JP2016026998A - Production method of lithium metal complex oxide having layer structure - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a lithium metal complex oxide having a layer structure especially excellent as a cathode active material of a battery loaded especially on an electric automobile or a hybrid automobile.SOLUTION: In a method, a raw material containing a lithium salt compound, a manganese salt compound, a nickel salt compound and a cobalt salt compound is mixed, pulverized, and then fired and cracked, and thereby a lithium metal complex oxide having a layer structure is produced. In the production method of the lithium metal complex oxide having the layer structure, after firing, cracking is performed with a high-speed rotary crusher having a rotational frequency of 4,000 rpm or higher.SELECTED DRAWING: None

Description

  INDUSTRIAL APPLICABILITY The present invention can be used as a positive electrode active material of a lithium battery, and particularly exhibits excellent performance as a positive electrode active material of a battery mounted on an electric vehicle (EV) or a hybrid electric vehicle (HEV). The present invention relates to a method for producing a lithium metal composite oxide having a layer structure.

  Lithium batteries, especially lithium secondary batteries, have features such as high energy density and long life, so they can be used for home appliances such as video cameras, portable electronic devices such as notebook computers and mobile phones. Used as a power source. Recently, the lithium secondary battery is also applied to a large battery mounted on an electric vehicle (EV), a hybrid electric vehicle (HEV), or the like.

  A lithium secondary battery is a secondary battery with a structure in which lithium is melted as ions from the positive electrode during charging, moves to the negative electrode and is stored, and reversely, lithium ions return from the negative electrode to the positive electrode during discharging. It is known to be caused by the potential of the positive electrode material.

Known positive electrode active materials for lithium secondary batteries include lithium manganese oxide (LiMn ₂ O ₄ ) having a spinel structure, and lithium metal composite oxides such as LiCoO ₂ , LiNiO ₂ , and LiMnO ₂ having a layer structure. ing. For example, LiCoO ₂ has a layer structure in which a lithium atomic layer and a cobalt atomic layer are alternately stacked via an oxygen atomic layer, has a large charge / discharge capacity, and is excellent in diffusibility of lithium ion storage / desorption. Currently, most of the commercially available lithium secondary batteries are lithium metal composite oxides having a layer structure such as LiCoO ₂ .

A lithium metal composite oxide having a layer structure such as LiCoO ₂ or LiNiO ₂ is represented by a general formula LiMeO ₂ (Me: transition metal). The crystal structure of the lithium metal composite oxide having these layer structures belongs to the space group R-3m ("-" is usually attached to the upper part of "3" and indicates reversal. The same applies hereinafter). Li ions, Me ions, and oxide ions occupy 3a sites, 3b sites, and 6c sites, respectively. It is known that a layer made of Li ions (Li layer) and a layer made of Me ions (Me layer) have a layered structure in which they are alternately stacked via O layers made of oxide ions.

Conventionally, regarding a lithium metal composite oxide (LiM _x O ₂ ) having a layer structure, for example, in Patent Document 1, an alkaline solution is added to a mixed aqueous solution of manganese and nickel to coprecipitate manganese and nickel, and lithium hydroxide is added. And an active material represented by the formula: LiNi _x Mn _1-x O ₂ (where 0.7 ≦ x ≦ 0.95) obtained by firing is disclosed.

Patent Document 2 is composed of oxide crystal particles containing three kinds of transition metals, the crystal structure of the crystal particles is a layered structure, and the arrangement of oxygen atoms constituting the oxide is cubic close-packed packing. , Li [Li _x ( _AP B _Q C _R ) _1-x ] O ₂ (wherein A, B and C are three different transition metal elements, −0.1 ≦ x ≦ 0.3, 0 .. 2 ≦ P ≦ 0.4, 0.2 ≦ Q ≦ 0.4, 0.2 ≦ R ≦ 0.4).

  In Patent Document 3, in order to provide a layered lithium nickel manganese composite oxide powder having a high bulk density, at least a lithium source compound, a nickel source compound, and a manganese source compound, which are pulverized and mixed, are mixed with a nickel atom [Ni]. Layered lithium-nickel-manganese composite oxide powder by drying and firing a slurry containing a molar ratio [Ni / Mn] of 0.7 to 9.0 as a molar ratio [Ni / Mn] to manganese atom [Mn] Then, a method for producing a layered lithium nickel manganese composite oxide powder in which the composite oxide powder is pulverized is disclosed.

Patent Document 4 discloses a lithium transition metal composite oxide having a crystallite size increased by mixing vanadium (V) and / or boron (B), that is, a general formula Li _X M _Y O _Z-δ. (Wherein M represents Co or Ni as a transition metal element, and satisfies the relationship of (X / Y) = 0.98 to 1.02 and (δ / Z) ≦ 0.03). Vanadium ((V + B) / M) = 0.001 to 0.05 (molar ratio) with respect to the transition metal element (M) that includes the transition metal composite oxide and constitutes the lithium transition metal composite oxide. A substance containing V) and / or boron (B), having a primary particle diameter of 1 μm or more, a crystallite diameter of 450 mm or more, and a lattice strain of 0.05% or less is disclosed.

In Patent Document 5, a group of Co, Ni, and Mn is provided for the purpose of providing a positive electrode active material for a non-aqueous secondary battery that is composed of primary particles that maintain high bulk density and battery characteristics and do not cause cracks. A lithium composite oxide in the form of monodispersed primary particles composed mainly of one element selected from lithium and lithium, wherein D50: is 3 to 12 μm and the specific surface area is 0.2 to 1.0 m. ² / g, bulk density is 2.1 g / cm ³ or more, and inflection point of volume reduction rate by Cooper plot method does not appear up to 3 ton / cm ² , positive electrode for non-aqueous secondary battery Active materials have been proposed.

Patent Document _{6, Li z Ni 1-w M} w O 2 ( where, M is Co, Al, Mg, Mn, Ti, Fe, Cu, Zn, at least one metal selected from the group consisting of Ga Element, and satisfies the following condition: 0 <w ≦ 0.25, 1.0 ≦ z ≦ 1.1)) Secondary particles formed by aggregating a plurality of the primary particles, the shape of the secondary particles is spherical or elliptical, and 95% or more of the secondary particles have a particle size of 20 μm or less. The average particle diameter of the secondary particles is 7 to 13 μm, the tap density of the powder is 2.2 g / cm ³ or more, and pores having an average diameter of 40 nm or less in pore distribution measurement by a nitrogen adsorption method the average volume is 0.001~0.008cm ³ / g, the secondary particles of Mean crushing strength has proposed a positive electrode active material for a non-aqueous electrolyte secondary battery which is a 15～100MPa.

  In Patent Document 7, for example, after pulverization with a wet pulverizer or the like until D50: becomes 2 μm or less, granulation drying is performed using a thermal spray dryer or the like, and the particle size distribution is measured by laser diffraction scattering. A lithium metal composite oxide having a layer structure characterized in that the ratio of the crystallite diameter to the average powder particle diameter (D50) determined by the method is 0.05 to 0.20.

JP-A-8-171910 JP 2003-17052 A Japanese Patent Laid-Open No. 2003-34536 JP 2004-253169 A JP 2004-355824 A JP 2007-257985 A Japanese Patent No. 4213768 (WO2008 / 091028)

  As a method for producing a lithium metal composite oxide having a layer structure, as described in Patent Document 1 and Patent Document 6 described above, after co-precipitation by adding an alkaline solution in a mixed aqueous solution in which raw materials are mixed and dissolved in water, A method of baking by adding lithium hydroxide or the like (referred to as “coprecipitation method”), and as described in Patent Document 3 and Patent Document 7, the raw materials are mixed and water is added to form a slurry. A production method (hereinafter referred to as “spray drying method”) is known as a main production method.

  When lithium metal composite oxide powder prepared by coprecipitation method is used as the positive electrode active material of lithium secondary battery, it has been found that although it exhibits excellent life characteristics, it tends to be inferior to the initial charge / discharge efficiency. It was. On the other hand, when lithium metal composite oxide powder prepared by spray drying method is used as the positive electrode active material of a lithium secondary battery, it exhibits excellent characteristics in terms of initial charge / discharge efficiency, but tends to have poor life characteristics. I understand. As described above, it has been difficult to develop a lithium metal composite oxide powder that exhibits excellent characteristics in both life characteristics and initial charge / discharge efficiency.

  The present invention provides a new lithium metal composite oxide powder that exhibits excellent characteristics in both life characteristics and initial charge / discharge efficiency when a lithium metal composite oxide having a layer structure is used for a positive electrode of a battery. It is intended to propose a manufacturing method that can be manufactured.

  The present invention produces a lithium metal composite oxide having a layer structure by mixing raw materials containing a lithium salt compound, a manganese salt compound, a nickel salt compound and a cobalt salt compound, pulverizing, firing and crushing. In this method, a method for producing a lithium metal composite oxide having a layered structure is proposed, which is pulverized by a high-speed rotary pulverizer having a rotational speed of 4000 rpm or higher after the firing.

According to the production method proposed by the present invention, for example, the general formula Li _{1 + x} M _1-x O ₂ (M: Mn, Co, Ni, and group 3 to group 11 elements of the periodic table) Laser diffraction scattering type particle size distribution measurement method for lithium metal composite oxide having a layer structure represented by any one or more of transition elements existing between them and typical elements up to the third period of the periodic table) D50 (referred to as “D50”) based on a volume-based particle size distribution obtained by measuring by the above method is obtained from secondary particles having a size larger than 4 μm and smaller than 20 μm and corresponding to the D50 by the following measuring method. The ratio of the primary particle area (referred to as “primary particle area / secondary particle area”) determined by the following measurement method to the particle area is 0.004 to 0.035, and a micro compression tester is used. Minimum value of the powder crushing strength required by crushing the body being greater than 70 MPa, it is possible to produce a lithium metal composite oxide having a layer structure.

(Measurement method of secondary particle area)
The lithium metal composite oxide (powder) is observed with an electron microscope, and five secondary particles having a size corresponding to D50 are selected at random. If the secondary particles are spherical, the length of the particles is set to the diameter. The area is calculated as (μm), and when the secondary particles are indefinite, the area is calculated by approximating a sphere, and the average value of the five areas is obtained as the secondary particle area (μm ² ). .
(Measurement method of primary particle area)
Lithium metal composite oxide (powder) is observed with an electron microscope, 5 secondary particles are randomly selected per field of view, and 10 primary particles are randomly selected from 5 selected secondary particles. When the primary particles are rod-shaped, the area is calculated with the longest part (μm) as the longest part of the grain boundary spacing and the shortest dimension (μm) as the grain boundary spacing, and when the primary particles are spherical, the grain boundary spacing is calculated. The area is calculated by setting the length of each particle as the diameter (μm), and the average value of the 50 areas is obtained as the primary particle area (μm ² ).

  If the lithium metal composite oxide obtained by the production method proposed by the present invention is used as a positive electrode material for a lithium secondary battery, it is excellent in any of the three characteristics of life characteristics, initial charge / discharge efficiency, and slurry characteristics. It can exhibit the characteristics. Therefore, according to the production method proposed by the present invention, it is particularly excellent as a positive electrode active material for a battery mounted on a vehicle, particularly a battery mounted on an electric vehicle (EV) or a hybrid electric vehicle (HEV). The lithium metal composite oxide can be provided.

It is a figure for demonstrating the structure of the cell for electrochemical evaluation produced by the battery characteristic evaluation of an Example. It is the graph which showed the relationship between minimum powder intensity | strength (MPa) and a capacity | capacitance maintenance factor (%) as a result of an Example and a comparative example. It is the graph which showed the relationship between D50 (micrometer) and slurry viscosity (relative index) as a result of an Example and a comparative example.

  Hereinafter, although embodiment of this invention is described, this invention is not limited to the following embodiment.

<The lithium metal composite oxide>
The lithium metal composite oxide of the present embodiment (hereinafter referred to as “the present lithium metal composite oxide”) is a lithium metal composite oxide having a layer structure represented by the general formula (1): Li _{1 + x} M _1-x O ₂ It is a powder mainly composed of physical particles. That is, it is a powder mainly composed of lithium metal composite oxide particles having a layer structure in which lithium atom layers and transition metal atom layers are alternately stacked via oxygen atom layers.

  In addition, unless otherwise specified, “with a main component” includes the meaning that allows other components to be included as long as the function of the main component is not hindered. The content ratio of the main component includes at least 50 mass%, particularly 70 mass% or more, especially 90 mass% or more, especially 95 mass% or more (including 100%) of the lithium metal composite oxide.

This lithium metal composite oxide may contain 1.0 wt% or less of SO ₄ as impurities and 0.5 wt% or less of other elements, respectively. This is because an amount of this level is considered to hardly affect the characteristics of the present lithium metal composite oxide.

  “1 + x” in the above formula (1) is 1.00 to 1.07, more preferably 1.01 or more and 1.07 or less, and more preferably 1.02 or more and 1.06 or less.

“M” in the above formula (1) represents Mn, Co, Ni, transition elements existing between Group 3 elements of the periodic table and Group 11 elements and the third period of the periodic table. Any one or more of the typical elements may be used.
Here, as transition elements existing between the Group 3 elements of the periodic table and the Group 11 elements and typical elements from the third period of the periodic table, for example, Al, V, Fe, Ti, Mg, Cr , Ga, In, Cu, Zn, Nb, Zr, Mo, W, Ta, Re, and the like.
“M” is, for example, any one of Mn, Co, Ni, Al, V, Fe, Ti, Mg, Cr, Ga, In, Cu, Zn, Nb, Zr, Mo, W, Ta, and Re. As long as it is as described above, it may be composed of only three elements of Mn, Co, and Ni, the three elements may include one or more of the other elements, and other structures may be employed.

When “M” in the above formula (1) contains three elements of Mn, Co and Ni, the molar ratio of Mn, Co and Ni is Mn: Co: Ni = 0.10 to 0.45: It is preferable that it is 0.05-0.40: 0.30-0.75, and Mn: Co: Ni = 0.10-0.40: 0.05-0.40: 0.30-0. More preferably, it is 75.
For example, when represented by the general formula (2): Li _{1 + x} (Mn _α Co _β Ni _γ ) _1-x O ₂ , the following ratio is preferable.
In the formula (2), the value of α is preferably 0.10 to 0.45, more preferably 0.15 or more and 0.40 or less, and particularly preferably 0.20 or more or 0.35 or less.
The value of β is 0.05 to 0.40, more preferably 0.05 or more and 0.30 or less, and more preferably 0.05 or more and 0.25 or less.
The value of γ is preferably 0.30 to 0.75, more preferably 0.40 or more and 0.65 or less, and particularly preferably 0.45 or more or 0.55.

  In the above general formulas (1) and (2), the atomic ratio of the oxygen amount is described as “2” for convenience, but may have some non-stoichiometry.

(D50)
In this lithium metal composite oxide, it is preferable that D50 by volume reference particle size distribution obtained by measurement by a laser diffraction / scattering particle size distribution measuring method is larger than 4 μm and smaller than 20 μm.
If the D50 of the present lithium metal composite oxide is larger than 4 μm, it is possible to prevent the particles from agglomerating and increase the slurry viscosity, and if it is smaller than 20 μm, the particles settle and become non-uniform during slurry storage. Can be prevented. Therefore, if the D50 of the present lithium metal composite oxide is larger than 4 μm and smaller than 20 μm, the coating property of the slurry can be improved.
From this point of view, the D50 of the present lithium metal composite oxide is more preferably 6 μm or more and 16 μm or less, more preferably 13 μm or less, and even more preferably 10 μm or less.

  In order to adjust the D50 of the present lithium metal composite oxide within the above range, it is preferable to adjust the D50 of the starting material, adjust the firing temperature or firing time, or adjust D50 by crushing after firing. However, it is not limited to these adjustment methods.

(Primary particle area / secondary particle area)
In the present lithium metal composite oxide, the secondary particle area obtained by the following measurement method is determined from the secondary particles having a size corresponding to D50 based on the volume-based particle size distribution obtained by measurement by the laser diffraction / scattering particle size distribution measurement method. The primary particle area ratio (referred to as “primary particle area / secondary particle area”) determined by the following measurement method is preferably 0.004 to 0.035.
If the primary particle area / secondary particle area is 0.035 or less, the area of the secondary particle surface in contact with the electrolytic solution is large, and lithium ions can be taken in and out smoothly, and the charge / discharge efficiency in the first cycle Can be high. On the other hand, if the primary particle area / secondary particle area is 0.004 or more, the interface between the primary particles in the secondary particles can be reduced, and as a result, the resistance inside the secondary particles can be reduced. The charge / discharge efficiency in the first cycle can be increased. Therefore, if it is this range, initial stage charge / discharge efficiency can be improved. However, it has been confirmed that such a tendency is different when D50 is 4 μm or less.
From such a viewpoint, the primary particle area / secondary particle area is more preferably 0.004 or more and 0.026 or less, and even more preferably 0.006 or more and 0.017 or less.

In order to adjust the primary particle area / secondary particle area of the present lithium metal composite oxide to the above range, for example, in the production method by the spray drying method described later, the pulverization strength in the crushing after firing or heat treatment as compared with the conventional technique Can be adjusted by decreasing D50 and increasing “primary particle area / secondary particle area”.
On the other hand, in the production method by the coprecipitation method to be described later, the average of the primary particles, for example, lowering the firing temperature, reducing the primary particle size of the coprecipitate powder, or firing in a carbon dioxide atmosphere, as compared with the prior art. Adjustment can be made by reducing the particle size to reduce the “primary particle area / secondary particle area”.
However, it is not limited to these adjustment methods.

In the present invention, the “primary particle” means a particle of the smallest unit that is composed of a plurality of crystallites and is surrounded by a grain boundary when observed with an SEM (scanning electron microscope, for example, 1000 to 5000 times). To do. Accordingly, the primary particles include single crystals and polycrystals. In this case, “crystallite” means the largest group that can be regarded as a single crystal, and can be obtained by performing XRD measurement and Rietveld analysis.
“Primary particle area” means the area of the surface of primary particles on an electron micrograph. The lithium metal composite oxide powder is observed using an electron microscope (for example, 1000 times), and secondary particles having a size corresponding to 5 D50s per field are randomly selected, and the magnification is adjusted as necessary. The primary particle is randomly selected from 5 selected secondary particles by 10 times, and when the primary particle is rod-shaped, the longest part of the grain boundary interval is the major axis (μm), the grain boundary The area is calculated as the short diameter (μm) of the interval, and when the primary particles are spherical, the area is calculated using the length of the grain boundary interval as the diameter (μm), and the average value of the 50 areas is the primary particle. It can be determined as the area (μm ² ).
At this time, the primary particle area of the primary particle image of the electron micrograph can be calculated using image analysis software.

On the other hand, in the present invention, the term “secondary particles” or “aggregated particles” refers to particles that are aggregated such that a number of primary particles share a part of their outer periphery (grain boundary) and are isolated from other particles. That means.
“Secondary particle area” means the area of secondary particles on a plane on an electron micrograph. For example, when a lithium metal composite oxide powder is observed using an electron microscope (for example, 1000 times), five secondary particles having a size corresponding to D50 are randomly selected, and when the secondary particles are spherical The area is calculated by setting the length of the grain boundary interval as the diameter (μm), and when the secondary particles are indefinite, the area is calculated by approximating the spherical shape, and the average value of the five areas is calculated as two It can be determined as the secondary particle area (μm ² ).
The laser diffraction / scattering particle size distribution measurement method is a measurement method in which agglomerated particles are regarded as one particle (aggregated particle) and the particle size is calculated. The D50 based on the volume-based particle size distribution obtained by the measurement method is 50% volume cumulative particle size, that is, the cumulative 50 from the smaller one of the cumulative percentage notation of the particle size measurement value converted to volume in the volume-based particle size distribution chart. % Diameter.

(Primary particle area)
The primary particle area of the lithium metal composite oxide powder is not particularly limited as long as the primary particle area / secondary particle area is in the above range. As a standard of the primary particle area of the present lithium metal composite oxide powder, it is preferably 0.002 μm ^{2 to} 13.0 μm ² , especially 0.007 μm ² or more or 13.0 μm ² or less. It is much more preferable that it is ² micrometers-4.0 micrometers ² .
The primary particle area of the present lithium metal composite oxide powder can be adjusted by selection from the raw material crystal state, firing conditions, and the like. However, it is not limited to such an adjustment method.

(Powder crushing strength)
In the present lithium metal composite oxide powder, the minimum value of the powder crushing strength obtained by crushing the powder using a micro compression tester is preferably greater than 70 MPa.
If the minimum value of the powder crushing strength of the present lithium metal composite oxide powder is greater than 70 MPa, when used as a positive electrode material for a lithium secondary battery, the positive electrode active material expands when the lithium secondary battery is charged and discharged. Even if contraction occurs, particle collapse can be suppressed. As a result, it is possible to increase the capacity maintenance rate particularly during a high temperature cycle.
From such a viewpoint, the minimum value of the powder crushing strength of the lithium metal composite oxide powder is preferably greater than 70 MPa, and more preferably 75 MPa or more.

In order to adjust the minimum value of the powder crushing strength of the lithium metal composite oxide powder to the above range, for example, in the manufacturing method by the spray drying method described later, the crushing after firing or heat treatment is strengthened compared to the conventional technology. Then, the minimum value of the powder crushing strength can be made larger than 70 MPa by increasing the “primary particle area / secondary particle area” by decreasing D50.
On the other hand, in the production method by the coprecipitation method to be described later, for example, the firing temperature is lowered, the average particle size of the primary particles of the coprecipitation powder is reduced, or the primary particles are baked in a carbon dioxide atmosphere. The minimum value of the powder crushing strength can be made larger than 70 MPa by reducing the “primary particle area / secondary particle area” by reducing the average particle diameter.
However, it is not limited to these adjustment methods.

(Production method)
Next, a method for producing the present lithium metal composite oxide powder will be described.

  The lithium metal composite oxide powder is prepared by weighing and mixing raw materials such as a lithium salt compound, a manganese salt compound, a nickel salt compound and a cobalt salt compound, pulverizing with a wet pulverizer, etc., granulating, and firing. Then, it can be obtained by heat treatment if necessary, pulverization under preferable conditions, and further classification if necessary.

Examples of the lithium salt compound as a raw material include lithium hydroxide (LiOH), lithium carbonate (Li ₂ CO ₃ ), lithium nitrate (LiNO ₃ ), LiOH · H ₂ O, lithium oxide (Li ₂ O), and other fatty acid lithium And lithium halide. Of these, lithium hydroxide salts, carbonates and nitrates are preferred.

The kind of manganese salt compound is not particularly limited. For example, manganese carbonate, manganese nitrate, manganese chloride, manganese dioxide and the like can be used, and among these, manganese carbonate and manganese dioxide are preferable. Among these, electrolytic manganese dioxide obtained by an electrolytic method is particularly preferable.
The kind of the nickel salt compound is not particularly limited, and for example, nickel carbonate, nickel nitrate, nickel chloride, nickel oxyhydroxide, nickel hydroxide, nickel oxide, etc. can be used, among which nickel carbonate, nickel hydroxide, nickel oxide are used. preferable.
The type of cobalt salt compound is not particularly limited, and for example, basic cobalt carbonate, cobalt nitrate, cobalt chloride, cobalt oxyhydroxide, cobalt hydroxide, cobalt oxide and the like can be used. Cobalt, cobalt oxide, and cobalt oxyhydroxide are preferred.

  The mixing of the raw materials is preferably carried out by adding a liquid medium such as water or a dispersant and wet-mixing to make a slurry. And when employ | adopting the spray-drying method mentioned later, it is preferable to grind | pulverize the obtained slurry with a wet grinder. However, dry pulverization may be performed.

The granulation method may be either wet or dry as long as the various raw materials pulverized in the previous step are dispersed in the granulated particles without being separated. A mixed granulation method, a spray drying granulation method, a pressure molding granulation method, or a flake granulation method using a roll or the like may be used. However, when wet granulation is performed, it is necessary to sufficiently dry before firing. As a drying method, it may be dried by a known drying method such as a spray heat drying method, a hot air drying method, a vacuum drying method, a freeze drying method, etc. Among them, the spray heat drying method is preferable. The spray heat drying method is preferably carried out using a heat spray dryer (spray dryer) (referred to herein as “spray drying method”).
However, it is also possible to produce a coprecipitated powder to be fired by, for example, a so-called coprecipitation method (referred to herein as “coprecipitation method”). In the coprecipitation method, after the raw material is dissolved in a solution, the coprecipitation powder can be obtained by adjusting the conditions such as pH and causing precipitation.

In the spray drying method, the powder strength is relatively low, and voids tend to occur between particles. Therefore, when the spray drying method is employed, the crushing strength is increased as compared with a conventional crushing method, for example, a crushing method using a coarse crusher having a rotation speed of about 1000 rpm. For example, by increasing the crushing strength by crushing with a high-speed rotary crusher etc., the primary lithium metal composite oxide powder is primary compared with the lithium metal composite oxide powder obtained by the conventional spray-drying method. It is preferable to adjust the particle area / secondary particle area to a range defined by the present invention by increasing the particle area / secondary particle area.
On the other hand, in the coprecipitation method, primary particles tend to be large and primary particle area / secondary particle area tends to be high. Therefore, when the coprecipitation method is adopted, the firing temperature is lowered, the firing time is shortened, or the primary particle size of the coprecipitation powder is reduced as compared with the conventional general coprecipitation method. Alternatively, it is preferable that the average particle diameter of the primary particles is reduced by reducing the primary particle area / secondary particle area by firing in a carbon dioxide atmosphere to adjust the range within the range defined by the present invention.

Firing is performed at a temperature higher than 800 ° C. and lower than 1000 ° C. in an air atmosphere, oxygen gas atmosphere, oxygen partial pressure adjusted atmosphere, carbon dioxide gas atmosphere, or other atmosphere in a firing furnace. (: Means the temperature when a thermocouple is brought into contact with the fired product in the firing furnace.), Preferably 810 to 1000 ° C., more preferably 810 to 950 ° C. for 0.5 to 30 hours. Baking is preferred. At this time, it is preferable to select firing conditions in which the transition metal is solid-solved at the atomic level and exhibits a single phase.
The kind of baking furnace is not specifically limited. For example, it can be fired using a rotary kiln, a stationary furnace, or other firing furnace.

  The heat treatment after firing is preferably performed when the crystal structure needs to be adjusted. Even if the heat treatment is performed under the conditions of an oxidizing atmosphere such as an atmosphere, an oxygen gas atmosphere, and an oxygen partial pressure adjusted under the atmosphere. Good.

The pulverization after firing or heat treatment is preferably performed using a high-speed rotary pulverizer as described above. If pulverization is performed by a high-speed rotary pulverizer, it is possible to pulverize a portion where the particles are aggregated or weakly sintered, and to suppress distortion of the particles. However, the present invention is not limited to a high-speed rotary pulverizer.
An example of a high-speed rotary pulverizer is a pin mill. The pin mill is known as a rotary disk crusher, and is a type of crusher that draws in powder from a raw material supply port by rotating a rotating disk with pins to make the inside negative pressure. Therefore, since the fine particles are light in weight, they are easy to ride on the air current and pass through the clearance in the pin mill, while the coarse particles are reliably crushed. Therefore, according to the pin mill, it is possible to surely solve the aggregation between the particles and the weak sintered portion, and to prevent the distortion from entering the particles.
The rotation speed of the high-speed rotary pulverizer is 4000 rpm or more, particularly 5000 to 12000 rpm, and more preferably 7000 to 10000 rpm.

  The classification after firing has technical significance of adjusting the particle size distribution of the agglomerated powder and removing foreign substances, and therefore, it is preferable to select and classify a sieve having a preferable size.

(Characteristics / Applications)
The lithium metal composite oxide powder can be effectively used as a positive electrode active material of a lithium battery after being crushed and classified as necessary.
For example, the lithium metal composite oxide powder is mixed with a conductive material made of carbon black or the like and a binder made of Teflon (Teflon is a registered trademark of DUPONT, USA) binder or the like to mix the positive electrode. Agent can be produced. Such a positive electrode mixture is used for the positive electrode, for example, a material that can store and desorb lithium such as lithium or carbon is used for the negative electrode, and lithium such as lithium hexafluorophosphate (LiPF ₆ ) is used for the non-aqueous electrolyte. A lithium secondary battery can be formed by using a salt dissolved in a mixed solvent such as ethylene carbonate-dimethyl carbonate. However, the present invention is not limited to the battery having such a configuration.

  A lithium battery including the present lithium metal composite oxide powder as a positive electrode active material exhibits excellent life characteristics (cycle characteristics) when it is repeatedly used for charge and discharge, and is particularly suitable for an electric vehicle (EV). ) And a hybrid electric vehicle (HEV: Hybrid Electric Vehicle), and is particularly excellent for use as a positive electrode active material of a lithium battery used as a power source for driving a motor.

A “hybrid vehicle” is a vehicle that uses two power sources, an electric motor and an internal combustion engine.
The term “lithium battery” is intended to encompass all batteries containing lithium or lithium ions in the battery, such as lithium primary batteries, lithium secondary batteries, lithium ion secondary batteries, and lithium polymer batteries.

<Explanation of words>

In the present specification, when expressed as “X to Y” (X and Y are arbitrary numbers), unless otherwise specified, “X is preferably greater than X” or “preferably Y”. It also includes the meaning of “smaller”.
In addition, when expressed as “X or more” (X is an arbitrary number) or “Y or less” (Y is an arbitrary number), it is “preferably greater than X” or “preferably less than Y”. Includes intentions.

  Next, the present invention will be further described based on examples and comparative examples, but the present invention is not limited to the examples shown below.

<Example 1>
First, sodium hydroxide and ammonia are supplied to an aqueous solution in which nickel sulfate, cobalt sulfate, and manganese sulfate are dissolved, and a molar ratio of nickel, cobalt, and manganese is 0.54: 0.19: 0.27 by a coprecipitation method. A metal composite hydroxide was produced.
The metal composite hydroxide produced in this way consists of spherical secondary particles in which a plurality of primary particles of 1 μm or less are assembled, and the obtained metal composite hydroxide has a D50 of 15 μm and a tap density of 2.2 g / cm ³ .

Next, after weighing the lithium carbonate and the metal composite hydroxide so that the ratio of the number of moles of Li to the total number of moles of metals other than Li (Ni, Co, Mn) is 1.04: 0.96. The mixture was sufficiently mixed using a ball mill, and the obtained mixed powder was fired at 910 ° C. for 20 hours using a stationary electric furnace.
The fired lump obtained by firing is put into a mortar and crushed with a pestle, and the sieved product sieved with a sieve opening of 5 mm is crushed with a high-speed rotary crusher (Pin Mill, manufactured by Hadano Sangyo Co., Ltd.). (Condition: Rotation speed: 10000 rpm), followed by classification with a sieve having an opening of 53 μm, and recovery of lithium transition metal oxide powder (sample) under the sieve.
As a result of chemical analysis of the collected lithium transition metal oxide powder (sample), it was Li _1.04 Ni _0.52 Co _0.19 Mn _0.25 O ₂ .

<Example 2>
A polycarboxylic acid ammonium salt (SN Dispersant 5468 manufactured by San Nopco Co., Ltd.) as a dispersant was added to the ion-exchanged water so that the solid content in the slurry was 6 wt%, and was sufficiently dissolved and mixed in the ion-exchanged water.

D50: 7 μm lithium carbonate, D50: 23 μm electrolytic manganese dioxide with a specific surface area of 40 m ² / g, D50: 14 μm cobalt oxyhydroxide, and D50: 22 μm nickel hydroxide in a molar ratio of Li: Weigh so that Mn: Ni: Co = 1.04: 0.26: 0.51: 0.19, and mix and stir in the above-described order in the above-described ion-exchanged water in which the dispersant is dissolved in advance. A slurry having a solid content concentration of 50 wt% was prepared. D50: was adjusted to 0.5 μm by pulverization with a wet pulverizer at 1300 rpm for 40 minutes.

The obtained pulverized slurry was granulated and dried using a thermal spray dryer (spray dryer, i-8 manufactured by Okawara Chemical Co., Ltd.). In this case, a rotating disk was used for spraying, and granulation drying was performed by adjusting the temperature so that the rotation speed was 24,000 rpm, the slurry supply amount was 3 kg / hr, and the outlet temperature of the drying tower was 100 ° C.
The obtained granulated powder was calcined at 450 ° C. in the atmosphere using a stationary electric furnace. Subsequently, the calcined powder was baked at 910 ° C. for 20 hours using a static electric furnace.
The fired mass obtained by firing is put in a mortar and crushed with a pestle, and the sieved product sieved with a sieve opening of 5 mm is crushed with a high-speed rotary crusher (Pin Mill, manufactured by Hadano Sangyo Co., Ltd.) ( (Crushing condition: 10000 rpm) and classification with a sieve having an opening of 53 μm, and the lithium transition metal oxide powder (sample) under the sieve was recovered.
As a result of chemical analysis of the collected lithium transition metal oxide powder (sample), it was Li _1.04 Ni _0.52 Co _0.19 Mn _0.25 O ₂ .

<Comparative Example 1>
A polycarboxylic acid ammonium salt (SN Dispersant 5468 manufactured by San Nopco Co., Ltd.) as a dispersant was added to the ion-exchanged water so that the solid content in the slurry was 6 wt%, and was sufficiently dissolved and mixed in the ion-exchanged water.

D50: 7 μm lithium carbonate, D50: 23 μm electrolytic manganese dioxide with a specific surface area of 40 m ² / g, D50: 14 μm cobalt oxyhydroxide, and D50: 22 μm nickel hydroxide in a molar ratio of Li: Weighed so that Mn: Ni: Co = 1.04: 0.26: 0.51: 0.19, mixed and stirred in the above order in ion-exchanged water in which the dispersant was dissolved in advance, and the solid content concentration A 50 wt% slurry was prepared. D50: was adjusted to 0.5 μm by pulverization with a wet pulverizer at 1300 rpm for 40 minutes.

The obtained pulverized slurry was granulated and dried using a thermal spray dryer (spray dryer, i-8 manufactured by Okawara Chemical Co., Ltd.). In this case, a rotating disk was used for spraying, and granulation drying was performed by adjusting the temperature so that the rotation speed was 24,000 rpm, the slurry supply amount was 3 kg / hr, and the outlet temperature of the drying tower was 100 ° C.
The obtained granulated powder was calcined at 450 ° C. in the atmosphere using a stationary electric furnace. Subsequently, the calcined powder was baked at 910 ° C. for 20 hours using a static electric furnace.
The fired lump obtained by firing was put in a mortar and crushed with a pestle and classified with a sieve having an opening of 53 μm, and a composite oxide powder (sample) under the sieve was collected.
The collected sample was subjected to classification rotor rotation speed: 14900 rpm, pulverization air pressure: 0.6 MPa, pulverization nozzle φ: 2.5 using a collision type pulverizer with a classification mechanism (Counterjet mill “100AFG / 50ATP” manufactured by Hosokawa Micron). × 3 used, pulverization was performed under the condition of powder supply amount: 4.5 kg / h, to obtain a lithium transition metal oxide powder (sample).
As a result of chemical analysis of the obtained lithium transition metal oxide powder (sample), it was Li _1.04 Ni _0.52 Co _0.19 Mn _0.25 O ₂ .

<Comparative Example 2>
A polycarboxylic acid ammonium salt (SN Dispersant 5468 manufactured by San Nopco Co., Ltd.) as a dispersant was added to the ion-exchanged water so that the solid content in the slurry was 6 wt%, and was sufficiently dissolved and mixed in the ion-exchanged water.

D50: 8 μm lithium carbonate, D50: 23 μm electrolytic manganese dioxide with a specific surface area of 40 m ² / g, D50: 14 μm cobalt oxyhydroxide, and D50: 22 μm nickel hydroxide in a molar ratio of Li: Weighed so that Mn: Ni: Co = 1.04: 0.26: 0.51: 0.19, mixed and stirred in the above order in ion-exchanged water in which the dispersant was dissolved in advance, and the solid content concentration A 50 wt% slurry was prepared. D50: was adjusted to 0.5 μm by pulverization with a wet pulverizer at 1300 rpm for 40 minutes.

The obtained pulverized slurry was granulated and dried using a thermal spray dryer (spray dryer, i-8 manufactured by Okawara Chemical Co., Ltd.). In this case, a rotating disk was used for spraying, and granulation drying was performed by adjusting the temperature so that the rotation speed was 24,000 rpm, the slurry supply amount was 3 kg / hr, and the outlet temperature of the drying tower was 100 ° C.
The obtained granulated powder was calcined at 450 ° C. in the atmosphere using a stationary electric furnace. Subsequently, the calcined powder was baked at 910 ° C. for 20 hours using a static electric furnace.
The fired lump obtained by firing was put in a mortar and crushed with a pestle and classified with a sieve having an opening of 53 μm, and a lithium transition metal oxide powder (sample) under the sieve was collected.
As a result of chemical analysis of the collected lithium transition metal oxide powder (sample), it was Li _1.04 Ni _0.52 Co _0.19 Mn _0.25 O ₂ .

<Comparative Example 3>
First, sodium hydroxide and ammonia are supplied to an aqueous solution in which nickel sulfate, cobalt sulfate, and manganese sulfate are dissolved, and by a coprecipitation method, the molar ratio of nickel, cobalt, and manganese is 0.54: 0.19: 0.27. A molten metal composite hydroxide was produced. The metal composite hydroxide is composed of spherical secondary particles in which a plurality of primary particles of 1 μm or less are assembled. The obtained metal composite hydroxide has a D50 of 15 μm and a tap density of 2.2 g / cm ^3. It was.

After weighing the lithium carbonate and the metal composite hydroxide so that the ratio of the number of moles of Li to the total number of moles of metals other than Li (Ni, Co, Mn) is 1.07: 0.93, these Were sufficiently mixed using a ball mill, and the obtained mixed powder was baked at 960 ° C. for 20 hours while flowing air using a stationary electric furnace.
The calcined powder obtained by calcining was obtained by crushing the calcined mass placed in a mortar with a pestle and classifying it with a sieve having an opening of 53 μm, and collecting the lithium transition metal oxide powder (sample) under the sieve.
As a result of chemical analysis of the collected lithium transition metal oxide powder (sample), it was Li _1.07 Ni _0.51 Co _0.18 Mn _0.24 O ₂ .

<Measurement of primary particle area>
The primary particle areas of the lithium transition metal oxide powders (samples) obtained in the examples and comparative examples were measured as follows. Using a scanning electron microscope (SEM), observe the sample (powder) at 1000 times, randomly select 5 secondary particles of D50 per field of view, and change the magnification to 5000 times. Then, 10 primary particles are selected at random from 5 selected secondary particles, and when the primary particles are rod-shaped, the longest part (μm) is the longest part of the grain boundary interval, and the short axis is the grain boundary interval. The area is calculated as (μm), and when the primary particles are spherical, the area is calculated using the length of the grain boundary interval as the diameter (μm), and the average value of the 50 areas is determined as the primary particle area (μm ^2). ).
In addition, the primary particle area calculated | required in this way was shown with the "primary particle area" in the table | surface and the graph.

<Measurement of D50>
About the lithium transition metal oxide powders (samples) obtained in the examples and comparative examples, a sample (powder) was used by using an automatic sample feeder for laser diffraction particle size distribution measuring device (“Microtorac SDC” manufactured by Nikkiso Co., Ltd.). ) In a water-soluble solvent and irradiated with 40 W ultrasonic waves for 360 seconds at a flow rate of 40%, and then obtained by measuring the particle size distribution using a laser diffraction particle size distribution analyzer “MT3000II” manufactured by Nikkiso Co., Ltd. D50 was obtained from the volume-based particle size distribution chart.
The water-soluble solvent used in the measurement was passed through a 60 μm filter, the solvent refractive index was 1.33, the particle permeability was transmissive, the particle refractive index was 2.46, the shape was non-spherical, and the measurement range was 0.133. ˜704.0 μm, the measurement time was 30 seconds, and the average value measured twice was D50.

<Measurement of secondary particle area>
Using a scanning electron microscope (SEM), the sample (powder) was observed at a magnification of 1000, and five secondary particles having a size corresponding to D50 obtained by measurement as described above were randomly selected, When the secondary particles are spherical, the area is calculated by setting the length of the grain boundary interval as the diameter (μm), and when the secondary particles are indefinite, the area is calculated by approximating the spherical shape. The average value of the individual areas was determined as the secondary particle area (μm ² ).

<Measurement of powder crushing strength>
Each of the lithium transition metal oxide powders (samples) obtained in the examples and comparative examples were each measured using a micro compression tester (manufactured by Shimadzu Corporation), and each D50 ± 2 μm secondary particle having a volume-based particle size distribution. Ten crushing strengths (MPa) were measured, and the minimum value among the ten measured values was defined as the minimum value (MPa) of the particle crushing strength.

<Evaluation method of shear stress and slurry viscosity>
8.0 g of lithium transition metal oxide powder (sample) obtained in Examples and Comparative Examples, 0.6 g of acetylene black (manufactured by Denki Kagaku Kogyo), and PVDF (manufactured by Kishida Chemical) in NMP (N-methylpyrrolidone) ) 5 g of 12 wt% dissolved solution was accurately measured, and 6 ml of NMP was added and mixed well to prepare a slurry.

The slurry produced as described above was evaluated using a slurry evaluation apparatus RheoStress 600 (manufactured by Thermo HAAKE). That is, the slurry is sandwiched between two upper and lower plates, the upper part is rotated, the rotation speed is continuously increased, and the shear stress [Pa] and the slurry viscosity when the shear rate reaches 1000 [1 / s]. [Pas] was measured for each sample.
Table 1 shows the shear stress and slurry viscosity of each example and comparative example as relative values when the numerical value of comparative example 2 is 100.

<Battery characteristics evaluation>
8.0 g of lithium transition metal oxide powder (sample) obtained in Examples and Comparative Examples, 1.0 g of acetylene black (manufactured by Denki Kagaku Kogyo), and PVDF (manufactured by Kishida Chemical) in NMP (N-methylpyrrolidone) ) 8.3 g of 12 wt% dissolved solution was accurately measured, and 5 ml of NMP was added thereto and mixed well to prepare a paste. This paste is placed on an aluminum foil as a current collector, coated with an applicator adjusted to a gap of 100 μm to 280 μm, vacuum-dried at 140 ° C. all day and night, punched out at φ16 mm, and pressed thick at 4 t / cm ² , A positive electrode was obtained.
Immediately before producing the battery, it was vacuum-dried at 120 ° C. for 120 minutes or more to remove the adhering moisture and incorporated into the battery. In addition, an average value of the weight of an aluminum foil having a diameter of 16 mm was obtained in advance, and the weight of the positive electrode mixture was obtained by subtracting the weight of the aluminum foil from the weight of the positive electrode. Further, the content of the positive electrode active material was determined from the mixing ratio of the lithium transition metal oxide powder (positive electrode active material), acetylene black, and PVDF.
The negative electrode was made of metal Li with a diameter of 19 mm and a thickness of 0.5 mm, and the electrolyte was a mixture of EC and DMC in a volume of 3: 7, and a solvent in which 1 mol / L of LiPF ₆ was dissolved as a solute was used. A cell for electrochemical evaluation shown in 1 (TOMCEL (registered trademark)) was prepared.

(Charge / discharge efficiency of 1 cycle)
Using the electrochemical cell prepared as described above, the charge / discharge efficiency of one cycle was determined by the method described below. That is, from the content of the positive electrode active material in the positive electrode, the capacity when charged at constant current and constant potential up to 4.3 V for 15 hours at 25 ° C. and 0.1 C is defined as the charge capacity (mAh / g). The discharge capacity (mAh / g) was defined as the capacity when a constant current was discharged up to 3.0V. The ratio of the discharge capacity to the charge capacity was defined as one cycle charge / discharge efficiency (%).

(High temperature cycle life evaluation: 60 ° C high temperature cycle characteristics)
A charge / discharge test was performed by the method described below using the electrochemical cell after the initial charge / discharge efficiency was evaluated as described above, and the high-temperature cycle life characteristics were evaluated.
Place the cell in an environmental tester set so that the environmental temperature for charging / discharging the battery is 60 ° C., prepare it for charging / discharging, and let it stand for 4 hours so that the cell temperature becomes the environmental temperature. The charge was set to 3.0 V to 4.3 V, charge was performed at a constant current of 0.1 C constant current, and discharge was performed at one cycle of charge and discharge at a constant current of 0.1 C, and then charge and discharge cycles were performed 30 times at 1 C.
The percentage (%) of the numerical value obtained by dividing the discharge capacity at the 31st cycle by the discharge capacity at the 2nd cycle was determined as the high temperature cycle life characteristic value.
Table 1 shows the high-temperature cycle life characteristic values of the examples and the comparative examples as relative values when the high-temperature cycle life characteristic value of the comparative example 1 is 100.

(Discussion)
From the results of Table 1 and FIG. 3 and the like, in the present lithium metal composite oxide, if D50 is larger than 4 μm, it is possible to effectively prevent the particles from aggregating and increasing the slurry viscosity. This proved to be more effective.
On the other hand, when D50 is 10 μm or more, it is the same in terms of slurry viscosity. On the other hand, when it is too large, particles settle and become non-uniform during storage of the slurry, and it was also found that D50 is preferably smaller than 20 μm. .

  Further, from the results of Table 1 and the like, it is understood that in the present lithium metal composite oxide, the charge / discharge efficiency in the first cycle can be increased if the primary particle area / secondary particle area is 0.035 or less. It was. This is because when the primary particle area / secondary particle area is 0.035 or less, the area of the secondary particle surface that comes into contact with the electrolytic solution increases, so that lithium ions can be smoothly taken in and out. It can be considered that this is because the charge / discharge efficiency in the first cycle can be increased. On the other hand, it was found that if the primary particle area / secondary particle area is 0.004 or more, the charge / discharge efficiency in the first cycle can be increased. This is because if the primary particle area / secondary particle area is 0.004 or more, the interface between the primary particles in the secondary particles decreases, and as a result, the resistance inside the secondary particles can be lowered. It can be considered that the charge / discharge efficiency in the first cycle can be increased.

  Furthermore, from the results of Table 1 and FIG. 2, in the present lithium metal composite oxide, if the minimum value of the powder crushing strength is larger than 70 MPa, especially 75 MPa or more, the capacity retention ratio at the high temperature cycle is increased. It turned out that it can raise effectively. If the minimum value of the powder crushing strength is greater than 70 MPa, when used as a positive electrode material of a lithium secondary battery, even if the lithium secondary battery is charged / discharged, expansion / contraction of the positive electrode active material occurs, It can be considered that this is because particle collapse can be suppressed. However, since the capacity retention rate does not change even when the minimum value of the powder crushing strength is 94 MPa or more, it is sufficient that the minimum value of the powder crushing strength is 100 MPa or more in terms of the capacity retention rate after 30 cycles. I also understood that.

The above embodiment has the general formula _{Li 1 + x M 1-x} O 2: is concerned with a lithium metal composite oxide can be represented by (M Mn, containing Co and Ni), the present invention Therefore, if the lithium metal composite oxide having a layer structure is used, the general formula Li _{1 + x} M _1-x O ₂ (M: Mn, Co, Ni, Al, The same applies to lithium metal composite oxides represented by V, Fe, Ti, Mg, Cr, Ga, In, Cu, Zn, Nb, Zr, Mo, W, Ta, or Re). Can think.

Claims (3)

A sodium compound and ammonia are supplied to an aqueous solution in which a raw material containing a manganese salt compound, a nickel salt compound and a cobalt salt compound is dissolved, and a metal composite hydroxide containing nickel, cobalt and manganese is produced by a coprecipitation method. Next, in a method for producing a lithium metal composite oxide having a layer structure by mixing lithium carbonate and the metal composite hydroxide, and firing and pulverizing the obtained mixed powder,
A method for producing a lithium metal composite oxide having a layer structure, characterized by crushing with a high-speed rotary pulverizer having a rotational speed of 4000 rpm or more after the firing. After the firing, the D50 (referred to as “D50”) based on the volume-based particle size distribution obtained by measuring by the laser diffraction scattering type particle size distribution measurement method by crushing with a high-speed rotary pulverizer having a rotation speed of 4000 rpm or more is from 4 μm. The ratio of the primary particle area obtained by the following measurement method to the secondary particle area obtained by the following measurement method from the secondary particles having a size corresponding to D50 that is larger than 20 μm (“primary particle area / The method for producing a lithium metal composite oxide having a layer structure according to claim 1, wherein the area is referred to as “secondary particle area” is 0.004 to 0.035.
(Measurement method of secondary particle area)
The lithium metal composite oxide is observed with an electron microscope, and five secondary particles having a size corresponding to D50 are randomly selected. When the secondary particles are spherical, the length of the particles is defined as the diameter (μm). The area is calculated, and when the secondary particles are indefinite, the area is calculated by approximating a spherical shape, and the average value of the five areas is obtained as the secondary particle area (μm ² ).
(Measurement method of primary particle area)
The lithium metal composite oxide is observed with an electron microscope, 5 secondary particles are randomly selected per field of view, and 10 primary particles are randomly selected from the 5 selected secondary particles. If the primary particle is spherical, the area is calculated with the longest part (μm) as the longest part of the grain boundary interval and the short diameter (μm) as the grain boundary distance. The area is calculated as the diameter (μm), and the average value of the 50 areas is determined as the primary particle area (μm ² ).   The method for producing a lithium metal composite oxide having a layer structure according to claim 1 or 2, wherein the crushing in a high-speed rotary crusher is performed using a pin mill.

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