WO2016067960A1 - Hydroxyde composite de nickel et son procédé de préparation - Google Patents

Hydroxyde composite de nickel et son procédé de préparation Download PDF

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Publication number
WO2016067960A1
WO2016067960A1 PCT/JP2015/079491 JP2015079491W WO2016067960A1 WO 2016067960 A1 WO2016067960 A1 WO 2016067960A1 JP 2015079491 W JP2015079491 W JP 2015079491W WO 2016067960 A1 WO2016067960 A1 WO 2016067960A1
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Prior art keywords
nickel composite
composite hydroxide
hydroxide
aqueous solution
carbonate
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PCT/JP2015/079491
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English (en)
Japanese (ja)
Inventor
寛子 大下
一臣 漁師
高木　正徳
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住友金属鉱山株式会社
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Priority claimed from JP2015125811A external-priority patent/JP6287970B2/ja
Application filed by 住友金属鉱山株式会社 filed Critical 住友金属鉱山株式会社
Priority to CN201580059107.6A priority Critical patent/CN107001070B/zh
Priority to EP15853848.8A priority patent/EP3225591B1/fr
Priority to US15/523,568 priority patent/US10294120B2/en
Publication of WO2016067960A1 publication Critical patent/WO2016067960A1/fr

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    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
    • C01G53/00—Compounds of nickel
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
    • H01M4/52—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of nickel, cobalt or iron
    • H01M4/525—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of nickel, cobalt or iron of mixed oxides or hydroxides containing iron, cobalt or nickel for inserting or intercalating light metals, e.g. LiNiO2, LiCoO2 or LiCoOxFy
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/10—Energy storage using batteries

Definitions

  • the present invention relates to a nickel composite hydroxide serving as a precursor of a positive electrode active material used as a positive electrode material in a non-aqueous electrolyte secondary battery such as a lithium ion secondary battery and a method for producing the same.
  • This application includes Japanese Patent Application No. 2014-221859 filed on October 30, 2014 in Japan and Japanese Patent Application No. 2015-2015 filed on June 23, 2015 in Japan. The priority is claimed on the basis of 125811, which is incorporated herein by reference.
  • a lithium ion secondary battery includes a negative electrode, a positive electrode, an electrolyte, and the like, and a material capable of detaching and inserting lithium is used as an active material for the negative electrode and the positive electrode.
  • lithium ion secondary batteries using a layered or spinel type lithium metal composite oxide as a positive electrode material have a high voltage of 4V. Therefore, practical use is progressing as a battery having a high energy density.
  • LiCoO 2 lithium cobalt composite oxide
  • the lithium cobalt composite oxide uses a rare and expensive cobalt compound as a raw material, it causes an increase in the cost of the active material and the battery, and an alternative to the active material is desired.
  • lithium nickel composite oxide (LiNiO 2 ), which can be expected to have a higher capacity using nickel cheaper than cobalt, has attracted attention.
  • Lithium-nickel composite oxide not only has a low cost but also has a lower electrochemical potential than lithium-cobalt composite oxide. Therefore, decomposition due to oxidation of the electrolyte is less problematic, and higher capacity can be expected. Since it shows a high battery voltage as well as the system, it has been actively developed.
  • the lithium-nickel composite oxide when a lithium ion secondary battery is produced using a material synthesized purely of nickel alone as a positive electrode active material, is inferior in cycle characteristics compared to cobalt-based materials, and also in a high temperature environment. When used or stored, there is a drawback that the battery performance is relatively easily lost.
  • Patent Document 1 in order to improve the self-discharge characteristics and cycle characteristics of the lithium ion secondary battery, Li x Ni a Co b M c O 2 (0.8 ⁇ x ⁇ 1.2, 0.01 ⁇ a ⁇ 0.99, 0.01 ⁇ b ⁇ 0.99, 0.01 ⁇ c ⁇ 0.3, 0.8 ⁇ a + b + c ⁇ 1.2, M is Al , V, Mn, Fe, Cu, and Zn) have been proposed.
  • LiNi x M 1-x O 2 (M is Co, Mn, Cr, Fe, V, Al) as a positive electrode active material that provides a non-aqueous electrolyte secondary battery with high capacity and excellent cycle characteristics.
  • Lithium-containing composite oxides, etc. which are one or more selected from the above and represented by x: 1> x ⁇ 0.5) have been proposed.
  • the lithium nickel composite oxide obtained by the manufacturing methods as described in Patent Documents 1 and 2 has higher charge capacity and discharge capacity than the lithium cobalt composite oxide and improved cycle characteristics. Only in the second charge / discharge, there is a problem that the discharge capacity is smaller than the charge capacity, and the so-called irreversible capacity defined by the difference between the two is large.
  • the lithium nickel composite oxide is usually manufactured from a step of mixing a nickel composite hydroxide with a lithium compound and baking.
  • the nickel composite hydroxide contains impurities such as sulfate radicals derived from raw materials in the manufacturing process of the nickel composite hydroxide. These impurities often inhibit the reaction with lithium in the step of mixing and baking the lithium compound, and lower the crystallinity of the lithium nickel composite oxide having a layered structure.
  • the lithium-nickel composite oxide having low crystallinity has a problem in that when a battery is formed as a positive electrode material, the Li diffusion in the solid phase is inhibited and the capacity is reduced. Furthermore, the impurities contained in the nickel composite hydroxide remain in the lithium nickel composite oxide even after mixing with the lithium compound and firing. Since these do not contribute to the charge / discharge reaction, when the battery is configured, the negative electrode material must be used in the battery by an amount corresponding to the irreversible capacity of the positive electrode material. As a result, the capacity per weight and volume of the battery as a whole is reduced, and excess lithium accumulated in the negative electrode as an irreversible capacity becomes a problem from the viewpoint of safety.
  • a lithium nickel composite oxide with a lower impurity content is required, but for that purpose, a nickel composite hydroxide with a lower impurity content is required.
  • the present invention provides a precursor of a positive electrode active material that can obtain a high-capacity non-aqueous electrolyte secondary battery by inhibiting the reaction with lithium and further reducing the amount of impurities that do not contribute to the charge / discharge reaction.
  • a nickel composite hydroxide and a method for producing the same are provided.
  • an alkaline solution is a mixed solution of an alkali metal hydroxide and a carbonate, so that the sulfate group which is an impurity is used.
  • the present invention has been completed with the knowledge that the above can be reduced.
  • Nickel composite hydroxide according to the present invention for achieving the above object, the general formula Ni 1-x-y Co x Al y (OH) 2 + ⁇ (0.05 ⁇ x ⁇ 0.35,0.01 ⁇ y ⁇ 0.2, x + y ⁇ 0.4, 0 ⁇ ⁇ ⁇ 0.5), and are spherical secondary particles formed by aggregation of a plurality of plate-like primary particles, and the secondary particles have an average
  • the particle size is 3 ⁇ m to 20 ⁇ m
  • the sulfate radical content is 1.0 mass% or less
  • the chlorine content is 0.5 mass% or less
  • the carbonate radical content is 1.0 mass% to 2.5 mass%. It is characterized by mass%.
  • the method for producing a nickel composite hydroxide according to the present invention is a method for producing a nickel composite hydroxide by producing a nickel composite hydroxide by a crystallization reaction.
  • a crystallization step of crystallization by adding an alkaline solution to a reaction solution containing a mixed aqueous solution, an ammonium ion supplier, and an aluminum source, wherein the alkaline solution is a mixed aqueous solution of an alkali metal hydroxide and a carbonate
  • the ratio [CO 3 2 ⁇ ] / [OH ⁇ ] of the carbonate to the alkali metal hydroxide in the mixed aqueous solution is 0.002 or more and 0.050 or less.
  • the present invention provides a nickel composite hydroxide with a low content of impurities that makes it possible to obtain a positive electrode active material for a non-aqueous electrolyte secondary battery having a small irreversible capacity. Further, in the present invention, such a nickel composite hydroxide can be easily manufactured, has high productivity, and extremely high industrial value.
  • Nickel composite hydroxide 2. Manufacturing method of nickel composite hydroxide 3. Positive electrode active material for non-aqueous electrolyte secondary battery 4. Manufacturing method of positive electrode active material for non-aqueous electrolyte secondary battery Nonaqueous electrolyte secondary battery
  • Nickel composite hydroxide> Nickel composite hydroxide of the present invention have the general formula Ni 1-x-y Co x Al y (OH) 2 + ⁇ (0.05 ⁇ x ⁇ 0.35,0.01 ⁇ y ⁇ 0.2, x + y ⁇ 0 .4, 0 ⁇ ⁇ ⁇ 0.5), and spherical secondary particles formed by aggregation of a plurality of plate-like primary particles, and the secondary particles have an average particle size of 3 to 20 ⁇ m.
  • the sulfate radical content is 1.0 mass% or less, the chlorine content is 0.5 mass% or less, and the carbonate radical content is 1.0 mass% to 2.5 mass%. It is a feature.
  • the characteristics of each element will be described in detail.
  • Nickel composite hydroxide is particulate, the composition has the general formula Ni 1-x-y Co x Al y (OH) 2 + ⁇ (0.05 ⁇ x ⁇ 0.35,0.01 ⁇ y ⁇ 0 .2, x + y ⁇ 0.4, 0 ⁇ ⁇ ⁇ 0.5).
  • x indicating the cobalt content is 0.05 ⁇ x ⁇ 0.35.
  • x indicating the cobalt content is 0.05 ⁇ x ⁇ 0.35, and considering the battery characteristics and cost of the positive electrode active material, 0.07 ⁇ x ⁇ 0.25 is preferable. More preferably, 0.10 ⁇ x ⁇ 0.20.
  • y indicating the aluminum content is 0.01 ⁇ y ⁇ 0.2, preferably 0.01 ⁇ y ⁇ 0.1.
  • the durability characteristics and safety of the battery can be improved.
  • the aluminum is adjusted so as to be uniformly distributed inside the particles, the above effect can be obtained with the whole particles, and a larger effect can be obtained with the same addition amount, and a decrease in capacity can be suppressed. There is. Since the effect expected when y is less than 0.01 because the amount of aluminum added is too small, it is not preferable.
  • the amount of aluminum added is too large and exceeds 0.2, the metal element contributing to the Redox reaction decreases, and the battery capacity of the positive electrode active material decreases, which is not preferable. Furthermore, the total atomic ratio of cobalt and aluminum is x + y ⁇ 0.4. When the atomic ratio of the total of cobalt and aluminum exceeds 0.4, the capacity of the obtained positive electrode active material is excessively reduced.
  • composition analysis method is not particularly limited, but can be determined from chemical analysis by ICP emission spectroscopy.
  • the nickel composite hydroxide is composed of spherical secondary particles formed by aggregation of a plurality of primary particles.
  • shape of the primary particles constituting the secondary particles various forms such as a plate shape, a needle shape, a rectangular parallelepiped shape, an elliptical shape, and a rhombohedral shape can be adopted.
  • the aggregated state of a plurality of primary particles can be applied to the present invention not only in the case of aggregation in a random direction but also in the case of aggregation in the major axis direction of the primary particles radially from the center.
  • plate-like and / or needle-like primary particles are aggregated in random directions to form secondary particles.
  • voids are formed almost uniformly between the primary particles, and when mixed with the lithium compound and fired, the molten lithium compound reaches the secondary particles, and the lithium is sufficiently diffused. Because it is.
  • the shape observation method of the primary particles and the secondary particles is not particularly limited, but can be measured by observing the cross section of the nickel composite hydroxide using a scanning electron microscope.
  • the average particle diameter of the nickel composite hydroxide is adjusted to 3 to 20 ⁇ m. An average particle size of less than 3 ⁇ m is not preferable because when the positive electrode is formed, the packing density of the particles decreases and the battery capacity per positive electrode volume decreases. On the other hand, if the average particle size exceeds 20 ⁇ m, the specific surface area of the positive electrode active material is decreased and the interface with the battery electrolyte is decreased, whereby the resistance of the positive electrode is increased and the output characteristics of the battery are decreased. . Therefore, if the nickel composite hydroxide has an average particle diameter of 3 to 20 ⁇ m, preferably adjusted to 3 to 15 ⁇ m, more preferably 4 to 12 ⁇ m, this positive electrode active material was used for the positive electrode. In the battery, the battery capacity per volume can be increased, the safety is high, and the cycle characteristics are good.
  • the measuring method of the average particle diameter is not particularly limited, but can be determined from, for example, a volume integrated value measured by a laser light diffraction / scattering particle size analyzer.
  • the nickel composite hydroxide contains sulfate radicals and chlorine as impurities. Sulfate radicals and chlorine are derived from the raw materials used in the crystallization process described later.
  • the nickel composite hydroxide has a sulfate radical content of 1.0 mass% or less, preferably 0.6 mass% or less, and a chlorine content of 0.5 mass% or less, preferably 0.3 mass% or less. It is.
  • the reaction with lithium is inhibited in the step of mixing with the lithium compound and firing, and the crystallinity of the lithium nickel composite oxide having a layered structure Reduce.
  • Lithium nickel composite oxide having low crystallinity has a problem in that when a battery is formed as a positive electrode material, Li diffusion in the solid phase is inhibited and the capacity is reduced.
  • the impurities contained in the nickel composite hydroxide remain in the lithium nickel composite oxide even after being mixed with the lithium compound and baked. Since these impurities do not contribute to the charge / discharge reaction, when the battery is configured, the negative electrode material has to be used in the battery by an amount corresponding to the irreversible capacity of the positive electrode material. As a result, the capacity per weight and volume of the battery as a whole is reduced, and excess lithium accumulated in the negative electrode as an irreversible capacity becomes a problem from the viewpoint of safety.
  • the nickel composite hydroxide has a carbonate radical content of 1.0% by mass to 2.5% by mass.
  • the carbonate radical contained in the nickel composite hydroxide is derived from the carbonate used in the crystallization step described later.
  • the carbonate radical is volatilized in the step of mixing and firing the nickel composite hydroxide and the lithium compound, and therefore does not remain in the lithium nickel composite oxide as the positive electrode material. If the carbonate radical content in the nickel composite hydroxide is in the range of 1.0% to 2.5% by weight, it is contained in the nickel composite hydroxide when mixed with the lithium compound and fired.
  • the carbonate group content can be determined, for example, by measuring the total carbon element content of the nickel composite hydroxide and converting the measured total carbon element amount into CO 3 .
  • the carbonate radical content is less than 1.0% by mass
  • the contact with the molten lithium compound becomes insufficient when mixed with the lithium compound and fired. Therefore, the crystallinity of the obtained lithium nickel composite oxide is lowered, and when a battery is constructed as the positive electrode material, there arises a problem that the capacity is reduced by inhibiting Li diffusion in the solid phase.
  • the carbonate group content exceeds 2.5% by mass, in the step of mixing with a lithium compound and baking to obtain a lithium nickel composite oxide, the generated carbon dioxide gas inhibits the reaction, and the lithium nickel composite oxide Crystallinity decreases.
  • the nickel composite hydroxide is preferably adjusted so that [(d90-d10) / average particle size], which is an index indicating the spread of the particle size distribution of the particles, is 0.55 or less.
  • the particle size distribution is wide and [(d90 ⁇ d10) / average particle size], which is an index indicating the spread of the particle size distribution, exceeds 0.55, the particle size is very small with respect to the average particle size. There are many fine particles and particles having a very large particle size (large particles) with respect to the average particle size.
  • a positive electrode is formed using a positive electrode active material in which a large amount of fine particles are present, heat may be generated due to a local reaction of the fine particles, safety is reduced, and fine particles having a large specific surface area are selectively used. Since it deteriorates, the cycle characteristics deteriorate, which is not preferable.
  • the particle size distribution of the positive electrode active material is adjusted so that the index [(d90-d10) / average particle size] indicating the spread of the particle size distribution of the particles is 0.55 or less, the fine particles and large particles Therefore, a battery using this positive electrode active material for the positive electrode is excellent in safety, and good cycle characteristics and battery output can be obtained.
  • d10 is the cumulative volume of all particles when the number of particles in each particle size is accumulated from the smallest particle size. It means the particle size which becomes 10% of the total volume. Further, d90 means a particle size in which the cumulative volume becomes 90% of the total volume of all particles when the number of particles in each particle size is accumulated from the smallest particle size.
  • the method for obtaining the average particle diameter and d90 and d10 is not particularly limited, but for example, it can be obtained from the volume integrated value measured with a laser light diffraction / scattering particle size analyzer.
  • the nickel composite hydroxide is preferably adjusted to have a specific surface area of 15 m 2 / g to 60 m 2 / g. This is because when the specific surface area is in the range of 15 m 2 / g to 60 m 2 / g, a particle surface area that can contact the molten lithium compound can be sufficiently obtained when mixed with the lithium compound and fired. On the other hand, when the specific surface area is less than 15 m 2 / g, the contact with the molten lithium compound is insufficient when mixed and fired with the lithium compound, the crystallinity of the resulting lithium nickel composite oxide is lowered, and the positive electrode material When the battery is configured, there is a problem that the capacity is reduced by inhibiting Li diffusion in the solid phase.
  • the manufacturing method of nickel composite hydroxide manufactures the above-mentioned nickel composite hydroxide by crystallization reaction.
  • the method for producing a nickel composite hydroxide has a pH value of 12.0 to 13.4 measured on a mixed aqueous solution containing nickel and cobalt, an aqueous solution containing an ammonium ion supplier and an aluminum source with a liquid temperature of 25 ° C. as a reference.
  • a nucleation step for nucleation in a reaction solution (hereinafter also referred to as an aqueous solution for nucleation) obtained by adding an alkaline solution so as to become a reaction solution containing nuclei formed in the nucleation step (Hereinafter also referred to as an aqueous solution for particle growth) is a particle growth step of growing nuclei by adding an alkaline solution so that the pH value measured with a liquid temperature of 25 ° C. as a reference is 10.5 to 12.0.
  • the alkali solution used is a mixed aqueous solution of alkali metal hydroxide and carbonate, and [CO 3 2 ⁇ ] / [OH ⁇ ] representing the mixing ratio of the alkali metal hydroxide and carbonate in the mixed aqueous solution is 0.002. It is 0.050 or less.
  • the particle size distribution of the obtained nickel composite hydroxide becomes wide.
  • the time when the nucleation reaction mainly occurs (nucleation process) and the time when the particle growth reaction mainly occurs (particle growth process) are clearly defined. Even if both steps are carried out in the same reaction vessel, the separation is characterized in that a composite hydroxide having a narrow particle size distribution can be obtained.
  • nucleation process In the nucleation step, an alkaline aqueous solution containing nickel and cobalt, an aqueous solution containing an ammonium ion supplier and an aluminum source is adjusted so that the pH value measured on the basis of a liquid temperature of 25 ° C. is 12.0 to 13.4. The solution is added, and the nickel composite hydroxide is nucleated in the resulting reaction solution (nucleation solution).
  • a sodium aluminate aqueous solution is preferably contained as an aluminum source.
  • the molar ratio of sodium to aluminum (Na / Al) in the aqueous sodium aluminate solution is preferably 1.5 to 3.0.
  • the ammonium concentration of the reaction solution is preferably adjusted within the range of 3 to 25 g / L.
  • a mixed aqueous solution containing nickel and cobalt, an ammonium ion supplier, and an aluminum source are placed in a reaction vessel, and an alkali solution is placed therein to adjust the pH, causing a crystallization reaction to produce nuclei.
  • an alkali solution is placed therein to adjust the pH, causing a crystallization reaction to produce nuclei.
  • the order in which the mixed aqueous solution, the ammonium ion supplier, the aluminum source, and the alkaline solution are put into the reaction tank is not particularly limited, and nucleation may be performed by putting them together.
  • the pH value of the reaction aqueous solution and the concentration of ammonium ions change with the nucleation. Therefore, the alkaline aqueous solution and the aqueous ammonia solution are supplied to the reaction aqueous solution together with the nickel cobalt mixed aqueous solution, and the pH of the reaction aqueous solution
  • the alkali solution and the ammonium ion supplier are appropriately added to the reaction vessel and controlled so that the value and the ammonium concentration are maintained at predetermined values.
  • nucleation step when a mixed aqueous solution containing nickel and cobalt, an aqueous alkaline solution, an ammonium ion supplier and an aluminum source are continuously supplied to the reaction aqueous solution, new nuclei are continuously generated in the reaction aqueous solution. Will continue.
  • nucleation step when a predetermined amount of nuclei is generated in the reaction solution, the nucleation reaction is terminated.
  • whether or not a predetermined amount of nuclei has been generated in the reaction solution can be determined by the amount of metal salt added to the reaction solution.
  • the pH value of the reaction solution (particle growth aqueous solution) containing nuclei formed in the nucleation step is 10.5 to 12.2.
  • the particle growth reaction is carried out by adjusting to be in the range of 0 to obtain nickel composite hydroxide particles. More specifically, the pH value of the reaction aqueous solution is controlled by adding an inorganic acid of the same type as the acid constituting the metal compound, for example, sulfuric acid or the like, or adjusting the supply amount of the alkaline aqueous solution.
  • the particle growth step when the pH value of the aqueous solution for particle growth becomes 12.0 or less, nuclei in the aqueous solution for particle growth grow to form a nickel composite hydroxide having a predetermined particle diameter.
  • the pH value of the aqueous solution for particle growth is in the range of 10.5 to 12.0, and the nucleus growth reaction takes precedence over the nucleus generation reaction. Nuclei are hardly generated.
  • the particle growth reaction when a predetermined amount of nickel composite hydroxide having a predetermined particle size is generated in the aqueous solution for particle growth, the particle growth reaction is terminated.
  • the amount of nickel composite hydroxide having a predetermined particle size is determined by the amount of metal salt added to the reaction aqueous solution.
  • the salt such as nickel salt and cobalt salt used in the mixed aqueous solution containing nickel and cobalt is not particularly limited as long as it is a water-soluble compound, but sulfate, nitrate, chloride, etc. may be used. it can. For example, nickel sulfate and cobalt sulfate are preferable.
  • the concentration of the mixed aqueous solution is preferably 1 mol / L to 2.6 mol / L, more preferably 1 mol / L to 2.2 mol / L in total of the metal salts. If the concentration is less than 1 mol / L, the resulting hydroxide slurry concentration is low and the productivity is poor. On the other hand, if it exceeds 2.6 mol / L, crystal precipitation and freezing occur at ⁇ 5 ° C. or less, which may clog the piping of the equipment, and it is necessary to keep the piping warm or warm, which is expensive.
  • the amount of the mixed aqueous solution supplied to the reaction tank is such that the concentration of the crystallized product at the time when the crystallization reaction is completed is approximately 30 g / L to 250 g / L, preferably 80 g / L to 150 g / L. It is preferable to do.
  • the crystallized substance concentration is less than 30 g / L, aggregation of primary particles may be insufficient, and when it exceeds 250 g / L, diffusion of the mixed aqueous solution to be added in the reaction vessel is sufficient. This is because the grain growth may be biased.
  • ammonia ion supplier is not particularly limited as long as it is a water-soluble compound, but ammonia, ammonium sulfate, ammonium chloride, ammonium carbonate, ammonium fluoride, and the like can be used. For example, ammonia and ammonium sulfate are preferably used. It is done.
  • the ammonium ion supplier is such that the ammonia concentration in the reaction solution is preferably 3 g / L to 25 g / L, more preferably 5 g / L to 20 g / L, and even more preferably 5 g / L to 15 g / L.
  • metal ions particularly Ni ions
  • the solubility of the metal ions increases, the growth of primary particles is promoted, and the dense nickel composite hydroxide particles are formed. It is easy to obtain.
  • nickel composite hydroxide particles having a uniform shape and particle size are easily obtained.
  • by setting the ammonia concentration in the reaction solution to 3 g / L to 25 g / L, it is easy to obtain nickel composite hydroxide particles having a more precise shape and particle size.
  • the solubility of metal ions may become unstable, primary particles having a uniform shape and particle size are not formed, and gel-like nuclei are formed. The particle size distribution may be broadened.
  • the ammonia concentration exceeds 25 g / L, the solubility of metal ions becomes too high, the amount of metal ions remaining in the reaction aqueous solution increases, and the composition may shift.
  • the concentration of ammonium ions can be measured with a general ion meter.
  • the alkaline solution is a mixed aqueous solution of alkali metal hydroxide and carbonate.
  • the ratio of carbonate to alkali metal hydroxide ([CO 3 2 ⁇ ] / [OH ⁇ ]) representing the mixing ratio of alkali metal hydroxide and carbonate is 0.002 or more and 0.050 or less, 0 0.005 or more and 0.030 or less is preferable, and 0.010 or more and 0.025 or less is more preferable.
  • the alkaline solution a mixed aqueous solution of alkali metal hydroxide and carbonate
  • anions such as sulfate radicals and chlorine remaining as impurities in the nickel composite hydroxide obtained in the crystallization step are converted to carbonate radicals and ions.
  • the carbonate radical is volatilized in the step of mixing and firing the nickel composite hydroxide and the lithium compound, and therefore does not remain in the lithium nickel composite oxide as the positive electrode material. Therefore, by exchanging sulfate radicals and chlorine with carbonate radicals, it is possible to reduce the number of impurities such as sulfate radicals and chlorine remaining in the nickel composite acid.
  • the alkali metal hydroxide is preferably at least one selected from lithium hydroxide, sodium hydroxide, and potassium hydroxide, and a compound that is easily dissolved in water is preferable because the amount added can be easily controlled.
  • the carbonate is preferably at least one selected from sodium carbonate, potassium carbonate, and ammonium carbonate, and a compound that is easily soluble in water is preferable because the amount added can be easily controlled.
  • the method for adding the alkaline solution to the reaction vessel is not particularly limited, and the pH value of the reaction solution is maintained within a predetermined range described later with a pump capable of flow rate control such as a metering pump. , May be added.
  • the aluminum source used in the crystallization step is preferably an aqueous sodium aluminate solution.
  • aluminum hydroxide precipitates at a lower pH than nickel hydroxide or cobalt hydroxide, so that aluminum hydroxide is likely to precipitate alone and has a narrow particle size distribution.
  • Nickel composite hydroxide cannot be obtained.
  • the sodium aluminate aqueous solution can be obtained, for example, by dissolving a predetermined amount of sodium aluminate in water to form an aqueous solution and adding a predetermined amount of sodium hydroxide.
  • the sodium in the sodium aluminate aqueous solution is more preferably in a molar ratio of 1.5 to 3.0 with respect to aluminum.
  • the amount of sodium that is, the amount of sodium hydroxide is out of the range of 1.5 to 3.0 in terms of molar ratio, the stability of the aqueous sodium aluminate solution decreases, and immediately after being added to the reaction vessel or before being added.
  • a mixed aqueous solution containing nickel and cobalt and a sodium aluminate aqueous solution may be simultaneously added to the reaction vessel.
  • the metal concentrations of nickel, cobalt, and aluminum and the addition flow rates of the mixed aqueous solution and the sodium aluminate aqueous solution are adjusted so as to meet the target composition ratio.
  • the pH value measured on the basis of 25 ° C. is 12.0 to 13.4 in an aqueous solution containing nickel and cobalt, an ammonium ion supplier, and an aluminum source.
  • a nucleation step in which an alkali solution is added to perform nucleation, and a reaction solution (particle growth aqueous solution) containing nuclei formed in the nucleation step has a pH value of 10 measured based on a liquid temperature of 25 ° C. More preferably, it comprises a particle growth step in which an alkali solution is added so as to be 5 to 12.0 and controlled to grow nuclei.
  • the nucleation reaction and the particle growth reaction do not proceed at the same time in the same tank, but mainly the time when the nucleation reaction (nucleation process) occurs and the time when the particle growth reaction (particle growth process) occurs mainly. It is characterized by clearly separating.
  • the pH value of the reaction aqueous solution is controlled so as to be in the range of 12.0 to 13.4, preferably 12.3 to 13.0 based on the liquid temperature of 25 ° C.
  • pH value exceeds 13.4
  • generated nucleus becomes too fine and there exists a problem which reaction aqueous solution gelatinizes.
  • the pH value is less than 12.0, a nucleus growth reaction occurs together with nucleation, so that the range of the particle size distribution of the nuclei formed becomes wide and non-uniform.
  • the nucleation step by controlling the pH value of the reaction aqueous solution to 12.0 to 13.4, it is possible to suppress the growth of the nuclei and cause only the nucleation, and the formed nuclei are homogeneous and The range of the particle size distribution can be narrow.
  • the pH value of the aqueous reaction solution it is necessary to control the pH value of the aqueous reaction solution to be in the range of 10.5 to 12.0, preferably 11.0 to 12.0 on the basis of the liquid temperature of 25 ° C.
  • the pH value exceeds 12.0, the number of newly generated nuclei increases and fine secondary particles are generated, so that a nickel composite hydroxide having a good particle size distribution cannot be obtained.
  • the pH value is less than 10.5, the solubility by ammonium ions is high, and the metal ions remaining in the liquid without being precipitated increase, so that the production efficiency is deteriorated.
  • the pH value of the reaction aqueous solution to 10.5 to 12.0 in the particle growth process, only the growth of nuclei generated in the nucleation process is preferentially caused and new nucleation is suppressed.
  • the resulting nickel composite hydroxide can be homogeneous and have a narrow particle size distribution range.
  • the pH value When the pH value is 12, it is a boundary condition between nucleation and particle growth, and therefore, it can be set as either a nucleation step or a particle growth step depending on the presence or absence of nuclei present in the reaction aqueous solution. . That is, if the pH value in the nucleation step is higher than 12 and a large amount of nuclei are produced, and if the pH value is set to 12 in the particle growth step, a large amount of nuclei are present in the reaction aqueous solution, so the growth of nuclei takes priority. As a result, nickel hydroxide having a narrow particle size distribution and a relatively large particle size can be obtained.
  • the pH value of the particle growth process may be controlled to a value lower than the pH value of the nucleation process.
  • the pH value of the particle growth process is It is preferably 0.5 or more lower than the pH value of the production step, more preferably 1.0 or more.
  • the nucleation process and the particle growth process are clearly separated according to the pH value, so that the nucleation process takes precedence in the nucleation process and almost no nucleus growth occurs. Only new nuclei are produced and almost no new nuclei are generated. For this reason, in the nucleation step, homogeneous nuclei with a narrow particle size distribution range can be formed, and in the particle growth step, nuclei can be grown homogeneously. Therefore, in the method for producing nickel composite hydroxide, uniform nickel composite hydroxide particles having a narrow particle size distribution range can be obtained.
  • the temperature of the reaction solution is preferably set to 20 to 80 ° C., more preferably 30 to 70 ° C., and further preferably 35 to 60 ° C.
  • the solubility of metal ions is low, so that nucleation is likely to occur and control becomes difficult.
  • the temperature exceeds 80 ° C. volatilization of ammonia is promoted, so that an excess ammonium ion supplier must be added to maintain a predetermined ammonia concentration, resulting in high cost.
  • reaction atmosphere The particle size and particle structure of the nickel composite hydroxide are also controlled by the reaction atmosphere in the crystallization process.
  • the atmosphere in the reaction vessel during the crystallization process is controlled to a non-oxidizing atmosphere, the growth of primary particles forming the nickel composite hydroxide is promoted, the primary particles are large and dense, and the particle size is appropriately large. Secondary particles are formed.
  • relatively large primary particles can be obtained by setting a non-oxidizing atmosphere having an oxygen concentration of 5.0% by volume or less, preferably 2.5% by volume or less, more preferably 1.0% by volume or less.
  • the growth of particles is promoted by the aggregation of the primary particles, and secondary particles having an appropriate size can be obtained.
  • the alkali metal in the alkaline solution is added.
  • the ratio of carbonate to hydroxide ([CO 3 2 ⁇ ] / [OH ⁇ ]) is 0.002 or more and 0.050 or less, so that the carbonate radical and the sulfate radical or chlorine of the impurity are ion-exchanged. To reduce residual sulfate radicals and chlorine.
  • the sulfate radical content in the obtained nickel composite hydroxide becomes 1.0 mass% or less, and the chlorine content becomes 0.5 mass% or less. Therefore, the positive electrode active material using this nickel composite hydroxide as a precursor has high crystallinity, can increase the battery capacity, and can provide a non-aqueous electrolyte secondary battery having high safety. Further, this nickel composite hydroxide production method can easily produce a nickel composite hydroxide, has high productivity, and has extremely high industrial value.
  • a positive electrode active material for a non-aqueous electrolyte secondary battery can be obtained using the nickel composite hydroxide described above as a precursor.
  • the positive electrode active material is made of a lithium-nickel composite oxide composed of a hexagonal lithium-containing composite oxide having a layered structure using nickel composite hydroxide as a raw material. Since the lithium nickel composite oxide has a predetermined composition and average particle size and is adjusted to a predetermined particle size distribution, it has excellent cycle characteristics and safety, small particle size, high particle size uniformity, It is suitable as a material for the positive electrode of an aqueous electrolyte secondary battery.
  • the positive electrode active material is composed of a lithium nickel cobalt aluminum composite oxide, and the composition thereof is represented by a general formula: Li t Ni 1-xy Co x Al y O 2 (where 0.97 ⁇ t ⁇ 1 .20, 0.05 ⁇ x ⁇ 0.35, 0.01 ⁇ y ⁇ 0.2, and x + y ⁇ 0.4.
  • the atomic ratio t of lithium is preferably in the above range (0.97 ⁇ t ⁇ 1.20).
  • the reaction resistance of the positive electrode in the nonaqueous electrolyte secondary battery using the obtained positive electrode active material increases, and the battery output decreases.
  • the atomic ratio t of lithium is larger than 1.20, the initial discharge capacity of the positive electrode active material is lowered and the reaction resistance of the positive electrode is also increased.
  • the atomic ratio t of lithium is preferably 0.97 ⁇ t ⁇ 1.20, and more preferably, the atomic ratio t of lithium is 1.05 or more.
  • the atomic ratio of cobalt is preferably 0.05 ⁇ x ⁇ 0.35, and more preferably 0.07 ⁇ x ⁇ 0.25, and 0.10 ⁇ x ⁇ 0. More preferably, it is 20.
  • the atomic ratio y of aluminum to the atoms of all metals other than lithium is preferably adjusted so that 0.01 ⁇ y ⁇ 0.2, and 0.01 ⁇ y ⁇ 0.1. It is more preferable to adjust so that it becomes.
  • the reason is that by adding aluminum in the positive electrode active material, the durability and safety of the battery can be improved when used as the positive electrode active material of the battery.
  • the positive electrode active material if the aluminum is adjusted so as to be uniformly distributed inside the particle, the effect of improving the durability and safety of the battery can be obtained throughout the particle, and the same addition amount is obtained.
  • the positive electrode active material when the atomic ratio y of aluminum to the atoms of all metals other than lithium is less than 0.01, cycle characteristics and safety are insufficient, which is not preferable. In addition, when the atomic ratio y of aluminum to atoms of all metals other than lithium in the positive electrode active material exceeds 0.2, the metal element contributing to the Redox reaction is decreased, and the battery capacity is decreased, which is not preferable.
  • the positive electrode active material has inherited the properties of the above-mentioned nickel composite hydroxide as a precursor, the sulfate radical content is 1.0 mass% or less, preferably 0.6 mass% or less, and the chlorine content. Is 0.5 mass% or less, preferably 0.3 mass% or less, and the carbonate radical content is 1.0 mass% to 2.5 mass%.
  • the average particle diameter of the positive electrode active material is 3 ⁇ m to 25 ⁇ m, the battery capacity per volume can be increased, the safety is high, and the cycle characteristics are also good.
  • the index indicating the spread of the particle size distribution of the positive electrode active material [(D90-D10) / average particle size] is 0.55 or less, and the proportion of particles and large particles is small.
  • the battery used in the above has excellent safety and can obtain good cycle characteristics and battery output.
  • the method for producing the positive electrode active material is not particularly limited as long as it can be produced from the nickel composite hydroxide described above. However, if the following method for producing the positive electrode active material is employed, the positive electrode active material is more reliably produced. This is preferable because it is possible.
  • the manufacturing method of the positive electrode active material is such that a nickel compound hydroxide as a raw material of the positive electrode active material is heat-treated and a lithium compound is mixed with the nickel composite hydroxide particles after the heat treatment step to remove moisture. Then, a mixing step for forming a mixture is performed, and a baking step for baking the mixture formed in the mixing step is performed. And in the manufacturing method of a positive electrode active material, a lithium nickel composite oxide, ie, a positive electrode active material, can be obtained by crushing the baked fired material.
  • the heat treatment step it may be heated to a temperature at which the residual moisture of the nickel composite hydroxide is removed, and the heat treatment temperature is not particularly limited, but is preferably 300 ° C to 800 ° C.
  • the heat treatment temperature is less than 300 ° C., the decomposition of the nickel composite hydroxide does not proceed sufficiently and the significance of performing the heat treatment step is diminished, which is not industrially appropriate.
  • the heat treatment temperature exceeds 800 ° C., the particles converted into the nickel composite oxide may sinter and aggregate.
  • the atmosphere in which the heat treatment is performed is not particularly limited, and is preferably performed in an air stream that can be easily performed.
  • the lithium-containing material to be mixed with the nickel composite hydroxide particles after the heat treatment is not particularly limited.
  • lithium hydroxide, lithium nitrate, lithium carbonate, or a mixture thereof is available. It is preferable in that it is easy. In particular, in view of ease of handling and quality stability, it is more preferable to use lithium hydroxide in the mixing step.
  • a general mixer can be used for the mixing process, and for example, a shaker mixer, a Laedige mixer, a Julia mixer, a V blender, or the like can be used.
  • a shaker mixer a Laedige mixer, a Julia mixer, a V blender, or the like can be used.
  • these mixers it is sufficient that the heat-treated particles and the lithium-containing material are sufficiently mixed to such an extent that a complex such as a composite hydroxide is not destroyed.
  • the lithium mixture is fired at 700 ° C. to 850 ° C., particularly preferably at 720 ° C. to 820 ° C.
  • the firing temperature of the lithium mixture is less than 700 ° C., the diffusion of lithium into the heat treated particles is not sufficiently performed, surplus lithium and unreacted particles remain, or the crystal structure is not sufficiently arranged, There arises a problem that sufficient battery characteristics cannot be obtained.
  • the firing time of the lithium mixture is preferably at least 3 hours or more, and more preferably 6 to 24 hours. This is because when the firing time of the lithium mixture is less than 3 hours, the lithium nickel composite oxide may not be sufficiently generated.
  • the atmosphere at the time of firing the lithium mixture is preferably an oxidizing atmosphere, and more preferably an atmosphere having an oxygen concentration of 18 volume% to 100 volume%.
  • the positive electrode active material obtained by this positive electrode active material production method has few impurities remaining inside and high crystallinity, so the capacity per unit weight and volume as a whole battery does not decrease, A positive electrode of a non-aqueous electrolyte secondary battery having a higher capacity than before can be obtained.
  • Non-aqueous electrolyte secondary battery The positive electrode active material described above is preferably used as a positive electrode active material for a non-aqueous electrolyte secondary battery.
  • the embodiment at the time of using for nonaqueous electrolyte secondary batteries is illustrated.
  • the nonaqueous electrolyte secondary battery employs a positive electrode using the positive electrode active material described above. Since the nonaqueous electrolyte secondary battery has substantially the same structure as a general nonaqueous electrolyte secondary battery except that the positive electrode active material described above is used as the positive electrode material, it will be briefly described.
  • the non-aqueous electrolyte secondary battery has a structure including a case, a positive electrode, a negative electrode, a non-aqueous electrolyte solution, and a separator housed in the case.
  • the positive electrode is a sheet-like member.
  • a positive electrode mixture paste obtained by mixing a positive electrode active material, a conductive material, and a binder is applied to the surface of an aluminum foil current collector and dried. Can be formed.
  • the negative electrode is a sheet-like member formed by applying a negative electrode mixture paste containing a negative electrode active material to the surface of a metal foil current collector such as copper and drying it.
  • the separator for example, a thin film such as polyethylene or polypropylene and a film having many fine pores can be used. In addition, if it has a function of a separator, it will not specifically limit.
  • the nonaqueous electrolytic solution is obtained by dissolving a lithium salt as a supporting salt in an organic solvent.
  • organic solvent ethylene carbonate, propylene carbonate, or the like can be used.
  • electrolyte salt LiPF 6 , LiBF 4 , LiClO 4 or the like can be used.
  • the non-aqueous electrolyte secondary battery having the above-described configuration has a positive electrode using the positive electrode active material having the nickel composite hydroxide as a precursor, the capacity per unit weight and volume as a whole battery. Has a high capacity, a small irreversible capacity, and a high safety.
  • the nickel composite hydroxides obtained by the crystallization steps described in Examples 1 to 15 and Comparative Examples 1 to 3 were washed, solid-liquid separated, dried and collected as a powder, and then various analyzes were performed by the following methods. .
  • the composition of the nickel composite hydroxide was measured with a high frequency inductively coupled plasma (ICP) emission spectrometer (ICPS-8100, manufactured by Shimadzu Corporation) after dissolving the sample in nitric acid.
  • ICP inductively coupled plasma
  • the sulfate radical content was determined by dissolving the sample with nitric acid and then measuring the elemental sulfur with an ICP emission spectrophotometer (ICPS-8100, manufactured by Shimadzu Corporation) and converting the measured amount of elemental sulfur to SO 4 .
  • ICP emission spectrophotometer ICPS-8100, manufactured by Shimadzu Corporation
  • the chlorine content was measured with an automatic titration apparatus (Hiranuma Sangyo Co., Ltd., COM-1600).
  • the carbonate radical content was determined by measuring the total carbon element content with a carbon sulfur analyzer (CS-600 manufactured by LECO) and converting the measured total carbon element amount into CO 3 .
  • the specific surface area was measured by a BET method using a specific surface area measuring device (manufactured by Yuasa Ionics Co., Ltd., Kantasorb QS-10).
  • the lithium nickel composite oxide was prepared and evaluated by the following method.
  • the nickel composite hydroxide particles produced in the examples and comparative examples were heat-treated at 700 ° C. for 6 hours in an air (oxygen: 21 vol%) air stream to recover the nickel composite oxide particles.
  • Mixing was performed using a shaker mixer apparatus (TURBULA Type T2C manufactured by Willy et Bacofen (WAB)).
  • the obtained mixture was calcined at 500 ° C. for 4 hours in an oxygen stream (oxygen: 100% by volume), then calcined at 730 ° C. for 24 hours, cooled and then crushed to obtain lithium nickel composite oxide. I got a thing.
  • the sulfate group content of the obtained lithium nickel composite oxide was determined by measuring the elemental sulfur using an ICP emission spectroscopic analyzer (ICPS-8100, manufactured by Shimadzu Corporation) after dissolving the sample in nitric acid. the amount of the element was determined by converting the SO 4.
  • ICP emission spectroscopic analyzer ICPS-8100, manufactured by Shimadzu Corporation
  • the Li-occupancy ratio indicating the crystallinity of the lithium-nickel composite oxide was calculated by performing a Rietveld analysis from a diffraction pattern obtained using an X-ray diffractometer (manufactured by Panalical, X'Pert PRO).
  • Example 1 The nickel composite hydroxide was produced as follows using the method of the present invention.
  • Appropriate amounts of 25% aqueous sodium hydroxide and 25% aqueous ammonia are added to the water in the reaction tank, and the pH of the reaction solution in the tank is 12.8 as a pH value measured with a liquid temperature of 25 ° C. as a reference. It was adjusted. Further, the ammonia concentration in the reaction solution was adjusted to 10 g / L.
  • Ni: Co 0.84: 0.16.
  • a predetermined amount of sodium aluminate was dissolved in water, and a 25% aqueous sodium hydroxide solution was added so that the ratio of sodium to aluminum was 1.7.
  • an alkali solution was prepared by dissolving sodium hydroxide and sodium carbonate in water such that [CO 3 2 ⁇ ] / [OH ⁇ ] was 0.025.
  • the mixed aqueous solution was added to the reaction solution in the reaction vessel at 12.9 ml / min.
  • a sodium aluminate aqueous solution, 25% aqueous ammonia, and an alkaline solution were also added to the reaction solution in the reaction tank at a constant rate, and the pH value was set to 12. with the ammonia concentration in the reaction solution maintained at 10 g / L. While controlling at 8 (nucleation pH value), crystallization was carried out for 2 minutes and 30 seconds to perform nucleation.
  • Example 2 a nickel composite hydroxide is obtained in the same manner as in Example 1 except that when adjusting the alkali solution, [CO 3 2 ⁇ ] / [OH ⁇ ] is 0.003. And evaluated.
  • Example 3 a nickel composite hydroxide is obtained in the same manner as in Example 1, except that when adjusting the alkaline solution, [CO 3 2 ⁇ ] / [OH ⁇ ] is 0.040. And evaluated.
  • Example 4 when sodium aluminate was dissolved in a predetermined amount of water, the same procedure as in Example 1 was performed except that a 25% sodium hydroxide aqueous solution had a ratio of sodium to aluminum of 1.0. Nickel composite hydroxide was obtained and evaluated.
  • Example 5 In Example 5, when dissolving a predetermined amount of sodium aluminate in water, nickel was added in the same manner as in Example 1 except that a 25% sodium hydroxide aqueous solution had a ratio of sodium to aluminum of 3.5. A composite hydroxide was obtained and evaluated.
  • Example 6 a nickel composite hydroxide was obtained and evaluated in the same manner as in Example 1 except that the pH of the nucleation step was 13.6.
  • Example 7 a nickel composite hydroxide was obtained and evaluated in the same manner as in Example 1 except that the pH of the nucleation step was 11.8.
  • Example 8 a nickel composite hydroxide was obtained and evaluated in the same manner as in Example 1 except that the pH of the particle growth step was 12.3.
  • Example 9 In Example 9, a nickel composite hydroxide was obtained and evaluated in the same manner as in Example 1 except that the pH of the particle growth step was 10.2.
  • Example 13 In Example 13, a nickel composite hydroxide was obtained and evaluated in the same manner as in Example 1 except that the alkali metal hydroxide in preparing the alkaline solution was potassium hydroxide and the carbonate was potassium carbonate. .
  • Example 14 nickel composite hydroxide was obtained and evaluated in the same manner as in Example 1 except that sodium carbonate was changed to ammonium carbonate and the ammonia concentration was adjusted to 20 g / L.
  • Example 15 In Example 15, a nickel composite hydroxide was obtained and evaluated in the same manner as in Example 1 except that the bath temperature was set to 35 ° C.
  • Comparative Example 1 a nickel composite hydroxide was obtained in the same manner as in Example 1 except that the alkali solution was only sodium hydroxide and [CO 3 2 ⁇ ] / [OH ⁇ ] was 0. evaluated.
  • Comparative Example 2 a nickel composite hydroxide is obtained in the same manner as in Example 1 except that when adjusting the alkaline solution, [CO 3 2 ⁇ ] / [OH ⁇ ] is 0.001. And evaluated.
  • Comparative Example 3 a nickel composite hydroxide is obtained in the same manner as in Example 1 except that when adjusting the alkaline solution, [CO 3 2 ⁇ ] / [OH ⁇ ] is 0.055. And evaluated.
  • Table 1 shows the production conditions of the nickel composite hydroxides of Examples 1 to 15 and Comparative Examples 1 to 3. Furthermore, the evaluation result of the obtained nickel composite hydroxide is shown in Table 2, and the evaluation result of the lithium nickel composite oxide is shown in Table 3.
  • the obtained nickel composite hydroxide had an average particle size of 3 to 20 ⁇ m or less, a sulfate radical content of 1.0 mass% or less, and a chlorine content. The amount is 0.5% by mass or less, and the carbonate content is 1.0% by mass to 2.5% by mass.
  • the lithium site occupancy ratio indicating the crystallinity in the case of the lithium nickel composite oxide exceeds 99.0%, and the lithium nickel excellent in crystallinity It turns out that complex oxide is obtained and it is useful as a positive electrode active material.
  • Na / Al in sodium aluminate is in the range of 1.5 to 3.0
  • the pH of the nucleation step is in the range of 12.0 to 13.4
  • the pH of the particle growth step is Examples 1 to 3 and 10 to 15 in the range of 10.5 to 12.0 have a narrower particle size distribution and appropriate specific surface area than Examples 4 to 9 which do not satisfy any of these. became.
  • nickel composite hydroxide particles are produced using the method for producing nickel composite hydroxide to which the present invention is applied, a lithium nickel composite oxide with high crystallinity is obtained, and a high capacity non-capacitance is obtained. It turns out that it is useful as a positive electrode material of an aqueous electrolyte secondary battery.
  • the nickel composite hydroxide of the present invention can be used not only for electric vehicles driven purely by electric energy but also as a precursor for battery materials for so-called hybrid vehicles used in combination with combustion engines such as gasoline engines and diesel engines. it can.
  • the power source for the electric vehicle includes not only a purely electric vehicle driven by electric energy but also a power source for a so-called hybrid vehicle used in combination with a combustion engine such as a gasoline engine or a diesel engine.
  • a non-aqueous electrolyte secondary battery including a positive electrode active material obtained using a product as a precursor can be suitably used as a power source for these hybrid vehicles.

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Abstract

L'invention concerne un hydroxyde composite de nickel contenant des quantités réduites de radical sulfate et de chlore sous forme d'impuretés. Ce procédé comprend une étape de cristallisation pour la cristallisation dans une solution de réaction obtenue par addition d'une solution alcaline à une solution aqueuse comprenant : une solution aqueuse mixte comprenant du nickel et du cobalt; un donneur d'ions ammonium; et une source d'aluminium, la solution alcaline étant une solution aqueuse mixte d'hydroxyde de métal alcalin et de carbonate. Le rapport du carbonate à l'hydroxyde de métal alcalin dans la solution aqueuse mixte, c'est-à-dire [CO3 2-]/[OH-], est régulé de manière à valoir 0,002 à 0,050, valeurs extrêmes incluses, pour ainsi obtenir de l'hydroxyde composite de nickel qui : est exprimé par Ni1-x-yCoxAly(OH)2+α (0,05≤x≤0,35, 0,01≤y≤0,2, x+y<0,4, 0≤α≤0,5); est sous la forme de particules sphériques secondaires formées par l'agrégation d'une pluralité de particules primaires en forme de plaque, les particules secondaires présentant un diamètre moyen de particule de 3 à 20 µm; et contient 1,0 % en masse ou moins d'un radical sulfate, 0,5 % en masse ou moins de chlore et 1,0 à 2,5 % en masse de radical carbonate.
PCT/JP2015/079491 2014-10-30 2015-10-20 Hydroxyde composite de nickel et son procédé de préparation WO2016067960A1 (fr)

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WO2020094482A1 (fr) * 2018-11-09 2020-05-14 Basf Se Procédé de fabrication d'un hydroxyde composite de nickel

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JP2012518871A (ja) * 2009-02-20 2012-08-16 ユミコア ソシエテ アノニム Ｌｉ蓄電池内での高い安全性と高出力とを兼備する非均質な正電極材料
JP2014156397A (ja) * 2014-05-30 2014-08-28 Sumitomo Metal Mining Co Ltd ニッケル含有水酸化物、ニッケル含有酸化物およびこれらの製造方法
JP2015128004A (ja) * 2013-12-27 2015-07-09 住友金属鉱山株式会社 非水電解質二次電池用正極活物質の前駆体とその製造方法及び非水電解質二次電池用正極活物質とその製造方法
JP2015191848A (ja) * 2014-03-28 2015-11-02 住友金属鉱山株式会社 非水電解質二次電池用正極活物質の前駆体とその製造方法、及び非水電解質二次電池用正極活物質とその製造方法

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JP2012518871A (ja) * 2009-02-20 2012-08-16 ユミコア ソシエテ アノニム Ｌｉ蓄電池内での高い安全性と高出力とを兼備する非均質な正電極材料
JP2015128004A (ja) * 2013-12-27 2015-07-09 住友金属鉱山株式会社 非水電解質二次電池用正極活物質の前駆体とその製造方法及び非水電解質二次電池用正極活物質とその製造方法
JP2015191848A (ja) * 2014-03-28 2015-11-02 住友金属鉱山株式会社 非水電解質二次電池用正極活物質の前駆体とその製造方法、及び非水電解質二次電池用正極活物質とその製造方法
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Publication number Priority date Publication date Assignee Title
WO2020094482A1 (fr) * 2018-11-09 2020-05-14 Basf Se Procédé de fabrication d'un hydroxyde composite de nickel
US12006230B2 (en) 2018-11-09 2024-06-11 Basf Se Process for making a nickel composite hydroxide

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