific surface area exceeds 60 m ² /g, when mixed with the lithium compound and sintered, crystal growth proceeds too much, and cation mixing occurs in which nickel is mixed into the lithium layer of the lithium transition metal composite oxide, which is a layered compound, and the charge/discharge capacity may decrease, which is not preferable. In more detail, it is more preferable that the specific surface area is adjusted to 30 to 50 m ² /g in order to further stabilize the above-mentioned battery characteristics.

In particular, nickel-cobalt-aluminum composite hydroxides containing aluminum differ from those not containing aluminum in terms of the unevenness of the particle surface, as well as the size and degree of aggregation of the primary particles. Therefore, the specific surface area of the nickel-cobalt-aluminum composite hydroxide according to one embodiment of the present invention is preferably set to 30 to 50 m ² /g as described above.

The method for measuring the specific surface area is not particularly limited, but it can be determined, for example, by the BET multipoint method, the BET single point method, or the nitrogen gas adsorption/desorption method.

Figure 1 shows a cross-sectional SEM photograph of a nickel-cobalt-aluminum composite hydroxide according to one embodiment of the present invention. As shown in Figure 1, the nickel-cobalt-aluminum composite hydroxide according to one embodiment of the present invention has a solid internal structure.

The nickel-cobalt-aluminum composite hydroxide according to one embodiment of the present invention can reliably reduce the sodium content, and provide a nickel-cobalt-aluminum composite hydroxide containing nickel, cobalt, and aluminum, which is a precursor of the positive electrode active material for lithium-ion secondary batteries that can achieve high capacity.

2. Lithium Nickel Cobalt Aluminum Composite Oxide
A lithium nickel cobalt aluminum composite oxide according to one embodiment of the present invention is composed of secondary particles formed by agglomeration of primary particles containing lithium, nickel, cobalt, and aluminum, or the primary particles and the secondary particles, and is characterized in that the sodium content in the lithium nickel cobalt aluminum composite oxide is less than 0.0005 mass%.

It is also preferable that the content of sulfate radicals in the lithium nickel cobalt aluminum composite oxide is 0.15% by mass or less, the content of chloride radicals is 0.005% by mass or less, and the Li site occupancy rate is 99.0% or more.

Here, a small amount of lithium may be washed away from the lithium nickel cobalt aluminum composite oxide by the water washing process described below. In addition, the more impurities there are in the lithium nickel cobalt aluminum composite oxide, the more adverse effects there are during the firing reaction with the lithium raw material, the worse the crystallinity is, and the more likely lithium is lost during the water washing process. Therefore, lithium nickel cobalt aluminum composite oxide containing aluminum shows a site occupancy rate with Li. Therefore, the Li site occupancy rate of the lithium nickel cobalt aluminum composite oxide according to one embodiment of the present invention is preferably 99.0% or more. This further improves the battery characteristics.

The nickel-cobalt-aluminum composite hydroxide can be mixed with a lithium compound and fired to produce lithium-nickel-cobalt-aluminum composite oxide. The lithium-nickel-cobalt-aluminum composite oxide can then be used as a raw material for the positive electrode active material of lithium-ion secondary batteries.

The lithium nickel cobalt aluminum composite oxide used as the positive electrode active material is obtained by mixing the precursor nickel cobalt aluminum composite hydroxide with lithium compounds such as lithium _carbonate ( _Li2CO3 : melting point 723°C), lithium hydroxide (LiOH: melting point 462°C), lithium nitrate ( _LiNO3 : melting point 261°C), lithium chloride (LiCl: melting point 613°C), and lithium sulfate _{( Li2SO4} : melting point 859°C), and then subjecting the mixture to a firing process.

As for the lithium compound, it is particularly preferable to use lithium carbonate or lithium hydroxide, taking into consideration ease of handling and stability of quality.

In this firing process, the carbonate, hydroxyl, nitrate, chlorine, and sulfate groups, which are also components of the lithium compound, volatilize, but a small portion remains in the positive electrode active material. As for other non-volatile components such as sodium, the particle size distribution, and specific surface area, the characteristics of the precursor nickel-cobalt-aluminum composite hydroxide are almost the same as those of the precursor.

After the above-mentioned firing process, the lithium nickel cobalt aluminum composite oxide containing aluminum is washed with water.

The lithium nickel cobalt aluminum composite oxide according to one embodiment of the present invention can provide a positive electrode active material for a lithium ion secondary battery that can reliably reduce the sodium content and achieve high capacity.

<3. Method for producing nickel-cobalt-aluminum composite hydroxide>
Next, a method for producing a nickel-cobalt aluminum composite hydroxide according to one embodiment of the present invention will be described with reference to Fig. 2. The method for producing a nickel-cobalt aluminum composite hydroxide according to one embodiment of the present invention is a method for producing a precursor of a positive electrode active material, which is composed of secondary particles formed by agglomeration of primary particles containing nickel, cobalt, and aluminum, or the primary particles and the secondary particles. As shown in Fig. 2, the method includes a crystallization step S10 and a washing step S20.

In the crystallization step S10, a raw material solution containing nickel, cobalt, and aluminum, a solution containing an ammonium ion donor, and an alkaline solution are added to obtain a reaction solution, and crystallization occurs to obtain a transition metal composite hydroxide. In the washing step S20, the transition metal composite hydroxide obtained in the crystallization step S10 is washed with a washing solution.

The alkaline solution in the crystallization step S10 is a mixed solution of an alkali metal hydroxide and a carbonate, and the molar ratio of the carbonate to the alkali metal hydroxide in the mixed solution, [CO ₃ ²⁻ ]/[OH ⁻ ], is 0.002 to 0.050, the crystallization step S10 is performed in a non-oxidizing atmosphere, and the washing solution in the washing step S20 is an ammonium hydrogen carbonate solution having a concentration of 0.05 mol/L or more. Each step will be described in detail below.

<3-1. Crystallization process>
In the crystallization step S10, a raw material solution containing nickel, cobalt, and aluminum, a solution containing an ammonium ion donor, and an alkaline solution are added to obtain a reaction solution, and crystallization is performed in the reaction solution to obtain a transition metal composite hydroxide. get.

The crystallization step S10 preferably further includes a nucleation step S11 and a particle growth step S12. In the nucleation step S11, an alkaline solution is added to generate nuclei in the reaction solution so that the pH measured at a liquid temperature of 25°C is 12.0 to 14.0, and in the particle growth step S12, an alkaline solution is preferably added to the reaction solution containing the nuclei formed in the nucleation step S11 so that the pH measured at a liquid temperature of 25°C is 10.5 to 12.0. Details will be described later.

In conventional continuous crystallization methods, the nucleation reaction and the nucleus growth reaction proceed simultaneously in the same reaction tank, resulting in a wide range of particle size distribution of the precursor. In contrast, the method for producing nickel-cobalt-aluminum composite hydroxide of the present invention clearly separates the time during which the nucleation reaction mainly occurs (nucleation process) from the time during which the particle growth reaction mainly occurs (particle growth process), thereby obtaining a transition metal composite hydroxide with a narrow particle size distribution even if both processes are carried out in the same reaction tank. In addition, by using a mixed solution of an alkali metal hydroxide and a carbonate as the alkaline solution, impurities such as sulfate radicals can be reduced.

The materials and conditions used in the method for producing nickel-cobalt-aluminum composite hydroxide of the present invention are described in detail below.

[Raw material solution containing nickel, cobalt, and aluminum]
Metal salts such as nickel salts and cobalt salts used in the raw material solution containing nickel, cobalt, and aluminum are not particularly limited as long as they are water-soluble compounds, and examples of such salts include sulfates, nitrates, chlorides, etc. For example, nickel sulfate and cobalt sulfate are preferably used.

The concentration of the raw material solution is preferably 1.0 to 2.6 mol/L, more preferably 1.0 to 2.2 mol/L, in terms of the total metal salts. If the concentration is less than 1.0 mol/L, the resulting hydroxide slurry will have a low concentration and will be less productive. On the other hand, if the concentration exceeds 2.6 mol/L, crystal precipitation or freezing will occur at temperatures below -5°C, which may clog the piping of the equipment, and the piping will need to be kept warm or heated, which will be costly.

Furthermore, the amount of raw material solution supplied to the reaction tank is preferably such that the crystallized product concentration at the end of the crystallization reaction is approximately 30 to 250 g/L, preferably 80 to 150 g/L. If the crystallized product concentration is less than 30 g/L, the primary particles may not aggregate sufficiently, and if it exceeds 250 g/L, the mixed aqueous solution added may not diffuse sufficiently in the reaction tank, resulting in uneven particle growth.

[Aluminum supplier]
It is preferable to use a solution containing sodium aluminate and sodium hydroxide as an aluminum supplier for the crystallization step. When other compounds, such as aluminum sulfate, are used, aluminum hydroxide precipitates at a lower pH than nickel hydroxide or cobalt hydroxide, so aluminum hydroxide is likely to precipitate alone, and it is not possible to obtain a nickel-cobalt-aluminum composite hydroxide with a narrow particle size distribution and uniform particle size.

The aluminum supply can be obtained, for example, by dissolving a predetermined amount of sodium aluminate in water to prepare an aqueous solution, and then adding a predetermined amount of sodium hydroxide. At this time, it is more preferable that the molar ratio of sodium to aluminum in the aluminum supply is 1.0 to 3.0. If the amount of sodium, i.e., the amount of sodium hydroxide, is outside the range of 1.0 to 3.0 in terms of molar ratio, the stability of the aluminum supply decreases, and aluminum hydroxide is likely to precipitate as fine particles immediately after or before it is added to the reaction tank. As a result, the coprecipitation reaction with nickel hydroxide and cobalt hydroxide becomes difficult to occur, and a nickel-cobalt-aluminum composite hydroxide with a wide particle size distribution and variable particle size is produced, and problems such as uneven dispersion of aluminum particles may occur, which is not preferable.

To uniformly disperse aluminum in the nickel-cobalt-aluminum composite hydroxide, a raw material solution containing nickel and cobalt and an aluminum supplier are added to the reaction tank at the same time. At this time, the metal concentrations of nickel, cobalt, and aluminum, and the flow rates of the raw material solution and aluminum supplier are adjusted to obtain the nickel-cobalt-aluminum composite hydroxide with the target composition ratio.

[Ammonium ion donor]
The ammonium ion donor in the reaction solution is not particularly limited as long as it is a water-soluble compound, and examples of the donor include ammonia water, ammonium sulfate, ammonium chloride, ammonium carbonate, and ammonium fluoride. For example, it is preferable to use ammonia water or ammonium sulfate.

The ammonium ion concentration in the reaction solution is adjusted to preferably 3 to 25 g/L, more preferably 10 to 20 g/L, and even more preferably 5 to 15 g/L. The presence of ammonium ions in the reaction solution causes metal ions, particularly nickel ions, to form ammine complexes, increasing the solubility of the metal ions and promoting the growth of primary particles, making it easier to obtain dense nickel-cobalt-aluminum composite hydroxide particles. Furthermore, because the solubility of the metal ions is stable, nickel-cobalt-aluminum composite hydroxide particles with a uniform shape and particle size are easily obtained. And, by setting the ammonium ion concentration in the reaction solution to 3 to 25 g/L, it is easier to obtain composite hydroxide particles that are denser and have a uniform shape and particle size.

If the ammonium ion concentration in the reaction solution is less than 3 g/L, the solubility of the metal ions may become unstable, and primary particles with uniform shape and particle size may not be formed, and gel-like nuclei may be generated, resulting in a wide particle size distribution. In contrast, if the ammonium ion concentration exceeds 25 g/L, the solubility of the metal ions may become too high, and the amount of metal ions remaining in the reaction solution may increase, causing a deviation in the composition. The concentration of ammonium ions can be measured using an ion electrode method (ion meter).

[Alkaline solution]
The alkaline solution is prepared by mixing an alkali metal hydroxide and a carbonate. The molar ratio of the alkali metal hydroxide to the carbonate, [CO ₃ ²⁻ ]/[OH ⁻ ], is 0.002 to 0.050. It is more preferable that the ratio is 0.005 to 0.030, and further more preferable that the ratio is 0.010 to 0.025.

By using a mixed solution of alkali metal hydroxide and carbonate as the alkaline solution, it is possible to replace and remove anions such as sulfate and chlorine that remain as impurities in the nickel-cobalt-aluminum composite hydroxide obtained in the crystallization process with carbonate. Carbonate is more easily volatilized by ignition than sulfate and chlorine, and is preferentially volatilized during the process of mixing and firing the nickel-cobalt-aluminum composite hydroxide with a lithium compound, so almost no carbonate remains in the lithium-nickel-cobalt-aluminum composite oxide, which is the positive electrode material.

If the ratio [CO ₃ ^2- ]/[OH ^- ] is less than 0.002, the replacement of the impurities sulfate and chlorine derived from the raw materials with carbonate ions becomes insufficient in the crystallization step, and these impurities become easily incorporated into the nickel-cobalt-aluminum composite hydroxide. On the other hand, even if the ratio [CO ₃ ^2- ]/[OH ^- ] exceeds 0.050, the reduction in the impurities sulfate and chlorine derived from the raw materials remains unchanged, and the excess carbonate added increases costs.

The alkali metal hydroxide is preferably one or more of lithium hydroxide, sodium hydroxide, and potassium hydroxide, and compounds that are easily soluble in water are preferred because the amount added is easy to control.

The carbonate is preferably one or more of sodium carbonate, potassium carbonate, and ammonium carbonate, and compounds that are easily soluble in water are preferred because the amount added is easy to control.

The method for adding the alkaline solution to the reaction tank is not particularly limited, and it may be added using a pump capable of controlling the flow rate, such as a metering pump, so that the pH of the reaction solution is maintained within the range described below.

[pH Control]
It is more preferable that the crystallization step S10 comprises a nucleation step S11 in which an alkaline solution is added to generate nuclei so that the pH of the reaction solution measured at a liquid temperature of 25° C. is 12.0 to 14.0, and a particle growth step S12 in which an alkaline solution is added to the particle growth solution containing the nuclei formed in the nucleation step S11 so that the pH of the solution measured at a liquid temperature of 25° C. is 10.5 to 12.0, thereby growing the nuclei.

In other words, the nucleation reaction and the particle growth reaction do not proceed at the same time in the same tank, but rather the time during which the nucleation reaction (nucleation step S11) mainly occurs and the time during which the particle growth reaction (particle growth step S12) mainly occurs are clearly separated. The nucleation step S11 and the particle growth step S12 are described in detail below.

<3-1-1. Nucleation process>
In the nucleation step S11, it is preferable to control the pH of the reaction solution to be in the range of 12.0 to 14.0 at a liquid temperature of 25° C. If the pH exceeds 14.0, the nuclei generated If the pH is less than 12.0, the nuclei will grow together with the nuclei formation, resulting in a wide range of particle size distribution of the nuclei. It may become inhomogeneous.

That is, in the nucleation step S11, by controlling the pH of the reaction solution in the range of 12.0 to 14.0, it is possible to suppress the growth of nuclei and cause only nucleation to occur, and the nuclei formed are homogeneous and have a narrower particle size distribution range.

<3-1-2. Particle growth process>
In the particle growth step S12, the pH of the reaction solution is preferably 10.5 to 12.0, more preferably 11.0 to 12.0, based on a liquid temperature of 25° C. If the pH exceeds 0.0, the number of newly generated nuclei increases, resulting in the generation of fine secondary particles, and it may not be possible to obtain hydroxides with a good particle size distribution. In the case of ammonium ions, the solubility of the metal ions is high, and the amount of metal ions that remain in the solution without being precipitated increases, which may result in a decrease in production efficiency.

In other words, by controlling the pH of the reaction solution in the particle growth step S12 to a range of 10.5 to 12.0, it is possible to preferentially cause the growth of only the nuclei generated in the nucleation step S11 and suppress the formation of new nuclei, and to obtain a nickel-cobalt-aluminum composite hydroxide that is homogeneous and has a narrower particle size distribution range.

In addition, since a pH of 12.0 is the boundary condition between nucleation and nucleus growth, the conditions can be set to either the nucleation process or the particle growth process depending on the presence or absence of nuclei in the reaction solution. In other words, if the pH of the nucleation process S11 is made higher than 12.0 to generate a large amount of nuclei, and then the pH is made 12.0 in the particle growth process S12, the large amount of nuclei is present in the reaction aqueous solution, so nucleus growth takes precedence, and the above hydroxide with a narrower particle size distribution and a relatively large particle size is obtained.

On the other hand, when no nuclei are present in the reaction solution, that is, when the pH is set to 12.0 in the nucleation step S11, there are no nuclei to grow, and nucleation takes precedence. By setting the pH in the particle growth step S12 to a value less than 12.0, the generated nuclei grow, resulting in a better hydroxide.

In either case, the pH of the particle growth process S12 may be controlled to a value lower than the pH of the nucleation process S11. In order to clearly separate nucleation and particle growth, it is preferable to set the pH of the particle growth process S12 at least 0.5 lower than the pH of the nucleation process S11, and more preferably at least 1.0 lower.

As described above, by clearly separating the nucleation step S11 and the particle growth step S12 by pH, nucleation takes precedence in the nucleation step S11, with little nucleus growth, and conversely, in the particle growth step S12, only nucleus growth occurs, with almost no new nuclei being generated. As a result, in the nucleation step S11, nuclei with a narrow particle size distribution range can be formed, and in the particle growth step S12, nuclei can be grown uniformly. Therefore, the method for producing nickel-cobalt-aluminum composite hydroxide can produce nickel-cobalt-aluminum composite hydroxide particles with a narrower particle size distribution range and more uniform.

[Reaction solution temperature]
In the reaction tank, the temperature of the reaction solution is preferably set to 20 to 80° C., more preferably 30 to 70° C., and even more preferably 35 to 60° C. If the temperature of the reaction solution is less than 20° C., the solubility of metal ions is low, so nucleation is likely to occur and control is difficult. On the other hand, if the temperature exceeds 80° C., the volatilization of ammonia is promoted, so that an excess of ammonium ion donor must be added to maintain a predetermined ammonia concentration, resulting in high costs.

[Reaction atmosphere]
The particle size and particle structure of the nickel-cobalt-aluminum composite hydroxide are also controlled by the reaction atmosphere in the crystallization step S10. Therefore, in the crystallization step S10, crystallization is performed in a non-oxidizing atmosphere. When the atmosphere in the reaction tank in the crystallization step S10 is controlled to a non-oxidizing atmosphere, the growth of the primary particles forming the nickel-cobalt-aluminum composite hydroxide is promoted, and the primary particles are large and dense, and secondary particles having a moderately large particle size are formed. In particular, by setting the non-oxidizing atmosphere in the crystallization step S10 with an oxygen concentration of 5.0 volume % or less, preferably 2.5 volume % or less, and more preferably 1.0 volume % or less, nuclei are generated from relatively large primary particles, and particle growth is promoted by the aggregation of the primary particles, so that secondary particles of a moderate size can be obtained. Therefore, a solid-type nickel-cobalt-aluminum composite hydroxide as shown in FIG. 1 is obtained. On the other hand, when the atmosphere in the reaction tank during the crystallization step is controlled to be an oxidizing atmosphere, the growth of the primary particles that form the nickel-cobalt-aluminum composite hydroxide is suppressed, and secondary particles that are made of fine primary particles and have a large number of spaces or fine voids dispersed in the center of the particles are formed.

A non-oxidizing atmosphere refers to a mixed atmosphere of oxygen with an oxygen concentration of 5.0% by volume or less, preferably 2.5% by volume or less, and more preferably 1.0% by volume or less, and an inert gas. Means for maintaining such a non-oxidizing atmosphere within the reaction vessel include circulating an inert gas such as nitrogen into the reaction vessel space, and further bubbling an inert gas into the reaction solution. The preferred flow rate of bubbling in the crystallization step S10 is 3 to 7 L/min, and more preferably about 5 L/min.

On the other hand, an oxidizing atmosphere refers to an atmosphere in which the oxygen concentration exceeds 5.0% by volume, preferably 10.0% by volume or more, and more preferably 15.0% by volume or more.

When creating a solid structure such as the nickel-cobalt-aluminum composite hydroxide according to one embodiment of the present invention, it is preferable to make the atmosphere in the reaction tank an inert atmosphere or a non-oxidizing atmosphere in which the oxygen concentration is controlled to 0.2% by volume or less during the crystallization step S10.

The nucleation step S11 and the particle growth step S12 have been described above, but the reaction atmosphere is controlled simultaneously while nucleation and particle growth are taking place.

<2-2. Cleaning process>
In the washing step S20, the transition metal composite hydroxide obtained in the crystallization step S10 is washed with a washing liquid.

[Cleaning fluid type]
In the washing step S20, washing is performed with a washing solution based on an alkali metal salt or ammonium salt of a carbonate, hydrogen carbonate (bicarbonate), or hydroxide. Preferably, the transition metal composite hydroxide is washed with a washing solution in which a carbonate, hydrogen carbonate (bicarbonate), or a mixture thereof is dissolved in water.

By doing so, it is possible to efficiently remove impurity anions such as sulfate and chlorine radicals by utilizing a substitution reaction with the carbonate ions and hydrogen carbonate ions (bicarbonate ions) in the cleaning solution. In addition, by using carbonates and hydrogen carbonates (bicarbonates), it is possible to suppress the inclusion of alkali metals such as sodium compared to when hydroxides are used. In addition, when hydroxides are used in transition metal composite hydroxides that have a porous structure, it is difficult to remove impurities inside the particles, and in this respect, too, it is more effective to use carbonates and hydrogen carbonates (bicarbonates).

As the carbonate, it is preferable to select sodium carbonate, potassium carbonate, or ammonium carbonate, and as the hydrogen carbonate (bicarbonate), it is preferable to select sodium hydrogen carbonate, potassium hydrogen carbonate, or ammonium hydrogen carbonate. Furthermore, by selecting an ammonium salt from among the carbonates and hydrogen carbonates (bicarbonates), it is possible to efficiently remove cations such as sodium, which are impurities, by utilizing a substitution reaction with the ammonium ions in the cleaning solution. Furthermore, by selecting ammonium hydrogen carbonate from among the ammonium salts, it is possible to most efficiently remove cations such as sodium.

This is because it is not only the replacement reaction between cations such as sodium and ammonium ions, but also the superior properties of ammonium bicarbonate compared to other salts, namely the high foaming efficiency of carbon dioxide gas when used as a cleaning solution, which is thought to contribute greatly to the removal of cations such as sodium.

[Concentration and pH]
The concentration of the ammonium bicarbonate solution, which is the cleaning solution, is 0.05 mol/L or more. If the concentration is less than 0.05 mol/L, the effect of removing impurities such as sulfate radicals, chlorine radicals, and sodium may decrease. If the concentration is 0.05 mol/L or more, the effect of removing these impurities remains unchanged. Therefore, adding an excess of ammonium bicarbonate (ammonium bicarbonate) increases costs and affects environmental loads such as wastewater standards, so it is preferable to set the upper limit concentration at about 1.0 mol/L.

The pH of the ammonium bicarbonate solution does not need to be adjusted if the concentration is 0.05 mol/L or more, and can be left at its natural pH. If the concentration is 0.05 to 1.0 mol/L, the pH will be in the range of approximately 8.0 to 9.0.

[Liquid temperature]
The temperature of the ammonium bicarbonate solution, which is the cleaning solution, is not particularly limited, but is preferably 15 to 50° C. If the temperature of the solution is within the above range, the substitution reaction with impurities and the bubbling effect of carbon dioxide gas generated from ammonium bicarbonate are more favorable, and the removal of impurities proceeds efficiently.

[Liquid volume]
The amount of the ammonium bicarbonate solution, which is the cleaning solution, is preferably 1 to 20 L per 1 kg of nickel-cobalt-aluminum composite hydroxide (slurry concentration is 50 to 1000 g/L). If the amount is less than 1 L, the impurity removal effect may not be sufficient. Even if an amount of the solution exceeding 20 L is used, the impurity removal effect remains the same, and an excessive amount of the solution increases costs, affects the environmental load such as wastewater standards, and is also a factor in increasing the load of the wastewater volume in wastewater treatment.

[Washing time]
The washing time with the ammonium hydrogen carbonate solution is not particularly limited as long as it can sufficiently remove impurities, but it is usually 0.5 to 2 hours.

[Cleaning method]
The washing method may be 1) a general washing method in which nickel-cobalt-aluminum composite hydroxide is added to an ammonium hydrogen carbonate solution to form a slurry, which is stirred and washed, and then filtered, or 2) a liquid-passing washing method in which a slurry containing nickel-cobalt-aluminum composite hydroxide produced by neutralization crystallization is supplied to a filter such as a filter press, and an ammonium hydrogen carbonate solution is passed through the slurry. Liquid-passing washing is more preferable because it has a high impurity removal effect, can perform filtration and washing continuously in the same equipment, and is highly productive.

After washing with the ammonium bicarbonate solution, the washing solution containing impurities washed out by the substitution reaction may adhere to the nickel-cobalt-aluminum composite hydroxide, so it is preferable to finally wash with water. Furthermore, after washing with water, it is preferable to perform a drying process (not shown) to dry the water adhering to the filtered nickel-cobalt-aluminum composite hydroxide.

The nickel-cobalt-aluminum composite hydroxide obtained through the washing step S20 is a precursor of a positive electrode active material composed of secondary particles in which primary particles containing nickel, cobalt, and aluminum are aggregated, or the primary particles and the secondary particles, and is characterized in that the sodium content contained in the nickel-cobalt-aluminum composite hydroxide is less than 0.0005% by mass.

The method for producing nickel-cobalt-aluminum composite hydroxide according to one embodiment of the present invention can reliably reduce the sodium content, and provide a method for producing nickel-cobalt-aluminum composite hydroxide containing nickel, cobalt, and aluminum, which is a precursor of the positive electrode active material for lithium-ion secondary batteries that can achieve high capacity.

Next, the nickel-cobalt-aluminum composite hydroxide, the method for producing the nickel-cobalt-aluminum composite hydroxide, and the lithium-nickel-cobalt-aluminum composite oxide according to one embodiment of the present invention will be described in detail with reference to examples. Note that the present invention is not limited to these examples.

For Examples 1 to 16 and Comparative Examples 1 to 8, the transition metal composite hydroxide obtained in the crystallization process was washed, filtered, and dried to recover the precursor nickel-cobalt-aluminum composite hydroxide, and then various analyses were performed using the following methods.

[composition]
The composition was analyzed by acid decomposition-ICP emission spectrometry, and a multi-type ICP emission spectrometry analyzer, ICPE-9000 (manufactured by Shimadzu Corporation), was used for the measurements.

[Sodium content]
The sodium content was analyzed by acid decomposition-atomic absorption spectrometry, and an atomic absorption spectrophotometer 240AA (manufactured by Agilent Technologies, Inc.) was used as an atomic absorption analyzer for the measurement.

[Sulfate content]
The sulfate radical content was determined by analyzing the total sulfur content by acid decomposition-ICP atomic emission spectrometry and converting the total sulfur content into sulfate radical (SO ₄ ²⁻ ). The measurement was performed using a multi-type ICP atomic emission spectrometry analyzer, ICPE-9000 (manufactured by Shimadzu Corporation).

[Chlorine content]
The chlorine radical content was analyzed by X-ray fluorescence spectrometry (XRF) either directly from the sample or by separating the chlorine radical contained in the sample in the form of silver chloride by distillation. For the measurement, an X-ray fluorescence analyzer, Axios (manufactured by Spectris, Inc.), was used.

[Average particle size and particle size distribution]
The average particle size (MV) and particle size distribution [(d90-d10)/average particle size] were determined from the volume-based distribution measured using a laser diffraction/scattering method, using a Microtrac MT3300EXII (manufactured by Microtrac Bell Co., Ltd.), a particle size distribution measuring device using a laser diffraction/scattering method.

[Specific surface area]
The specific surface area was analyzed by a nitrogen gas adsorption/desorption method according to the BET single point method, and a gas flow type specific surface area measuring device, Macsorb 1200 series (manufactured by Mountec Co., Ltd.), was used for the measurement.

[Production and evaluation of positive electrode active material]
Furthermore, the lithium metal composite oxide, more specifically the lithium nickel cobalt aluminum composite oxide, which is the positive electrode active material made from the nickel cobalt aluminum composite hydroxide of the present invention, was produced and evaluated by the following method.

[A. Production of positive electrode active material]
The precursor nickel-cobalt-aluminum composite hydroxide was heat-treated at 700°C for 6 hours in an air stream (oxygen: 21% by volume), and the metal composite oxide was recovered. Furthermore, lithium hydroxide, a lithium compound, was weighed out so that Li/Me=1.025, and mixed with the recovered metal composite oxide to prepare a lithium mixture. A shaker mixer (TURBULA-Type T2C manufactured by WAB) was used for the mixing operation.

Next, the lithium mixture was calcined in an oxygen (oxygen: 100% by volume) stream at 500°C for 4 hours, then sintered at 730°C for 24 hours, cooled, and crushed to obtain lithium nickel cobalt aluminum composite oxide.

[B. Evaluation of Positive Electrode Active Material]
The above-mentioned analytical method and analytical equipment were used to analyze the sodium content, sulfate content, and chlorine content of the obtained lithium nickel cobalt aluminum composite oxide. The Li site occupancy rate, which indicates the crystallinity of the lithium nickel cobalt aluminum composite oxide, was calculated by performing Rietveld analysis from a diffraction pattern measured using an X-ray diffraction analyzer (XRD). The measurement was performed using an X-ray diffraction analyzer X'Pert-PRO (manufactured by Spectris Co., Ltd.). The Li site occupancy rate indicates the proportion of lithium element in the lithium layer (Li site) of the layered structure of the lithium nickel cobalt aluminum composite oxide. The Li site occupancy rate is correlated with battery characteristics, and the higher the Li site occupancy rate, the better the battery characteristics.

The conditions for the examples and comparative examples are explained below.

Example 1
In Example 1, 0.9 L of water was placed in a crystallization reaction tank (5 L) in the crystallization step, and the temperature inside the tank was set to 50° C. while stirring. Nitrogen gas was circulated through the reaction tank to create a nitrogen atmosphere. The oxygen concentration in the reaction tank space at this time was 2.0% by volume.

An appropriate amount of 25% sodium hydroxide aqueous solution and 25% ammonia water, which is an ammonium ion donor, were added to the water in the reaction tank, and the pH of the reaction solution in the tank was adjusted to 12.8, measured based on a liquid temperature of 25°C. The ammonium ion concentration of the reaction solution was also adjusted to 10 g/L.

Next, nickel sulfate and cobalt chloride were dissolved in water to prepare a raw material solution of 2.0 mol/L. In this raw material solution, the elemental molar ratio of each metal was adjusted to Ni:Co = 0.84:0.16. Separately, a predetermined amount of sodium aluminate was dissolved in water, and 25% sodium hydroxide solution was added to the solution so that the molar ratio of sodium to aluminum was 1.7 to prepare an aluminum supplier. Furthermore, sodium hydroxide, which is an alkali metal hydroxide, and sodium carbonate, which is a carbonate, were dissolved in water so that [CO ₃ ^2- ]/[OH ^- ] was 0.025 to prepare an alkaline solution.

The raw material solution was added to the reaction solution in the reaction tank at 12.9 ml/min, and the ammonium ion donor and alkaline solution were also added to the reaction solution at a constant rate. Nucleation was performed by controlling the pH to 12.8 (nucleation step pH) while maintaining the ammonium ion concentration in the reaction solution at 10 g/L, and carrying out crystallization for 2 minutes and 30 seconds. The addition rate of the aluminum donor was adjusted so that the molar ratio of metal elements in the slurry was Ni:Co:Al = 81:16:3.

After that, 64% sulfuric acid was added until the pH of the reaction solution reached 11.6 (particle growth process pH) measured at a liquid temperature of 25°C. After the pH of the reaction solution reached 11.6, measured at a liquid temperature of 25°C, the supply of the raw material solution, aluminum donor, ammonium ion donor, and alkaline solution was resumed, and the pH was controlled at 11.6 while crystallization was continued for 4 hours to grow particles, thereby obtaining a transition metal composite hydroxide.

The obtained transition metal composite hydroxide was subjected to solid-liquid separation using a filter press filter, and then impurities were removed by passing 5 L of the washing solution through the filter press filter per 1 kg of transition metal composite hydroxide using a 0.05 mol/L ammonium bicarbonate solution as a washing solution, and then water was passed through the filter press filter for washing. The water adhering to the washed transition metal composite hydroxide was then dried to obtain the precursor nickel-cobalt-aluminum composite hydroxide.

Example 2
In Example 2, a nickel-cobalt-aluminum composite hydroxide was obtained in the same manner as in Example 1, except that the addition rate of the aluminum supplier was adjusted so that the molar ratio of metal elements in the slurry was Ni:Co:Al=78:15:7.

Example 3
In Example 3, a nickel-cobalt-aluminum composite hydroxide was obtained in the same manner as in Example 1, except that the addition rate of the aluminum supplier was adjusted so that the molar ratio of metal elements in the slurry was Ni:Co:Al=74:14:12.

Example 4
In Example 4, a nickel-cobalt-aluminum composite hydroxide was obtained in the same manner as in Example 1, except that the addition rate of the aluminum supplier was adjusted so that the molar ratio of metal elements in the slurry was Ni:Co:Al=69:13:18.

Example 5
In Example 5, a nickel-cobalt-aluminum composite hydroxide was obtained in the same manner as in Example 1, except that the alkaline solution was prepared such that [CO ₃ ²⁻ ]/[OH ⁻ ] was adjusted to 0.003.

Example 6
In Example 6, a nickel-cobalt-aluminum composite hydroxide was obtained in the same manner as in Example 1, except that the alkaline solution was adjusted so that [CO ₃ ²⁻ ]/[OH ⁻ ] was 0.048.

(Example 7)
In Example 7, a nickel-cobalt-aluminum composite hydroxide was obtained in the same manner as in Example 1, except that in preparing the aluminum donor, a 25% sodium hydroxide solution was added to a solution in which sodium aluminate was dissolved in water so that the ratio of sodium to aluminum became 1.0.

(Example 8)
In Example 8, a nickel-cobalt-aluminum composite hydroxide was obtained in the same manner as in Example 1, except that in preparing the aluminum donor, a 25% aqueous solution of sodium hydroxide was added to a solution in which sodium aluminate was dissolved in water so that the ratio of sodium to aluminum was 3.0.

(Example 9)
In Example 9, a nickel-cobalt-aluminum composite hydroxide was obtained in the same manner as in Example 1, except that the pH in the nucleation step was 13.6.

(Example 10)
In Example 10, a nickel-cobalt-aluminum composite hydroxide was obtained in the same manner as in Example 1, except that the pH in the nucleation step was 12.3.

Example 11
In Example 11, a nickel-cobalt-aluminum composite hydroxide was obtained in the same manner as in Example 1, except that the pH in the particle growth step was 11.8.

Example 12
In Example 12, a nickel-cobalt-aluminum composite hydroxide was obtained in the same manner as in Example 1, except that the pH in the particle growth step was 10.6.

Example 13
In Example 13, a nickel-cobalt-aluminum composite hydroxide was obtained in the same manner as in Example 1, except that when preparing the alkaline solution, potassium hydroxide was used as the alkali metal hydroxide and potassium carbonate was used as the carbonate.

(Example 14)
In Example 14, a nickel-cobalt-aluminum composite hydroxide was obtained in the same manner as in Example 1, except that, when preparing the alkaline solution, ammonium carbonate was used as the carbonate and the ammonium ion concentration was adjusted to 20 g/L.

(Example 15)
In Example 15, a nickel-cobalt-aluminum composite hydroxide was obtained in the same manner as in Example 1, except that the temperature in the tank was set to 35° C.

(Example 16)
In Example 16, a nickel-cobalt-aluminum composite hydroxide was obtained in the same manner as in Example 1, except that an ammonium bicarbonate solution with a concentration of 1.00 mol/L was used as the cleaning liquid.

(Comparative Example 1)
In Comparative Example 1, a nickel-cobalt-aluminum composite hydroxide was obtained in the same manner as in Example 1, except that only sodium hydroxide was used to prepare the alkaline solution and [CO ₃ ²⁻ ]/[OH ⁻ ] was not taken into consideration.

(Comparative Example 2)
In Comparative Example 2, a nickel-cobalt-aluminum composite hydroxide was obtained in the same manner as in Example 1, except that the alkaline solution was adjusted so that [CO ₃ ²⁻ ]/[OH ⁻ ] was 0.001.

(Comparative Example 3)
In Comparative Example 3, a nickel-cobalt-aluminum composite hydroxide was obtained in the same manner as in Example 1, except that the alkaline solution was adjusted so that [CO ₃ ²⁻ ]/[OH ⁻ ] was 0.055.

(Comparative Example 4)
In Comparative Example 4, a nickel-cobalt-aluminum composite hydroxide was obtained in the same manner as in Example 1, except that the washing step was omitted and washing with an ammonium hydrogen carbonate solution was not performed.

(Comparative Example 5)
In Comparative Example 5, a nickel-cobalt-aluminum composite hydroxide was obtained in the same manner as in Example 1, except that an ammonium bicarbonate solution with a concentration of 0.02 mol/L was used as the cleaning liquid.

(Comparative Example 6)
In Comparative Example 6, a nickel-cobalt-aluminum composite hydroxide was obtained in the same manner as in Example 1, except that an ammonium carbonate solution was used as the cleaning liquid.

(Comparative Example 7)
In Comparative Example 7, a nickel-cobalt-aluminum composite hydroxide was obtained in the same manner as in Example 1, except that a sodium hydrogen carbonate solution was used as the cleaning liquid.

(Comparative Example 8)
In Comparative Example 8, a nickel-cobalt-aluminum composite hydroxide was obtained in the same manner as in Example 1, except that a sodium carbonate solution was used as the cleaning liquid.

The above conditions and results are shown in Tables 1 and 2.

(comprehensive evaluation)
As shown in Tables 1 and 2, in Examples 1 to 16, the conditions of the crystallization step and the washing step in the nickel-cobalt-aluminum composite hydroxide precursor were all within the preferred ranges. Therefore, not only in the nickel-cobalt-aluminum composite hydroxide but also in the lithium-nickel-cobalt-aluminum composite oxide, which is the positive electrode active material, the sodium content, sulfate content, and chlorine content were sufficiently reduced in the impurity removal. Furthermore, in the lithium-nickel-cobalt-aluminum composite oxide, the Li site occupancy rate exceeded 99.0%, resulting in excellent crystallinity and improved battery characteristics.

In particular, the sodium content of both the precursor and the positive electrode active material showed very good results, with all example data being less than the quantitative (analytical) value (0.0005% by mass).

The lower limit of quantification here means the minimum amount or minimum concentration at which a target component can be analyzed (quantified) using a certain analytical method. The minimum amount (value) at which a signal of the target component can be detected in a measurement is called the detection limit, and the minimum amount (value) at which the signal of the target component obtained in a measurement is reliable is called the lower limit of measurement. Furthermore, the lower limit of quantification can be calculated by multiplying the lower limit of measurement by the dilution factor, which indicates how much the original analytical sample has been concentrated or diluted in the process of preparing the analytical sample into the measurement specimen liquid.

In other words, the sodium content in this invention is 0.05 μg/mL, which is the lower limit of measurement for an atomic absorption spectrometer, and because 1 g of the analytical sample was acid-decomposed to prepare 100 mL of measurement specimen liquid (dilution ratio: 100 times), the lower limit of quantification is 5 ppm (μg/g), or 0.0005% by mass.

In contrast, in Comparative Examples 1 to 8, the [CO ₃ ²⁻ ]/[OH ⁻ ] ratio when preparing the alkaline solution and the concentration of the ammonium bicarbonate solution used as the cleaning liquid were not within the preferred range, or a cleaning liquid other than ammonium bicarbonate solution was used, so that the excellent effects of the Examples were not obtained.

As a result of the above, we have been able to provide a nickel-cobalt-aluminum composite hydroxide containing nickel, cobalt, and aluminum, which is a precursor of a positive electrode active material for lithium-ion secondary batteries that can reliably reduce the sodium content in particular and increase capacity, a method for producing the nickel-cobalt-aluminum composite hydroxide, and a lithium-nickel-cobalt-aluminum composite oxide. Furthermore, it is expected that this will also lead to the provision of lithium-ion secondary batteries with excellent characteristics.

Although each embodiment and each example of the present invention has been described in detail above, it will be readily apparent to those skilled in the art that many modifications are possible that do not substantially deviate from the novel features and effects of the present invention. Therefore, all such modifications are intended to be included within the scope of the present invention.

For example, a term described at least once in the specification or drawings together with a different term having a broader or synonymous meaning may be replaced with that different term anywhere in the specification or drawings. Furthermore, the nickel-cobalt-aluminum composite hydroxide, the method for producing the nickel-cobalt-aluminum composite hydroxide, and the configuration and operation of the lithium-nickel-cobalt-aluminum composite oxide are not limited to those described in the embodiments and examples of the present invention, and various modifications are possible.

S10 Crystallization process, S11 Nucleation process, S12 Particle growth process, S20 Washing process

Claims (5)

A nickel-cobalt-aluminum composite hydroxide, which is a precursor of a positive electrode active material, is composed of secondary particles in which primary particles containing nickel, cobalt, and aluminum are aggregated, or the primary particles and the secondary particles,
The nickel-cobalt-aluminum composite hydroxide has a sodium content of less than 0.0005% by mass and a chlorine radical content of 0.01% by mass or less. 2. The nickel-cobalt-aluminum composite hydroxide according to claim 1, wherein the nickel-cobalt-aluminum composite hydroxide has a specific surface area of 30 to 50 m ² /g. The nickel-cobalt-aluminum composite hydroxide according to claim 1 or 2, characterized in that the content of sulfate radicals contained in the nickel-cobalt-aluminum composite hydroxide is 0.2 mass% or less. The nickel-cobalt-aluminum composite hydroxide according to any one of claims 1 to 3, characterized in that the index showing the spread of the particle size distribution of the nickel-cobalt-aluminum composite hydroxide, [(d90-d10)/average particle size], is 0.55 or less. The nickel-cobalt-aluminum composite hydroxide according to any one of claims 1 to 4 _, characterized in that the nickel-cobalt-aluminum composite hydroxide is represented by the general formula: _{Ni1-x- yCoxAly} (OH) _2+a (wherein 0.05≦x≦0.35, 0.01≦y≦0.20, x+y<0.40, and 0≦a≦0.5).