JP2020172425A - Lithium metal composite oxide powder, positive electrode active material for lithium secondary battery, and method for producing lithium metal composite oxide powder - Google Patents

Abstract

To provide a lithium metal composite oxide powder.SOLUTION: Provide is a lithium metal composite oxide powder having a layered structure and containing at least Li, Ni, and an element X, where R(90), which is the value of R at the point in which the cumulative frequency from the smaller R side is 90% based on 100% of the total, is from 1.7 to 3.7 inclusive in the cumulative frequency distribution curve of R as defined below: R is the value of (O/(Ni+X)), which is the ratio of the amount of substance (O) of oxygen to the total amount of substance (Ni+X) of nickel and the element X in one particle of lithium metal composite oxide contained in the lithium metal composite oxide powder. The amounts of substance of nickel, the element X and oxygen are determined by energy dispersive X-ray (EDX) spectroscopy with an acceleration voltage of 1100 V, for one particle of lithium metal composite oxide.SELECTED DRAWING: None

Description

The present invention relates to a lithium metal composite oxide powder, a positive electrode active material for a lithium secondary battery, and a method for producing a lithium metal composite oxide powder.

Lithium metal composite oxide powder is used as the positive electrode active material for lithium secondary batteries.
Lithium secondary batteries are already being put to practical use not only in small power sources for mobile phones and laptop computers, but also in medium-sized or large-sized power sources for automobiles and power storage applications, and further increase in capacity and capacity. Long-term durability is required.

Various studies have been conducted on lithium metal composite oxide powders. For example, Patent Document 1 states that nickel has a valence of 2.0 to 2.5 and manganese has a valence of 3. for the purpose of increasing the capacity of a lithium secondary battery, improving long-term storage stability and cycle life. A positive electrode active material composed of a lithium ion-containing composite oxide having a valence of 5 to 4.0 is described.
Further, in Patent Document 2, for the purpose of suppressing self-discharge, LiNiO ₂ powder or LiNi _1-x M _x O ₂ (however, 0 <x ≦ 0.4, M = Co, Mn, B, Al, V, P) , Mg, Ti), and the positive electrode active material having a sulfur content of 0.5% by weight or less is described.

Japanese Unexamined Patent Publication No. 2003-203633 Japanese Unexamined Patent Publication No. 10-162830

In the invention described in Patent Document 1 or 2, there is room for further improvement from the viewpoint of suppressing self-discharge.

The present invention has been made in view of the above circumstances, and provides a method for producing a lithium metal composite oxide powder having a small amount of self-discharge, a positive electrode active material for a lithium secondary battery, and a lithium metal composite oxide powder. With the goal.

That is, the present invention includes the following inventions [1] to [27].
[1] It has a layered structure and has at least Li, Ni and element X (element X is Co, Mn, Fe, Cu, Ti, Mg, Ca, Sr, Ba, Al, W, Mo, Nb, Zn, Sn, A lithium metal composite oxide powder containing (one or more elements selected from the group consisting of Zr, Cr, Ga, Ge, Pd, Ag, Cd, In, V, B, Si, S, F and P). In the cumulative frequency distribution curve of R defined below, the value R (90) of R at the point where the cumulative frequency from the smaller side of R is 90% when the whole is 100% is 1.7. A lithium metal composite oxide powder having a value of 3.7 or less. R is the ratio (O / (Ni + X) of the amount of substance (O) of oxygen to the total amount of substance (Ni + X) of nickel and element X in one particle of lithium metal composite oxide contained in the lithium metal composite oxide powder. )).
The amount of substance of nickel, element X and oxygen is determined by energy dispersive X-ray (EDX) spectroscopy with an accelerating voltage of 1100 V for one lithium metal composite oxide particle.
[2] In the cumulative frequency distribution curve of R, the value R (10) of R at the point where the cumulative frequency from the smaller side of R is 10% when the whole is 100% is 1.1 or more and 3 The lithium metal composite oxide powder according to [1], which is 0.3 or less.
[3] In the cumulative frequency distribution curve of R, the value R (50) of R at the point where the cumulative frequency from the smaller side of R is 50% when the whole is 100% is 1.5 or more 2 7. The lithium metal composite oxide powder according to [1] or [2], which is 7 or less.
[4] The lithium metal composite oxide powder according to any one of [1] to [3], which satisfies the following formula (I).
Li [Li _m (Ni _(1-n) X _n ) _1-m ] O ₂ ... (I)
(−0.1 ≦ m ≦ 0.2, 0 <n ≦ 0.7)
[5] The lithium metal composite oxide powder according to [4], wherein m of the formula (I) is 0 <m ≦ 0.2.
[6] The lithium metal composite oxide powder according to any one of [1] to [5], which comprises core particles and a coating.
[7] The lithium metal composite oxide powder according to [6], wherein the coating material contains a lithium-containing composite compound of Li and element M. However, the element M is one or more selected from Al, B, Si, S, Nb, F and P.
[8] The lithium metal composite oxide powder according to any one of [1] to [7], further containing a single particle.
[9] The 50% cumulative diameter (D ₅₀ ) is 0.5 μm in the 10% cumulative diameter (D ₁₀ ), 50% cumulative diameter (D ₅₀ ), and 90% cumulative diameter (D ₉₀ ) obtained from the particle size distribution measurement values. The lithium metal composite oxide powder according to any one of [1] to [8], which is 10 μm or less and further satisfies the relationship of the following formula (A).
0.3 ≤ (D _90- D ₁₀ ) / D ₅₀ ≤ 3 ... (A)
[10] A positive electrode active material for a lithium secondary battery containing the lithium metal composite oxide powder according to any one of [1] to [9].
[11] A method for producing a lithium metal composite oxide powder, which comprises the following steps (a) to (c) in the following order.
Step (a) A step of mixing a precursor containing at least Ni and a lithium compound containing Li and firing the mixture to obtain a raw material compound.
Step (b) A step of bringing the raw material compound into contact with a coating raw material containing at least one element M selected from the group consisting of Al, B, Si, S, Nb, F and P to obtain a raw material mixture.
Step (c) A step of heat-treating the raw material mixture at a temperature of 200 ° C. or higher to 600 ° C. or lower.
[12] The step (b) is a step (b1) of bringing the coating raw material solution 1 containing the element M into contact with the raw material compound to obtain a raw material mixture, and after the step (b1), the step ( The step (b1-A) is provided before c), wherein the solvent contained in the raw material mixture is removed and the content of the solvent in the raw material mixture is adjusted to 30% by mass or less, according to [11]. A method for producing a lithium metal composite oxide powder.
[13] The lithium metal composite oxide according to [12], wherein the step (b1) is a step (b1-1) of spraying and contacting the coating raw material solution 1 with the raw material compound to obtain a raw material mixture. How to make powder.
[14] The lithium metal composite oxidation according to [12] or [13], wherein in the step (b1), the raw material compound is adjusted to a temperature of −20 ° C. or higher and 300 ° C. or lower and brought into contact with the coating raw material solution 1. Method of manufacturing product powder.
[15] The lithium metal composite oxidation according to [13] or [14], wherein the Sauter mean diameter D ₃₂ of the spray droplet of the coating raw material solution 1 is 10 μm or more and 500 μm or less in the step (b1-1). Method of manufacturing material powder.
[16] In the step (b1-1), the ratio of the median diameter DP ₅₀ of the raw material compound to the Sauter mean diameter D ₃₂ of the sprayed droplets when spraying the coating raw material solution 1 (DP ₅₀ / D). ₃₂ ) The method for producing a lithium metal composite oxide powder according to any one of [13] to [15], wherein the diameter is 0.001 or more and 10 or less.
[17] In the step (b1), the temperature of the coating raw material solution 1 when the coating raw material solution 1 is brought into contact with the raw material compound is −20 ° C. or higher and 300 ° C. or lower, [12] to [16]. ] The method for producing a lithium metal composite oxide powder according to any one of the above.
[18] Described in any one of [12] to [17], wherein the concentration of the element M in the coating raw material solution 1 in the step (b1) is 0.001 mol / L or more and 100 mol / L or less. Method for producing lithium metal composite oxide powder.
[19] In the step (b1), the ratio (M / Li) of the amount of substance of the element M to the amount of substance of lithium contained in the raw material mixture is 0.1 or more and 50 or less [12] to [ 18] The method for producing a lithium metal composite oxide powder according to any one of.
However, the amount of substance of lithium contained in the raw material mixture is the amount excluding lithium contained in the crystal structure of the raw material compound contained in the raw material mixture.
[20] The step (b) is a step (b2) of immersing the raw material compound in a coating raw material solution 2 containing the element M and lithium to obtain a raw material mixture, and after the step (b2). The step (b2-A) of removing the solvent contained in the raw material mixture and adjusting the content of the solvent in the raw material mixture to 30% by mass or less is provided before the step (c). ]. The method for producing a lithium metal composite oxide powder.
[21] The lithium metal composite oxide powder according to [20], wherein in the step (b2), the amount of the coating raw material solution 2 with respect to the raw material compound is 0.1 times or more and 10 times or less on a weight basis. Production method.
[22] The method for producing a lithium metal composite oxide powder according to [20] or [21], wherein the temperature of the coating raw material solution 2 is −20 ° C. or higher and 80 ° C. or lower.
[23] Described in any one of [20] to [22], wherein the concentration of Li contained in the coating raw material solution 2 in the step (b2) is 0.01 mol / L or more and 10 mol / L or less. Method for producing lithium metal composite oxide powder.
[24] In the step (b2), the ratio (M / Li) of the amount of substance of the element M to the amount of substance of lithium contained in the raw material mixture is 0.1 or more and 50 or less, [20] to [ 23] The method for producing a lithium metal composite oxide powder according to any one of.
However, the amount of substance of lithium contained in the raw material mixture is the amount excluding lithium contained in the crystal structure of the raw material compound contained in the raw material mixture.
[25] The ratio (M / Li) of the amount of substance of element M to the amount of substance of lithium contained in the raw material mixture in the step (b) is 0.1 or more and 50 or less, according to [11]. Method for producing lithium metal composite oxide powder.
However, the amount of substance of lithium contained in the raw material mixture is the amount excluding lithium contained in the crystal structure of the raw material compound contained in the raw material mixture.
[26] In the step (b), the ratio (M / (Ni + X)) of the element M contained in the coating raw material to the total amount (Ni + X) of the metal elements excluding Li contained in the raw material compound is 0 in molar ratio. The method for producing a lithium metal composite oxide powder according to any one of [11] to [25], which is .0001 or more and 0.05 or less.
[27] The method for producing a lithium metal composite oxide powder according to any one of [11] to [26], wherein the raw material compound satisfies the following formula (II).
Li [Li _p (Ni _(1-q-r) Co _q X1 _r ) _1-p ] O ₂ ... (II)
(−0.1 ≦ p ≦ 0.2, 0 ≦ q ≦ 0.4, 0 ≦ r ≦ 0.4, 1-q−r ≧ 0.3, X1 is Mn, Fe, Cu, Ti, Mg, One or more elements selected from the group consisting of Ca, Sr, Ba, Al, W, Mo, Nb, Zn, Sn, Zr, Cr, Ga, Ge, Pd, Ag, Cd, In and V.)

Furthermore, the following aspects can be mentioned as aspects of the present invention.
[28] A positive electrode for a lithium secondary battery containing the positive electrode active material for a lithium secondary battery according to [10].
[29] A lithium secondary battery having the positive electrode for the lithium secondary battery according to [28].

According to the present invention, it is possible to provide a method for producing a lithium metal composite oxide powder in which the amount of self-discharge is suppressed, a positive electrode active material for a lithium secondary battery, and a lithium metal composite oxide powder.

It is a schematic block diagram which shows an example of a lithium ion secondary battery. It is a schematic block diagram which shows an example of a lithium ion secondary battery.

In the present specification, the "self-discharge amount" means a characteristic that when a charged battery is stored at a high temperature, the discharge capacity after storage is lower than the discharge capacity before storage, and before high temperature storage. It means the difference between the discharge capacity and the discharge capacity after high temperature storage.
As used herein, the term "primary particles" means particles having no grain boundaries in appearance and constituting secondary particles.
In the present specification, the "secondary particles" are particles formed by agglutination of the primary particles, and mean particles having a spherical or substantially spherical shape. Usually, the secondary particles are formed by aggregating 10 or more of the primary particles. Secondary particles are aggregates of primary particles.
In the present specification, the “single particle” means a particle that exists independently of the secondary particle and has no particle boundary in appearance, for example, a particle having a particle diameter of 0.5 μm or more. .. A single particle is a particle produced by the growth of a single crystal nucleus.
Since the primary particles aggregate to form secondary particles, the particle size is not large, and the particle size is about 0.1 μm or more and less than 0.5 μm. In the present specification, those having a particle diameter of less than 0.5 μm are referred to as primary particles, and those having a particle diameter of 0.5 μm or more are referred to as single particles.
As used herein, the term "layered structure" means a crystal structure in which layers formed from lithium atoms, transition metal atoms, and oxygen atoms are laminated.

The cumulative volumetric particle size of the lithium metal composite oxide powder is measured by the laser diffraction scattering method. As a specific measurement method, first, 0.1 g of lithium metal composite oxide powder is put into 50 ml of a 0.2 mass% sodium hexametaphosphate aqueous solution to obtain a dispersion liquid in which the lithium metal composite oxide powder is dispersed.
Next, the particle size distribution of the obtained dispersion is measured using a Microtrack MT3300EXII (laser diffraction scattering particle size distribution measuring device) manufactured by Microtrack Bell Co., Ltd., and a volume-based cumulative particle size distribution curve is obtained.
Then, in the obtained cumulative particle size distribution curve, the value of the particle size at the point where the cumulative volume from the fine particle side is 50% is 50% cumulative volume particle size (D ₅₀ (μm)) when the whole is 100%. ). Further, when the whole is 100%, the value of the particle diameter at the point where the cumulative volume from the fine particle side is 10% is the 10% cumulative volume particle size (D ₁₀ (μm)). Further, when the whole is 100%, the value of the particle diameter at the point where the cumulative volume from the fine particle side is 90% is the 90% cumulative volume particle size (D ₉₀ (μm)).

<Lithium metal composite oxide powder>
The lithium metal composite oxide powder of the present embodiment has a layered structure. The lithium metal composite oxide powder of the present embodiment contains at least Li, Ni and element X.
Elements X are Co, Mn, Fe, Cu, Ti, Mg, Ca, Sr, Ba, Al, W, Mo, Nb, Zn, Sn, Zr, Cr, Ga, Ge, Pd, Ag, Cd, In, V. , B, Si, S, F and P, one or more elements selected from the group.

≪R≫
In the lithium metal composite oxide powder of the present embodiment, R is defined as follows.
R is the ratio (O / (Ni + X) of the amount of substance (O) of oxygen to the total amount of substance (Ni + X) of nickel and element X in one particle of lithium metal composite oxide contained in the lithium metal composite oxide powder. )).

R is the amount of substance of oxygen atom with respect to the total amount of substance of nickel atom and element X in the surface region of the lithium metal composite oxide particle. Here, the "surface region of the lithium metal composite oxide particles" refers to a region having a thickness of 5 nm in the depth direction from the outermost surface of the lithium metal composite oxide particles.

In the present embodiment, "the value of R is large" means that a surface region in which oxygen atoms are excessive is formed on the surface of the particles of the lithium metal composite oxide. It also means that a surface region lacking nickel or element X is formed.
When the lithium metal composite oxide comprises core particles and a coating, "a large value of R" means that the core particles are less exposed.

In the present embodiment, "the value of R is small" means that a surface region having a small amount of oxygen atoms is formed on the surface of the particles of the lithium metal composite oxide. It also means that a surface region in which nickel and element X are excessively present is formed.
When the lithium metal composite oxide comprises core particles and a coating, "small R value" means that the core particles are highly exposed.

In the cumulative frequency distribution curve of R defined above, when the whole is 100%, the value of R at the point where the cumulative frequency from the smaller side of R is 90% is defined as R (90). The lithium metal composite oxide powder of the present embodiment has an R (90) of 1.7 or more and 3.7 or less.

How to obtain the cumulative frequency distribution curve of R in this embodiment will be described below.
The amount of substance of nickel, element X and oxygen is determined by energy dispersive X-ray (EDX) spectroscopy with an accelerating voltage of 1100 V for one lithium metal composite oxide particle.
Using a scanning electron microscope-energy dispersive X-ray (EDX) spectroscopy (JSM-7900F) manufactured by JEOL Ltd., 50 EDX plane analysis is performed for each primary particle of the lithium metal composite oxide. Specifically, an SEM image of the lithium metal composite oxide powder is acquired with a field of view of 5000 times. Ten particles are randomly selected from the particles contained in the field of view. This operation is performed in 5 fields of view, and analysis of 50 particles is performed.
According to the above EDX plane analysis, R of a region having a thickness of 5 nm in the depth direction from the outermost surface of the lithium metal composite oxide particles can be measured.
When the lithium metal composite oxide comprises core particles and a coating, the R of the coating is measured by EDX surface analysis.

From the obtained EDX spectrum, the ratio (O / (Ni + X)) of the molar amount (O) of the substance amount to the total amount of substance (Ni + X) of Ni and the element X on each particle surface is calculated.
The accelerating voltage at this time is 1100V.

Further, a cumulative frequency distribution curve is created from the calculated R of 50 particles. The value of R at the point where the cumulative frequency from the smaller side of R is 90% is R (90), the value of R at the point where it is 10% is R (10), and the value of R at the point where it is 50% is R. (50).

When the lithium metal composite oxide powder is used as the positive electrode active material for a lithium secondary battery, the surface of the particles of the lithium metal composite oxide powder comes into contact with the electrolytic solution. Oxygen is desorbed from the surface of the particles of the lithium metal composite oxide powder during charging, especially in a high temperature environment, when it comes into contact with the electrolytic solution. The desorbed oxygen oxidatively decomposes the electrolytic solution on the particle surface of the lithium metal composite oxide powder.

At that time, in order to adjust the metal valence balance in the lithium metal composite oxide powder due to oxygen desorption, self-discharge due to the reduction of the metal valence of Ni etc. contained in the charged lithium metal composite oxide powder. Will progress.
Since such an action occurs, when the number of oxygen atoms present on the surface of the particles of the lithium metal composite oxide powder is excessive, the oxygen atoms are desorbed, the electrolytic solution is oxidatively decomposed by this, and the value of a metal such as Ni is further increased. The number reduction is promoted and self-discharge progresses.

On the other hand, when the number of oxygen atoms present on the surface of the particles of the lithium metal composite oxide powder is too small, the formation of the layered structure of the lithium metal composite oxide powder becomes insufficient.
If the layered structure is insufficiently formed, the crystal structure on the surface of the particles of the lithium metal composite oxide powder is likely to be disturbed during charging. In this case, the disordered crystals hinder the desorption and insertion of lithium, the lithium element is not effectively utilized, and the battery capacity may be lowered. Further, if the crystal structure is disturbed, defects of constituent elements are likely to occur on the surface of the lithium metal composite oxide, and self-discharge proceeds.

In this embodiment, R (90) is set to a specific range, and the amount of oxygen atoms present on the surface of the particles of the lithium metal composite oxide powder is controlled.
In the present embodiment, R (90) is preferably 1.9 or more, more preferably 2.0 or more, and even more preferably 2.1 or more. Further, 3.5 or less is preferable, 3.2 or less is more preferable, and 3.0 or less is further preferable.
The above upper limit value and lower limit value can be arbitrarily combined. In the present embodiment, 1.9 or more and 3.5 or less are preferable, 2.0 or more and 3.2 or less are more preferable, and 2.1 or more and 3.0 or less are further preferable.

When R (90) is not more than the above upper limit value, it means that there are few lithium metal composite oxide particles having an excessive proportion of oxygen atoms present on the surface of the lithium metal composite oxide particles. In this case, less oxygen is desorbed from the surface of the lithium metal composite oxide particles during charging, and self-discharge due to oxidative decomposition of the electrolytic solution is less likely to proceed.
When R (90) is at least the above lower limit value, it means that a regular layered structure is formed on the surface of the lithium metal composite oxide particles. Therefore, deficiency of constituent elements and trapping of lithium are less likely to occur, and self-discharge is less likely to proceed.

The lithium metal composite oxide powder of the present embodiment preferably has an R (10) of 1.1 or more and 3.3 or less. The R (10) is preferably 1.3 or more, more preferably 1.5 or more, and even more preferably 1.7 or more. Further, 3.0 or less is preferable, 2.7 or less is more preferable, and 2.4 or less is further preferable.
The above upper limit value and lower limit value can be arbitrarily combined. In the present embodiment, 1.3 or more and 3.0 or less are preferable, 1.5 or more and 2.7 or less are more preferable, and 1.7 or more and 2.4 or less are further preferable.

When R (10) is in the above range, it means that the abundance of the lithium metal composite oxide powder in which the crystal structure is disturbed is small because the number of oxygen atoms is too small. In such a case, it means that a regular layered structure is formed on the surface of the lithium metal composite oxide particles. Therefore, the loss of the constituent elements is less likely to occur, and the self-discharge is less likely to proceed.

The lithium metal composite oxide powder of the present embodiment preferably has an R (50) of 1.5 or more and 2.7 or less. R (50) is preferably 1.7 or more, more preferably 1.9 or more, and even more preferably 2.0 or more. Further, 2.6 or less is preferable, 2.5 or less is more preferable, and 1.4 or less is further preferable.
The above upper limit value and lower limit value can be arbitrarily combined. In the present embodiment, 1.7 or more and 2.6 or less are preferable, 1.9 or more and 2.5 or less are more preferable, and 2.0 or more and 2.4 or less are further preferable.

When R (50) is in the above range, it means that the abundance of oxygen atoms on the surface of the particles of the lithium metal composite oxide powder is appropriately controlled, and the amount of impurities formed that do not contribute to charging and discharging is small. Examples of this impurity include oxides that do not contain lithium. Since there are few impurities, the resistance during charging and discharging can be reduced.

(Layered structure)
In the present embodiment, the crystal structure of the lithium metal composite oxide powder is a layered structure, and more preferably a hexagonal crystal structure or a monoclinic crystal structure.

The hexagonal crystal structure is P3, P3 ₁ , P3 ₂ , R3, P-3, R-3, P312, P321, P3 ₁ 12, P3 ₁ 21, P3 ₂ 12, P3 ₂ 21, R32, P3 m1, P31m, P3c1, P31c, R3m, R3c, P-31m, P-31c, P-3m1, P-3c1, R-3m, R-3c, P6, P6 ₁ , P6 ₅ , P6 ₂ , P6 ₄ , P6 _{3 , P6, P6 / m, P6} 3 / m, P622, P6 1 22, P6 5 22, P6 2 22, P6 4 22, P6 3 22, P6mm, P6cc, P6 3 cm, P6 3 mc, P- It belongs to any one space group selected from the group consisting of 6m2, P-6c2, P-62m, P-62c, P6 / mmm, P6 / mcc, P6 ₃ / mcm, and P6 ₃ / mmc.

The monoclinic crystal structure is P2, P2 ₁ , C2, Pm, Pc, Cm, Cc, P2 / m, P2 ₁ / m, C2 / m, P2 / c, P2 ₁ / c, C2 /. It belongs to any one space group selected from the group consisting of c.

Of these, in order to obtain a lithium secondary battery with a high discharge capacity, the crystal structure is a hexagonal crystal structure belonging to the space group R-3m or a monoclinic crystal structure belonging to C2 / m. The structure is more preferable, and the hexagonal crystal structure belonging to the space group R-3m is particularly preferable.

<< Composition formula (I) >>
The lithium metal composite oxide powder of the present embodiment is preferably represented by the following composition formula (I).
Li [Li _m (Ni _(1-n) X _n ) _1-m ] O ₂ ... (I)
(−0.1 ≦ m ≦ 0.2, 0 <n ≦ 0.7)

From the viewpoint of obtaining a lithium secondary battery having good cycle characteristics, m in the composition formula (I) is preferably more than 0, more preferably 0.01 or more, and further preferably 0.02 or more. .. Further, from the viewpoint of obtaining a lithium secondary battery having a higher initial coulombic efficiency, m in the composition formula (I) is preferably 0.1 or less, more preferably 0.08 or less, and 0.06. The following is more preferable.
The upper limit value and the lower limit value of m can be arbitrarily combined.
In the present embodiment, 0 <m ≦ 0.2 is preferable, and 0 <m ≦ 0.1 is more preferable.

From the viewpoint of obtaining a lithium secondary battery having a high discharge capacity, the upper limit of n in the composition formula (I) is preferably 0.7 or less, more preferably 0.5 or less, and 0.45. It is more preferably 0.2 or less, and particularly preferably 0.2 or less. The lower limit of n is preferably 0 or more, more preferably 0.05 or more, further preferably 0.10 or more, and particularly preferably 0.12 or more.
The upper limit value and the lower limit value of y1 can be arbitrarily combined.

<< Composition formula (I) -1 >>
From the viewpoint of enhancing the effect of the present application, the lithium metal composite oxide powder of the present embodiment is more preferably represented by the following composition formula (I) -1.
_{Li [Li m1 (Ni (1} -n12-n13-n14) Co n12 X1 n13 M1 n14) 1-m1] O 2 ··· (I) -1
(−0.1 ≦ m1 ≦ 0.2, 0 ≦ n12 ≦ 0.4, 0 ≦ n13 ≦ 0.4, 0 ≦ n14 ≦ 0.05, 0 <n12 + n13 + n14 ≦ 0.7, X1 is Mn, Fe, One or more selected from the group consisting of Cu, Ti, Mg, Ca, Sr, Ba, Al, W, Mo, Nb, Zn, Sn, Zr, Cr, Ga, Ge, Pd, Ag, Cd, In and V. And M1 is one or more selected from the group consisting of B, Si, S, F and P.)

From the viewpoint of obtaining a lithium secondary battery having good cycle characteristics, m1 in the composition formula (I) -1 is preferably more than 0, more preferably 0.01 or more, and more preferably 0.02 or more. More preferred. Further, from the viewpoint of obtaining a lithium secondary battery having a higher initial coulombic efficiency, m1 in the composition formula (I) -1 is preferably 0.1 or less, more preferably 0.08 or less, and 0. It is more preferably .06 or less.
The upper limit value and the lower limit value of m1 can be arbitrarily combined.
In the present embodiment, 0 <m1 ≦ 0.2 is preferable, and 0 <m1 ≦ 0.1 is more preferable.

From the viewpoint of obtaining a lithium secondary battery having a high discharge capacity, the upper limit of n12 + n13 + n14 in the composition formula (I) -1 is preferably 0.7 or less, more preferably 0.5 or less, and 0. It is more preferably .45 or less, and particularly preferably 0.2 or less. The lower limit of n12 + n13 + n14 is preferably 0 or more, more preferably 0.05 or more, further preferably 0.10 or more, and particularly preferably 0.12 or more.
The upper limit value and the lower limit value of n12 + n13 + n14 can be arbitrarily combined.

Further, from the viewpoint of obtaining a lithium secondary battery having a low internal resistance of the battery, n12 in the composition formula (I) -1 is preferably 0.005 or more, more preferably 0.01 or more, and 0. It is more preferably 0.05 or more. Further, from the viewpoint of obtaining a lithium secondary battery having high thermal stability, n12 in the composition formula (I) -1 is more preferably 0.35 or less, and further preferably 0.33 or less.
The upper limit value and the lower limit value of n12 can be arbitrarily combined.
In this embodiment, 0 <n12 ≦ 0.4 is preferable.

Further, from the viewpoint of obtaining a lithium secondary battery having high cycle characteristics, n13 in the composition formula (I) -1 is preferably 0.01 or more, more preferably 0.02 or more, and 0.04. The above is more preferable. Further, from the viewpoint of obtaining a lithium secondary battery having high storage stability at a high temperature (for example, in an environment of 60 ° C.), n13 in the composition formula (I) -1 is preferably 0.30 or less, preferably 0.25 or less. Is more preferable, and 0.20 or less is further preferable.
The upper limit value and the lower limit value of n13 can be arbitrarily combined.

Further, from the viewpoint of obtaining a lithium secondary battery having a low internal resistance of the battery, n14 in the composition formula (I) -1 preferably exceeds 0, more preferably 0.0005 or more, and 0.001 or more. Is more preferable. Further, from the viewpoint of obtaining a lithium secondary battery having a large discharge capacity at a high current rate, n14 in the composition formula (I) -1 is preferably 0.04 or less, more preferably 0.03 or less. , 0.02 or less is more preferable.
The upper limit value and the lower limit value of n14 can be arbitrarily combined.

X1 in the composition formula (I) -1 is Mn, Fe, Cu, Ti, Mg, Ca, Sr, Ba, Al, W, Mo, Nb, Zn, Sn, Zr, Cr, Ga, Ge, Pd, Ag. , Cd, In and V represent one or more metals selected from the group.

Further, from the viewpoint of obtaining a lithium secondary battery having high cycle characteristics, X1 in the composition formula (I) -1 is one or more selected from the group consisting of Mn, Ti, Mg, Al, W, Nb and Zr. It is preferably a metal, and from the viewpoint of obtaining a lithium secondary battery having high thermal stability, it is preferably one or more metals selected from the group consisting of Al, W, Nb, and Zr.

M1 in the composition formula (I) -1 represents one or more elements selected from the group consisting of B, Si, S, F and P.

Further, from the viewpoint of obtaining a lithium secondary battery having a low internal resistance of the battery, M2 in the composition formula (I) -1 is preferably one or more elements selected from the group consisting of B, Nb and P. , B and P are preferably one or more elements selected from the group.

≪Covering≫
The lithium metal composite oxide powder of the present embodiment preferably includes core particles and a coating material that coats the core particles. The coating is preferably a coating layer or coating particles. The coating preferably contains a lithium-containing composite compound of Li and element M. The element M is preferably one or more selected from Al, Zr, and M1 in the composition formula (I) -1, and more preferably one or more selected from Al, Zr, B, Nb, and P, and B, Nb. And one or more selected from P are more preferable, and one or more selected from B and P are particularly preferable.

The coating preferably contains a lithium-containing composite compound. From the viewpoint of reducing the resistance of the battery, the lithium-containing composite compound is more preferably a lithium-containing composite oxide. Examples of the lithium-containing composite oxide include lithium-boron-oxygen compound, lithium-niob-oxygen compound, and lithium-phosphorus-oxygen compound.

The lithium-containing composite compound is crystalline or amorphous, and is preferably amorphous. By coating the core particles with an amorphous lithium-containing composite compound, the core particles and the coating material are well bonded, and the coating material is suppressed from falling off due to expansion and contraction of the core particles due to the charge / discharge reaction. Excellent cycle characteristics.

From the viewpoint of enhancing the effect of the present invention, the ratio of the amount of substance of element M in the coating to the sum (Ni + X) of the amount of substance of Ni and element X in the composition formula (I) in the lithium metal composite oxide powder. (M / (Ni + X)) is preferably 0.05 mol% or more and 5 mol% or less. (M / (Ni + X)) is more preferably 4 mol% or less, further preferably 3 mol% or less, and particularly preferably 2 mol% or less. (M / (Ni + X)) is more preferably 0.1 mol% or more, further preferably 0.2 mol% or more, and particularly preferably 0.3 mol% or more. The above upper limit value and lower limit value can be arbitrarily combined.
Examples of the combination include 0.1 mol% or more and 4 mol% or less, 0.2 mol% or more and 3 mol% or less, and 0.3 mol% or more and mol% or less.

In the present embodiment, the composition of the coating can be confirmed by using STEM-EDX element line analysis, inductively coupled plasma emission analysis, electron probe microanalyzer analysis, etc. of the secondary particle cross section. The crystal structure of the coating layer or the coating particles can be confirmed by using powder X-ray diffraction or electron diffraction.

In the present embodiment, the lithium metal composite oxide powder preferably contains single particles.
Since the primary particles aggregate to form the secondary particles, the particles are not grown large, and the particle diameter is about 0.1 μm or more and less than 0.5 μm. In the present specification, those having an average particle size of less than 0.5 μm are defined as primary particles, and those having an average particle size of 0.5 μm or more are defined as single particles.

In addition, single particles have smaller surface energy and are excellent in stability as compared with fine primary particles and secondary particles formed by aggregating primary particles. Therefore, it is presumed that irreversible reactions such as decomposition of the electrolytic solution are suppressed on the surface of the single particle, resulting in a lithium metal composite oxide powder in which self-discharge is unlikely to occur.

From the viewpoint of suppressing self-discharge, the ratio of the number of single particles to the total number of single particles and secondary particles contained in the lithium metal composite oxide powder is preferably 20% or more, more preferably 30% or more, and more preferably 50% or more. Is particularly preferable. The upper limit is not particularly limited, but is 100% or less, preferably 90% or less.

The lithium metal composite oxide powder of the present embodiment has a 50% cumulative diameter (D ₁₀ ), a 50% cumulative diameter (D ₅₀ ), and a 90% cumulative diameter (D ₉₀ ) determined from the particle size distribution measurement values. It is preferable that (D ₅₀ ) is 0.5 μm or more and 10 μm or less, and further satisfies the relationship of the following formula (A).
0.3 ≤ (D _90- D ₁₀ ) / D ₅₀ ≤ 3 ... (A)

The lower limit of the 50% cumulative diameter (D ₅₀ ) is preferably 1.0 μm or more, more preferably 1.5 μm or more, still more preferably 2.0 μm or more. The upper limit of the 50% cumulative diameter (D ₅₀ ) is preferably 8.0 μm or less, more preferably 6.0 μm or less, still more preferably 5.0 μm or less. The upper and lower limits of the 50% cumulative diameter (D ₅₀ ) can be arbitrarily combined. In the present embodiment, 1.0 μm or more and 8.0 μm or less is preferable, 1.5 μm or more and 6.0 μm or less is more preferable, and 2.0 μm or more and 5.0 μm or less is further preferable.

The lower limit of the relationship represented by the formula (A) is preferably 0.4 or more, more preferably 0.5 or more, and particularly preferably 0.6 or more. The upper limit of the relationship represented by the formula (A) is preferably 2.5 or less, more preferably 2.0 or less, and particularly preferably 1.5 or less. The upper limit value and the lower limit value of the relationship represented by the formula (A) can be arbitrarily combined. In the present embodiment, 0.4 or more and 2.5 or less is preferable, 0.5 or more and 2.0 or less is more preferable, and 0.6 or more and 1.5 or less is particularly preferable.

<Positive electrode active material for lithium secondary batteries>
The present embodiment is a positive electrode active material for a lithium secondary battery containing the lithium metal composite oxide powder of the present invention.

<Manufacturing method of lithium metal composite oxide powder>
The method for producing a lithium metal composite oxide powder of the present embodiment includes the following steps (a) to (c) in the following order.
Step (a) A step of mixing a precursor containing at least Ni and a lithium compound and firing the mixture to obtain a raw material compound.
Step (b) A step of bringing the raw material compound into contact with a coating raw material containing at least one element M selected from the group consisting of Al, B, Si, S, Nb, F and P to obtain a raw material mixture.
Step (c) A step of heating the raw material mixture at a temperature of 200 ° C. or higher to 600 ° C. or lower.

[Step (a)]
The step (a) is a step of mixing a precursor containing at least Ni and a lithium compound and firing the mixture to obtain a raw material compound. The raw material compound means a calcined product of a precursor and a lithium compound.

-Precursor In producing the lithium metal composite oxide powder, first, a precursor containing at least Ni is produced. In the following, a precursor containing at least Ni may be referred to as a “precursor” or a “composite metal compound”.
The precursors are Co and element X1 (Mn, Fe, Cu, Ti, Mg, Ca, Sr, Ba, Al, W, Mo, Nb, Zn, Sn, Zr, Cr, Ga, Ge, Pd, Ag, Cd, It is preferable to use a composite metal compound containing one or more elements selected from the group consisting of In and V). As the composite metal compound, a composite metal hydroxide or a composite metal oxide is preferable.

(Manufacturing process of composite metal compound)
The composite metal compound can be produced by a commonly known batch co-precipitation method or continuous co-precipitation method. Hereinafter, the production method thereof will be described in detail by taking a composite metal hydroxide containing nickel, cobalt and manganese as an example.

First, a nickel cobalt manganese composite metal hydroxide is produced by reacting a nickel salt solution, a cobalt salt solution, a manganese salt solution, and a complexing agent by a co-precipitation method, particularly a continuous method described in JP-A-2002-201028. To manufacture.

The nickel salt which is the solute of the nickel salt solution is not particularly limited, and for example, any one of nickel sulfate, nickel nitrate, nickel chloride and nickel acetate can be used. As the cobalt salt which is the solute of the cobalt salt solution, for example, any one of cobalt sulfate, cobalt nitrate, and cobalt chloride can be used. As the manganese salt which is the solute of the manganese salt solution, for example, any one of manganese sulfate, manganese nitrate, and manganese chloride can be used.

The above metal salts are used in a ratio corresponding to the composition ratio of the composition formula. That is, it is used in a ratio of nickel salt: cobalt salt: manganese salt = (1-y1-z1): y1: z1.
Further, in a meeting where the ratio corresponding to the composition ratio of the above formula (II) is used, for example, the ratio of nickel salt: cobalt salt: manganese salt = (1-q-r): q: r may be used. .. Further, water is used as a solvent for the nickel salt solution, the cobalt salt solution, the manganese salt solution, and the zirconium salt solution.

The complexing agent can form a complex with nickel, cobalt, and manganese ions in an aqueous solution. Examples thereof include ammonium ion feeders (ammonium sulfate, ammonium chloride, ammonium carbonate, ammonium fluoride, etc.), hydrazine, ethylenediaminetetraacetic acid, nitrilotriacetic acid, uracildiacetic acid, and glycine. The complexing agent may or may not be contained. When the complexing agent is contained, the amount of the complexing agent contained in the metal salt solution of the element X and the mixed solution containing the complexing agent is, for example, a molar ratio of more than 0 to the total number of moles of the metal salt of the element X. It is 2.0 or less.

In the batch co-precipitation method or the continuous co-precipitation method, an alkali metal hydroxide (for example, sodium hydroxide or potassium hydroxide) is added if necessary in order to adjust the pH value of the aqueous solution.
In the reaction, the temperature of the reaction vessel is controlled within the range of, for example, 20 ° C. or higher and 80 ° C. or lower, preferably 30 ° C. or higher and 70 ° C. or lower.

The pH value in the reaction vessel is controlled, for example, in the range of pH 9 or more and pH 13 or less, preferably pH 11 or more and pH 13 or less when the temperature of the aqueous solution is 40 ° C.

The substances in the reaction vessel are appropriately stirred. Each solution is prepared under the condition that the temperature of the reaction vessel is maintained at 40 ° C. or higher and the ratio of the mass of nickel, cobalt, and manganese as a metal to the mass of the alkali metal hydroxide is 0.9 or higher. By mixing and stirring, the sphericality of the secondary particles can be controlled to the desired range of the present invention. As the reaction vessel, a type that overflows can be used in order to separate the formed reaction precipitate.

Further, the inside of the reaction vessel may be in an appropriate oxygen-containing atmosphere or in the presence of an oxidizing agent while maintaining an inert atmosphere. In order to create an oxygen-containing atmosphere in the reaction vessel, an oxygen-containing gas may be introduced into the reaction vessel.
Examples of the oxygen-containing gas include oxygen gas, air, and a mixed gas of these and an oxygen-free gas such as nitrogen gas. Among the above, a mixed gas is preferable from the viewpoint of easily adjusting the oxygen concentration in the oxygen-containing gas.

By appropriately controlling the concentration of the metal salt supplied to the reaction vessel, the stirring speed, the reaction temperature, the reaction pH, the firing conditions described later, etc., the finally obtained positive electrode active material for a lithium secondary battery can be obtained with desired physical properties. Can be controlled.

After the above reaction, the obtained reaction precipitate is washed with water and then dried to isolate a nickel cobalt manganese composite hydroxide as a nickel cobalt manganese composite compound. Further, if necessary, it may be washed with a weak acid water or an alkaline solution containing sodium hydroxide or potassium hydroxide. In the above example, the nickel-cobalt-manganese composite hydroxide is produced, but the nickel-cobalt-manganese composite oxide may be prepared.

When preparing a composite oxide of nickel and element X from a composite hydroxide of nickel and element X, it is oxidized by firing at a temperature of 300 ° C. or higher and 800 ° C. or lower for 1 hour or more and 10 hours or less. The materialization step may be carried out.
For example, a nickel cobalt manganese composite oxide can be prepared by firing a nickel cobalt manganese composite hydroxide. The firing time is preferably 1 hour or more and 30 hours or less, which is the total time from the start of temperature rise to the end of temperature retention. The heating rate of the heating step to reach the maximum holding temperature is preferably 180 ° C./hour or more, more preferably 200 ° C./hour or more, and particularly preferably 250 ° C./hour or more.

-Lithium compound The lithium compound used in the present invention is one of lithium carbonate, lithium nitrate, lithium acetate, lithium hydroxide, lithium oxide, lithium chloride, and lithium fluoride, or a mixture of two or more. can do. Among these, either one or both of lithium hydroxide and lithium carbonate is preferable.
When lithium hydroxide contains lithium carbonate as an impurity, the content of lithium carbonate in lithium hydroxide is preferably 5% by mass or less.

A method of mixing the precursor and the lithium compound will be described.
After drying the precursor, it is mixed with the lithium compound. The drying conditions are not particularly limited, and examples thereof include any of the following drying conditions 1) to 3).
1) Conditions under which the precursor is not oxidized or reduced. Specifically, it is a drying condition in which the oxide is maintained as an oxide, or the hydroxide is dried as a hydroxide.
2) Conditions under which the precursor is oxidized. Specifically, it is a drying condition for oxidizing from a hydroxide to an oxide.
3) Conditions under which the precursor is reduced. Specifically, it is a drying condition for reducing oxides to hydroxides.

For the conditions under which oxidation / reduction is not carried out, an inert gas such as nitrogen, helium or argon may be used. Oxygen or air may be used under conditions where the hydroxide is oxidized.
Further, under the condition that the precursor is reduced, a reducing agent such as hydrazine or sodium sulfite may be used under an inert gas atmosphere.

After the precursor is dried, classification may be carried out as appropriate.

The above lithium compounds and precursors are mixed in consideration of the composition ratio of the final target product. For example, the mixture is mixed with the lithium compound so that the ratio of the number of lithium atoms to the number of metal atoms contained in the precursor is greater than 1.0. That is, in the obtained lithium metal composite oxide, the lithium compound and the nickel cobalt manganese composite hydroxide have a molar ratio of more than 1 between lithium and the total of metal elements excluding lithium (total of elements X). To mix.
The ratio of the number of lithium atoms to the number of metal atoms is preferably 1.05 or more, more preferably 1.10 or more. A lithium-nickel-containing composite metal oxide is obtained by firing a mixture of the nickel-containing composite metal hydroxide and the lithium compound in a subsequent firing step.

The precursor and a lithium compound containing Li are mixed and fired to obtain a fired product.
For firing, dry air, an oxygen atmosphere, an inert atmosphere, or the like is used depending on the desired composition.
If necessary, it may be fired a plurality of times.

The firing temperature of the precursor and the lithium compound is not particularly limited, but is preferably 600 ° C. or higher and 1100 ° C. or lower, and more preferably 650 ° C. or higher and 1050 ° C. or lower.
When the firing temperature is at least the above lower limit value, a positive electrode active material for a lithium secondary battery having a strong crystal structure can be obtained. Further, when the firing temperature is not more than the above upper limit value, the volatilization of lithium on the surface of the lithium metal composite oxide can be reduced.
The firing temperature in the present specification means the temperature of the atmosphere in the firing furnace, and is the maximum holding temperature in the main firing step (hereinafter, may be referred to as the maximum holding temperature), and a plurality of heating steps are performed. In the case of the main firing step having, it means the temperature when heating at the maximum holding temperature in each heating step.

The firing time is preferably 3 hours or more and 50 hours or less. If the firing time exceeds 50 hours, the battery performance tends to be substantially inferior due to the volatilization of lithium. If the firing time is less than 3 hours, crystal development tends to be poor and battery performance tends to be poor. It is also effective to perform temporary firing before the above firing. The temperature of the tentative firing is preferably 300 ° C. or higher and 850 ° C. or lower for 1 to 10 hours. However, the temperature of the temporary firing is lower than that of the main firing.
In the present embodiment, the heating rate of the heating step to reach the maximum holding temperature is preferably 180 ° C./hour or more, more preferably 200 ° C./hour or more, and particularly preferably 250 ° C./hour or more.
The rate of temperature rise in the heating step to reach the maximum holding temperature is calculated from the time from the start of the temperature rise to the time to reach the holding temperature described later in the firing apparatus.

The firing step preferably has a plurality of firing steps at different firing temperatures. For example, it is preferable to have a first firing step and a second firing step in which the firing is performed at a higher temperature than the first firing step. Further, it may have different firing stages of firing temperature and firing time.

In the present embodiment, by firing the mixture in the presence of an inert melting agent, the reaction of the mixture can be promoted and the amount of oxygen on the particle surface of the obtained lithium metal composite oxide powder can be controlled within a preferable range. Further, the inert melting agent may remain in the lithium metal composite oxide powder after firing, or may be removed by washing with a cleaning liquid after firing. In the present embodiment, it is preferable to clean the fired lithium metal composite oxide powder with pure water, an alkaline cleaning solution, or the like.

When the mixture is fired in the presence of an inert melting agent, the R (90) of the obtained lithium metal composite oxide can be controlled within the preferable range of the present embodiment by adjusting the holding temperature in the firing. By adjusting the holding temperature during calcination in the presence of an inert melt, the reaction between the lithium compound and the precursor in the calcination step is promoted, and the formation of impurity phases such as oxygen-rich oxides is suppressed. A lithium metal composite oxide powder having an appropriately controlled amount of oxygen on the particle surface can be obtained.

The holding temperature in firing may be appropriately adjusted according to the type of transition metal element used, the type and amount of the precipitant and the inert melting agent.
In the present embodiment, the holding temperature may be set in consideration of the melting point of the inert melting agent described later, and is performed in the range of the melting point of the inert melting agent minus 100 ° C. or higher and the melting point of the inert melting agent plus 100 ° C. or lower. Is preferable.
Specific examples of the holding temperature include a range of 200 ° C. or higher and 1150 ° C. or lower, preferably 300 ° C. or higher and 1050 ° C. or lower, and more preferably 500 ° C. or higher and 1000 ° C. or lower.

The time for holding at the holding temperature is 0.1 hour or more and 20 hours or less, preferably 0.5 hours or more and 10 hours or less. The rate of temperature rise to the holding temperature is usually 50 ° C./hour or more and 400 ° C./hour or less, and the rate of temperature decrease from the holding temperature to room temperature is usually 10 ° C./hour or more and 400 ° C./hour or less. Further, as the firing atmosphere, air, oxygen, nitrogen, argon or a mixed gas thereof can be used.

The inert melting agent that can be used in the present embodiment is not particularly limited as long as it does not easily react with the mixture during firing. In the present embodiment, a fluoride of one or more elements (hereinafter referred to as “A”) selected from the group consisting of Na, K, Rb, Cs, Ca, Mg, Sr and Ba, and a chloride of A. , A carbonate, A sulfate, A nitrate, A phosphate, A hydroxide, A molybdenate and A strontium salt, one or more selected from the group. ..

Fluoride of A includes NaF (melting point: 993 ° C.), KF (melting point: 858 ° C.), RbF (melting point: 795 ° C.), CsF (melting point: 682 ° C.), CaF ₂ (melting point: 1402 ° C.), MgF ₂ (Melting point: 1263 ° C.), SrF ₂ (melting point: 1473 ° C.) and BaF ₂ (melting point: 1355 ° C.).

Chlorides of A include NaCl (melting point: 801 ° C.), KCl (melting point: 770 ° C.), RbCl (melting point: 718 ° C.), CsCl (melting point: 645 ° C.), CaCl ₂ (melting point: 782 ° C.), MgCl ₂ (Melting point: 714 ° C.), SrCl ₂ (melting point: 857 ° C.) and NaCl ₂ (melting point: 963 ° C.).

The carbonates of A include Na ₂ CO ₃ (melting point: 854 ° C), K ₂ CO ₃ (melting point: 899 ° C), Rb ₂ CO ₃ (melting point: 837 ° C), Cs ₂ CO ₃ (melting point: 793 ° C). , CaCO ₃ (melting point: 825 ° C.), MgCO ₃ (melting point: 990 ° C.), SrCO ₃ (melting point: 1497 ° C.) and BaCO ₃ (melting point: 1380 ° C.).

Sulfates of A include Na ₂ SO ₄ (melting point: 884 ° C), K ₂ SO ₄ (melting point: 1069 ° C), Rb ₂ SO ₄ (melting point: 1066 ° C), Cs ₂ SO ₄ (melting point: 1005 ° C). , CaSO ₄ (mp: 1460 ℃), MgSO ₄ (mp: 1137 ℃), SrSO ₄ (mp: 1605 ° C.) and BaSO ₄ (mp: 1580 ° C.) can be mentioned.

The nitrates of A include NaNO ₃ (melting point: 310 ° C), KNO ₃ (melting point: 337 ° C), RbNO ₃ (melting point: 316 ° C), CsNO ₃ (melting point: 417 ° C), Ca (NO ₃ ) ₂ (melting point). : 561 ° C.), Mg (NO ₃ ) ₂ , Sr (NO ₃ ) ₂ (melting point: 645 ° C.) and Ba (NO ₃ ) ₂ (melting point: 596 ° C.).

Phosphates of A include Na ₃ PO ₄ , K ₃ PO ₄ (melting point: 1340 ° C), Rb ₃ PO ₄ , Cs ₃ PO ₄ , Ca ₃ (PO ₄ ) ₂ , Mg ₃ (PO ₄ ) ₂ ( Melting point: 1184 ° C.), Sr ₃ (PO ₄ ) ₂ (melting point: 1727 ° C.) and Ba ₃ (PO ₄ ) ₂ (melting point: 1767 ° C.).

Hydroxides of A include NaOH (melting point: 318 ° C.), KOH (melting point: 360 ° C.), RbOH (melting point: 301 ° C.), CsOH (melting point: 272 ° C.), Ca (OH) ₂ (melting point: 408 ° C.). ), Mg (OH) ₂ (melting point: 350 ° C.), Sr (OH) ₂ (melting point: 375 ° C.) and Ba (OH) ₂ (melting point: 853 ° C.).

Examples of the molybdate of A include Na ₂ MoO ₄ (melting point: 698 ° C), K ₂ MoO ₄ (melting point: 919 ° C), Rb ₂ MoO ₄ (melting point: 958 ° C), and Cs ₂ MoO ₄ (melting point: 956 ° C). ), CaMoO ₄ (melting point: 1520 ° C.), MgMoO ₄ (melting point: 1060 ° C.), SrMoO ₄ (melting point: 1040 ° C.) and BaMoO ₄ (melting point: 1460 ° C.).

The tungstate A, _Na 2 WO ₄ (mp: 687 ° _C.), can be exemplified _{K 2 WO 4, Rb 2 WO} 4, Cs 2 WO 4, CaWO 4, MgWO 4, SrWO 4 and BaWO ₄ ..

In the present embodiment, two or more kinds of these inert melting agents can be used. When two or more types are used, the melting point may decrease. Among these inert melts, examples of the inert melt for obtaining a lithium metal composite oxide powder having higher crystallinity include hydroxide of A, carbonate and sulfate of A, and chloride of A. It is preferably any one or a combination thereof. Further, as A, it is preferable that either one or both of sodium (Na) and potassium (K) are used. That is, among the above, the particularly preferable inert melting agent is selected from the group consisting of NaOH, KOH, NaCl, KCl, Na ₂ CO ₃ , K ₂ CO ₃ , Na ₂ SO ₄ , and K ₂ SO _4. More than a seed.

In the present embodiment, when one or more selected from the group consisting of potassium sulfate, sodium sulfate and potassium carbonate is used as the inert melting agent, the obtained lithium metal composite oxide powder R (10) is used. It can be controlled to a preferable range of the embodiment. By firing in the presence of the inert melting agent, oxygen required for the mixture of the lithium compound and the precursor at the time of firing is sufficiently supplied through the inert melting agent, so that lithium with less oxygen deficiency on the particle surface. A metal composite oxide powder is obtained.

In the present embodiment, the abundance of the inert melting agent at the time of firing may be appropriately selected. In order for the R (90) of the obtained lithium metal composite oxide to be within the range of the present embodiment, the abundance of the inert melting agent at the time of firing is 0.1 part by mass or more with respect to 100 parts by mass of the lithium compound. It is preferably present, and more preferably 1 part by mass or more. Further, if necessary, an inert melting agent other than the above-mentioned inert melting agents may be used in combination. Examples of the melting agent include ammonium salts such as NH ₄ Cl and NH ₄ F.

The raw material compound is obtained by firing.
Pure water or an alkaline cleaning solution can be used for cleaning the inert melting agent remaining in the raw material compound after firing.
Examples of the alkaline cleaning solution include LiOH (lithium hydroxide), NaOH (sodium hydroxide), KOH (potassium hydroxide), Li ₂ CO ₃ (lithium carbonate), Na ₂ CO ₃ (sodium carbonate), and K ₂ CO _3. Examples thereof include an aqueous solution of one or more hydroxides selected from the group consisting of (potassium carbonate) and (NH ₄ ) ₂ CO ₃ (ammonium carbonate) and hydrates thereof. Ammonia can also be used as the alkali.

The temperature of the cleaning liquid used for cleaning is preferably 15 ° C. or lower, more preferably 10 ° C. or lower, and even more preferably 8 ° C. or lower. By controlling the temperature of the cleaning liquid within the above range without freezing, it is possible to suppress excessive elution of lithium ions from the crystal structure of the raw material compound into the cleaning liquid during cleaning.

In the cleaning step, as a method of bringing the cleaning liquid into contact with the raw material compound, a method of adding the raw material compound into the aqueous solution of each cleaning liquid and stirring the mixture, a method of using the aqueous solution of each cleaning liquid as shower water and applying the raw material compound to the raw material compound, Examples thereof include a method in which the raw material compound is put into the aqueous solution of the cleaning liquid and stirred, the raw material compound is separated from the aqueous solution of each cleaning liquid, and then the aqueous solution of each cleaning liquid is used as shower water and applied to the raw material compound after separation.

After cleaning, a step of separating the raw material compound from the cleaning liquid by filtration or the like and drying it may be carried out.

The raw material compound preferably satisfies the following formula (II).
Li (Li _p (Ni _(1-q-r) Co _q X1 _r ) _1-p ) O ₂ ... (II)
(−0.1 ≦ p ≦ 0.2, 0 ≦ q ≦ 0.4, 0 ≦ r ≦ 0.4, 1-q−r ≧ 0.3, X1 is Mn, Fe, Cu, Ti, Mg, One or more elements selected from the group consisting of Ca, Sr, Ba, Al, W, Mo, Nb, Zn, Sn, Zr, Cr, Ga, Ge, Pd, Ag, Cd, In and V).

The raw material compound preferably has a surplus lithium amount of 1% by mass or less, which is obtained as a conversion value from the result of neutralization titration. The amount of excess lithium refers to the content of Li element calculated from the total amount of lithium carbonate and lithium hydroxide contained in the residual alkali obtained as a conversion value from the result of neutralization titration of the raw material compound. The excess lithium amount is the amount of lithium that is not contained in the crystal structure of the raw material compound.
By adjusting the amount of surplus lithium in the raw material compound to the above range, the coating raw material described later reacts with the surplus lithium to form a coating layer in which the core particles are uniformly coated, and R (90) of the present embodiment is used. It becomes easier to control within the range.

[Step (b)]
The step (b) is a step of bringing the coating raw material containing the element M into contact with the raw material compound to obtain a raw material mixture.
The element M is at least one element selected from the group consisting of Al, B, Si, S, Nb, F and P.

The step (b) may be a step (b1) of bringing the coating raw material solution 1 containing the element M into contact with the raw material compound to obtain a raw material mixture.
The step (b1) may be a step (b1-1) of spraying and contacting the coating raw material solution 1 with the raw material compound to obtain a raw material mixture.
The step (b) may be a step (b2) of immersing the raw material compound in the coating raw material solution 2 containing the element M and lithium to obtain a raw material mixture.
The step (b) may be a step (b3) of bringing the powdered coating raw material containing the element M into contact with the powdered raw material compound to obtain a raw material mixture.

-Coating Raw Material The coating raw material preferably contains a coating compound containing at least one element selected from the group consisting of Al, B, Si, S, Nb, F and P. The coating compounds include, for example, Al ₂ O ₃ , H ₃ BO ₃ , HBO ₂ , H ₂ B ₄ O ₇ , HB ₅ O ₈ , B ₂ O ₃ , H ₄ SiO ₄ , H ₂ SiO ₃ , H ₂ Si _2. O ₅ , SiO ₂ , H ₂ SO ₄ , H ₂ SO ₃ , H ₂ S ₂ O ₃ , H ₂ SO ₆ , H ₂ SO ₈ , Nb ₂ O ₅ , LiF, H ₃ PO ₄ , H ₄ P ₂ O ₇ , H ₃ PO ₃ , H ₃ PO ₂ , Li ₃ PO ₄ , any one, or a mixture of two or more can be used. Among these, H ₃ BO ₃ , B ₂ O ₃ , Nb ₂ O ₅ , and Li ₃ PO ₄ are preferable.

・ Process (b1)
The case where the step (b) is a step (b1) of bringing the coating raw material solution 1 containing the element M into contact with the raw material compound to obtain a raw material mixture will be described.
The step (b1) may be used in a solution state (coating raw material solution 1) in which the coating compound is dispersed and dissolved in a solvent. As the solvent of the coating raw material solution, water or an organic solvent can be used, and water is preferable.

When the coating raw material solution 1 is used as the coating raw material, the following methods can be mentioned as a method for bringing the coating raw material solution 1 into contact with the raw material compound.
A method of immersing a raw material compound in the coating raw material solution 1. Here, "immersing" includes putting the raw material compound into the coating raw material solution 1 or stirring after putting it.
A method of applying the coating raw material solution 1 as a shower solution to the raw material compound.
A method of spraying a coating raw material solution 1 as a spray liquid onto a raw material compound.
After immersing the raw material compound in the coating raw material solution 1, the raw material compound is separated from the coating raw material solution 1. Next, a method in which the coating raw material solution 1 is used as a shower solution and brought into contact with the separated raw material compound to obtain a raw material mixture.

When the coating raw material solution 1 is used as the coating raw material, the solvent contained in the raw material mixture is removed after the step (b1) and before the step (c) described later, and the content of the solvent in the raw material mixture is 30. It is preferable to include a step (b1-A) for adjusting to mass% or less.
The content of the solvent contained in the raw material mixture is more preferably 25% by mass or less, and particularly preferably 20% by mass or less.
In this case, step (a), step (b1), step (b1-A) and step (c) are provided in this order.

When the coating raw material solution 1 is used as the coating raw material, "a method of immersing the raw material compound in the coating raw material solution 1 and bringing it into contact", "a method of spraying the coating raw material solution 1 as a spray solution and contacting the raw material compound", Alternatively, "a method of applying the coating raw material solution 1 as a shower liquid to the raw material compound" is preferable. The coating raw material can be uniformly adhered to the particle surface of the raw material compound by immersing it in the solution, contacting it with a spray liquid, or contacting it with a shower liquid.

・ ・ Process (b1-1)
The case where the step (b1) is a step (b1-1) of spraying the coating raw material solution 1 onto the raw material compound and bringing them into contact with each other to obtain a raw material mixture will be described.
When the coating raw material solution 1 is sprayed and brought into contact with the raw material compound as a spray liquid, it is preferable to adjust the temperature of the raw material compound to −20 ° C. or higher and 300 ° C. or lower, and spray the coating raw material solution 1 to bring it into contact. In order to suppress excessive extraction of Li from the raw material compound by the reaction between the raw material compound and hot water, the upper limit of the temperature of the raw material compound is preferably 270 ° C, more preferably 240 ° C, further preferably 210 ° C. 180 ° C. is particularly preferable. Further, the lower limit of the temperature of the raw material compound is preferably 0 ° C., more preferably 30 ° C., in order to prevent the coating raw material solution 1 from freezing, and Li is extracted from the raw material compound by the solution after contact with the raw material compound. 70 ° C. is more preferable, and 100 ° C. is particularly preferable, because the solution after contact with the raw material compound is immediately evaporated in order to suppress the reaction.
The upper and lower limits of the temperature of the raw material compound can be arbitrarily combined.

When the coating raw material solution 1 is sprayed onto the raw material compound as a spray liquid and brought into contact with the raw material compound, the Sauter mean diameter D _{32 of} the spray droplets is preferably 10 μm or more and 500 μm or less. The upper limit of the Sauter mean diameter D ₃₂ of the spray droplets is preferably 400 μm, more preferably 300 μm, further preferably 250 μm, and particularly preferably 200 μm in order to suppress the occurrence of uneven dispersion of the coating element M. Further, in order to prevent the productivity from being excessively lowered, the lower limit of the Sauter mean diameter D ₃₂ of the spray droplet is preferably 15 μm, more preferably 20 μm, further preferably 25 μm, and particularly preferably 30 μm.
The upper and lower limits of the Sauter mean diameter D ₃₂ of the spray droplets can be arbitrarily combined.

When the coating raw material solution 1 is sprayed onto the raw material compound as a spray liquid and brought into contact with the raw material compound, the ratio of the median diameter DP ₅₀ of the raw material compound to the Sauter mean diameter D ₃₂ of the sprayed droplets when the coating raw material solution is sprayed, DP _50. The / D ₃₂ is preferably 0.001 or more and 10 or less. The upper limit of DP ₅₀ / D ₃₂ is preferably 5, more preferably 1, even more preferably 0.7, and particularly preferably 0.5, in order to prevent an excessive decrease in productivity. Further, in order to suppress the occurrence of uneven dispersion of the coating element M, the lower limit of DP ₅₀ / D ₃₂ is preferably 0.003, more preferably 0.005, further preferably 0.007, and 0.01. Especially preferable.
The upper and lower limits of DP ₅₀ / D ₃₂ can be combined arbitrarily.

When the coating raw material solution 1 is sprayed as a spray liquid and brought into contact with the raw material compound, the solution temperature of the coating raw material solution 1 when the coating raw material solution 1 is brought into contact with the raw material compound is preferably −20 ° C. or higher and 300 ° C. or lower. .. The upper limit of the solution temperature is preferably 270 ° C., more preferably 240 ° C., even more preferably 210 ° C., and 180 ° C. in order to suppress excessive extraction of Li from the raw material compound by the reaction between the raw material compound and hot water. Is particularly preferable. Further, the lower limit of the solution temperature is preferably 0 ° C., more preferably 30 ° C., in order to prevent the coating raw material solution 1 from freezing, and suppresses Li from being extracted from the raw material compound by the solution after contact with the raw material compound. In order to immediately evaporate the solution after contact with the raw material compound, 70 ° C. is more preferable, and 100 ° C. is particularly preferable.
The upper and lower limits of the solution temperature can be arbitrarily combined.

When the coating raw material solution 1 is sprayed onto the raw material compound as a spray solution and brought into contact with the raw material compound, the concentration of the element M in the coating raw material solution 1 is preferably 0.001 mol / L or more and 100 mol / L or less. In order to suppress the occurrence of uneven dispersion of the coating element M, the upper limit of the concentration of the element M in the coating raw material solution 1 is preferably 80 mol / L, more preferably 70 mol / L, further preferably 60 mol / L, and 50 mol. / L is particularly preferable. Further, in order to prevent the productivity from being excessively lowered, the lower limit of the concentration of the element M in the coating raw material solution 1 is preferably 0.003 mol / L, more preferably 0.005 mol / L, and 0.007 mol. / L is more preferable, and 0.01 mol / L is particularly preferable.
The upper limit value and the lower limit value of the concentration of the element M in the coating raw material solution 1 can be arbitrarily combined.

When the coating raw material solution 1 is sprayed onto the raw material compound as a spray liquid and brought into contact with the raw material compound, the ratio (M / Li) of the substance amount of the element M to the substance amount of lithium contained in the raw material mixture is 0.1 or more and 50 or less. Is preferable. Here, the amount of substance of lithium contained in the raw material mixture is the amount excluding lithium contained in the crystal structure of the raw material compound contained in the raw material mixture. In order to prevent the element M from forming a resistance layer without forming a compound with Li, the upper limit of M / Li is preferably 30, more preferably 20, further preferably 10, and particularly preferably 5.
Further, in order to prevent the resistance reduction effect of the coating element M from diminishing, the lower limit of M / Li is preferably 0.2, more preferably 0.5, further preferably 1.0, and particularly 1.5. preferable.
The upper limit value and the lower limit value of M / Li can be arbitrarily combined.

・ Process (b2)
The case where the step (b) is a step (b2) of immersing the raw material compound in the coating raw material solution 2 containing the element M and lithium to obtain a raw material mixture will be described.
The lithium contained in the coating raw material solution 2 may be one in which unreacted residual lithium contained in the raw material compound is eluted in the solution, or may be one in which a lithium compound is separately added to the coating raw material solution. ..

When the raw material compound is immersed in the coating raw material solution 2, the amount of the coating raw material solution 2 with respect to the raw material compound is preferably 0.1 times or more and 10 times or less on a weight basis. In order to prevent Li from being excessively extracted from the raw material compound, the upper limit of the amount of the coating raw material solution 2 with respect to the raw material compound is preferably 8, more preferably 7, further preferably 6, and particularly preferably 5. Further, in order to maintain the fluidity of the slurry, the lower limit of the amount of the coating raw material solution 2 with respect to the raw material compound is preferably 0.3, more preferably 0.5, further preferably 0.7, and particularly preferably 1.
The upper limit value and the lower limit value of the amount of the coating raw material solution 2 with respect to the raw material compound can be arbitrarily combined.

When the raw material compound is immersed in the coating raw material solution 2, the temperature of the coating raw material solution 2 is preferably adjusted to −20 ° C. or higher and 80 ° C. or lower. The upper limit of the temperature of the coating raw material solution 2 is preferably 60 ° C., more preferably 50 ° C., and 40 ° C. in order to prevent excessive elution of lithium ions from the crystal structure of the raw material compound into the coating raw material solution. ° C is more preferred, and 30 ° C is particularly preferred. In order to prevent the coating raw material solution 2 from freezing, the lower limit of the temperature of the coating raw material solution 2 is preferably −15 ° C., more preferably −10 ° C., further preferably −5 ° C., and particularly preferably 0 ° C.
The upper limit value and the lower limit value of the temperature of the coating raw material solution 2 can be arbitrarily combined.

When the raw material compound is immersed in the coating raw material solution 2, the concentration of Li contained in the coating raw material solution 2 is preferably 0.01 mol / L or more and 10 mol / L or less. In order to prevent excess impurities Li from remaining in the raw material mixture, the upper limit of the concentration of Li contained in the coating raw material solution 2 is preferably 5 mol / L, more preferably 2 mol / L, and further preferably 1 mol / L. It is preferable, and 0.5 mol / L is particularly preferable.
Further, in order to prevent the element M from forming a resistance layer without forming a compound with Li, the lower limit of the concentration of Li contained in the coating raw material solution 2 is preferably 0.015 mol / L, preferably 0.018 mol. / L is more preferable, 0.020 mol / L is further preferable, and 0.22 mol / L is particularly preferable.
The upper limit value and the lower limit value of the concentration of Li contained in the coating raw material solution 2 can be arbitrarily combined.

When the raw material compound is immersed in the coating raw material solution 2, the ratio (M / Li) of the substance amount of the element M to the substance amount of lithium contained in the raw material mixture is preferably 0.1 or more and 50 or less. .. Here, the amount of substance of lithium contained in the raw material mixture is the amount excluding lithium contained in the crystal structure of the raw material compound contained in the raw material mixture. In order to prevent the element M from forming a resistance layer without forming a compound with Li, the upper limit of M / Li is preferably 30, more preferably 20, further preferably 10, and particularly preferably 5. Further, in order to prevent the resistance reduction effect of the coating element M from diminishing, the lower limit of M / Li is preferably 0.2, more preferably 0.5, further preferably 1.0, and particularly 1.5. preferable.
The upper limit value and the lower limit value of M / Li can be arbitrarily combined.

・ Process (b3)
The case where the step (b) is a step (b3) of bringing a powdery coating raw material containing an element M into contact with a powdery raw material compound to obtain a raw material mixture will be described.
When the coating raw material and the raw material compound are brought into contact with each other, when a powdered coating compound is used as the coating raw material, the coating raw material and the raw material compound are mixed and contacted in the powder state to obtain a raw material mixture.

The ratio (M / Li) of the amount of substance of the element M to the amount of substance of lithium contained in the raw material mixture is preferably 0.1 or more and 50 or less. Here, the amount of substance of lithium contained in the raw material mixture is the amount excluding lithium contained in the crystal structure of the raw material compound contained in the raw material mixture. In order to prevent the element M from forming a resistance layer without forming a compound with Li, the upper limit of M / Li is preferably 30, more preferably 20, further preferably 10, and particularly preferably 5. Further, in order to prevent the resistance reduction effect of the coating element M from diminishing, the lower limit of M / Li is preferably 0.2, more preferably 0.5, further preferably 1.0, and particularly 1.5. preferable.
The upper limit value and the lower limit value of M / Li can be arbitrarily combined.

The ratio (M / (Ni + X)) of the element M contained in the coating raw material to the total amount (Ni + X) of the metal elements excluding Li contained in the raw material compound in the step (b) is 0.001 or more and 0.05 in terms of molar ratio. The following is preferable. The upper limit of M / (Ni + X) is preferably 0.04 in order to prevent the weight ratio of the core particle portion of the lithium metal composite oxide undergoing the charge / discharge reaction from being excessively lowered due to the excessive coating layer. 0.03 is more preferable, 0.025 is further preferable, and 0.02 is particularly preferable. Further, in order to prevent the resistance reducing effect of the coating element M from diminishing, the lower limit of M / (Ni + X) is preferably 0.002, more preferably 0.003, further preferably 0.0035, and 0.004. Is particularly preferable.
The upper limit value and the lower limit value of M / (Ni + X) can be arbitrarily combined.
By setting the ratio of the element M in the coating material within the above range, it becomes easy to control R (90) within the range of the present embodiment.

[Step (c)]
The step (c) is a step of heat-treating the raw material mixture obtained in the step (b) at a temperature of 200 ° C. or higher to 600 ° C. or lower.

-Heat treatment step From the viewpoint of uniformly dispersing the coating on the surface of the particles of the lithium metal composite oxide powder, the heating temperature in the heat treatment step is more preferably 250 ° C. or higher, and particularly preferably 300 ° C. or higher.
Further, the heating temperature in the heat treatment step is more preferably 550 ° C. or lower, and particularly preferably 500 ° C. or lower, from the viewpoint of suppressing thermal decomposition of the coating material and solid solution of the coating raw material into the raw material compound.
By heating in the above temperature range, it becomes easy to control R (90) within the range of the present embodiment.
After heating, the lithium metal composite oxide powder of the present embodiment is obtained.

[Arbitrary process]
In the present embodiment, it is preferable to clean the lithium metal composite oxide powder after the heating step by using pure water, an alkaline cleaning solution, or the like as a cleaning solution.
Examples of the alkaline cleaning solution include LiOH (lithium hydroxide), NaOH (sodium hydroxide), KOH (potassium hydroxide), Li ₂ CO ₃ (lithium carbonate), Na ₂ CO ₃ (sodium carbonate), and K ₂ CO _3. Examples thereof include an aqueous solution of one or more anhydrides selected from the group consisting of (potassium carbonate) and (NH ₄ ) ₂ CO ₃ (ammonium carbonate), and an aqueous solution of the hydrate of the anhydride. Ammonia can also be used as the alkali.

In the cleaning step, as a method of bringing the cleaning liquid into contact with the lithium metal composite oxide powder, a method of putting the lithium metal composite oxide powder into each cleaning liquid and stirring it, or a method of using each cleaning liquid as shower water and lithium metal composite A method of sprinkling on an oxide powder, or by putting a lithium metal composite oxide powder into the cleaning liquid and stirring the mixture, the lithium metal composite oxide powder is separated from each cleaning liquid, and then each cleaning liquid is separated as shower water. A method of applying to the later lithium metal composite oxide powder can be mentioned.

The temperature of the cleaning liquid used for cleaning is preferably 15 ° C. or lower, more preferably 10 ° C. or lower, and even more preferably 8 ° C. or lower. By controlling the temperature of the cleaning liquid to a temperature at which the cleaning liquid does not freeze within the above range, it is possible to suppress excessive elution of lithium ions from the crystal structure of the lithium metal composite oxide powder into the cleaning liquid during cleaning.

The lithium metal composite oxide powder obtained by firing is pulverized after undergoing an arbitrary cleaning step and appropriately classified to obtain a positive electrode active material for a lithium secondary battery applicable to a lithium secondary battery.
The positive electrode active material for a lithium secondary battery of the present embodiment may contain a lithium metal composite oxide powder different from the lithium metal composite oxide powder of the present embodiment.

<Lithium secondary battery>
Next, a configuration of a lithium secondary battery suitable for use as the positive electrode active material of the present embodiment will be described.
Further, a positive electrode suitable for use as a positive electrode active material for a lithium secondary battery containing the positive electrode active material powder of the present embodiment will be described.
Further, a lithium secondary battery suitable for use as a positive electrode will be described.

An example of a lithium secondary battery suitable for use as the positive electrode active material of the present embodiment includes a positive electrode and a negative electrode, a separator sandwiched between the positive electrode and the negative electrode, and an electrolytic solution arranged between the positive electrode and the negative electrode. ..

1A and 1B are schematic views showing an example of a lithium secondary battery. The cylindrical lithium secondary battery 10 is manufactured as follows.

First, as shown in FIG. 1A, a pair of strip-shaped separators 1, a strip-shaped positive electrode 2 having a positive electrode lead 21 at one end, and a strip-shaped negative electrode 3 having a negative electrode lead 31 at one end are divided into a separator 1, a positive electrode 2, and a separator. The electrode group 4 is formed by laminating 1 and the negative electrode 3 in this order and winding them.

Next, as shown in FIG. 1B, after accommodating the electrode group 4 and an insulator (not shown) in the battery can 5, the bottom of the can is sealed, the electrode group 4 is impregnated with the electrolytic solution 6, and the positive electrode 2 and the negative electrode 3 are arranged. Place the electrolyte between. Further, the lithium secondary battery 10 can be manufactured by sealing the upper part of the battery can 5 with the top insulator 7 and the sealing body 8.

The shape of the electrode group 4 is, for example, a columnar shape such that the cross-sectional shape when the electrode group 4 is cut in the direction perpendicular to the winding axis is a circle, an ellipse, a rectangle, or a rectangle with rounded corners. Can be mentioned.

Further, as the shape of the lithium secondary battery having such an electrode group 4, the shape defined by IEC60086, which is a standard for batteries defined by the International Electrotechnical Commission (IEC), or JIS C 8500 can be adopted. .. For example, a cylindrical shape, a square shape, or the like can be mentioned.

Further, the lithium secondary battery is not limited to the above-mentioned winding type configuration, and may have a laminated configuration in which a laminated structure of a positive electrode, a separator, a negative electrode, and a separator is repeatedly laminated. Examples of the laminated lithium secondary battery include so-called coin-type batteries, button-type batteries, and paper-type (or sheet-type) batteries.

Hereinafter, each configuration will be described in order.
(Positive electrode)
The positive electrode can be manufactured by first preparing a positive electrode mixture containing a positive electrode active material, a conductive material and a binder, and supporting the positive electrode mixture on a positive electrode current collector.

(Conductive material)
A carbon material can be used as the conductive material of the positive electrode. Examples of the carbon material include graphite powder, carbon black (for example, acetylene black), and fibrous carbon material. Since carbon black is fine and has a large surface area, it is possible to improve the conductivity inside the positive electrode by adding a small amount to the positive electrode mixture to improve charge / discharge efficiency and output characteristics, but if too much is added, it depends on the binder. Both the binding force between the positive electrode mixture and the positive electrode current collector and the binding force inside the positive electrode mixture decrease, which causes an increase in internal resistance.

The ratio of the conductive material in the positive electrode mixture is preferably 5 parts by mass or more and 20 parts by mass or less with respect to 100 parts by mass of the positive electrode active material. When a fibrous carbon material such as graphitized carbon fiber or carbon nanotube is used as the conductive material, this ratio can be reduced.

(binder)
As the binder contained in the positive electrode, a thermoplastic resin can be used. Examples of this thermoplastic resin include polyvinylidene fluoride (hereinafter, may be referred to as PVdF), polytetrafluoroethylene (hereinafter, may be referred to as PTFE), ethylene tetrafluoride, propylene hexafluoride, and vinylidene fluoride. Fluororesin such as copolymer, propylene hexafluoride / vinylidene fluoride-based copolymer, ethylene tetrafluoride / perfluorovinyl ether-based copolymer; polyolefin resin such as polyethylene and polypropylene; can be mentioned.

Two or more kinds of these thermoplastic resins may be mixed and used. Fluororesin and polyolefin resin are used as binders, and the ratio of fluororesin to the entire positive electrode mixture is 1% by mass or more and 10% by mass or less, and the ratio of polyolefin resin is 0.1% by mass or more and 2% by mass or less. It is possible to obtain a positive electrode mixture having high adhesion to the current collector and high bonding force inside the positive electrode mixture.

(Positive current collector)
As the positive electrode current collector of the positive electrode, a band-shaped member made of a metal material such as Al, Ni, or stainless steel can be used. Of these, Al is used as a forming material and processed into a thin film because it is easy to process and inexpensive.

Examples of the method of supporting the positive electrode mixture on the positive electrode current collector include a method of pressure molding the positive electrode mixture on the positive electrode current collector. Further, the positive electrode mixture is made into a paste using an organic solvent, and the obtained positive electrode mixture paste is applied to at least one surface side of the positive electrode current collector, dried, pressed and fixed to the positive electrode current collector. The mixture may be carried.

When the positive electrode mixture is made into a paste, the organic solvents that can be used include amine solvents such as N, N-dimethylaminopropylamine and diethylenetriamine; ether solvents such as tetrahydrofuran; ketone solvents such as methyl ethyl ketone; methyl acetate. Ester-based solvents such as dimethylacetamide and amide-based solvents such as N-methyl-2-pyrrolidone (hereinafter, may be referred to as NMP);

Examples of the method of applying the paste of the positive electrode mixture to the positive electrode current collector include a slit die coating method, a screen coating method, a curtain coating method, a knife coating method, a gravure coating method and an electrostatic spray method.

The positive electrode can be manufactured by the method described above.
(Negative electrode)
The negative electrode of the lithium secondary battery need only be capable of doping and dedoping lithium ions at a potential lower than that of the positive electrode, and is an electrode in which a negative electrode mixture containing a negative electrode active material is supported on a negative electrode current collector. An electrode made of the negative electrode active material alone can be mentioned.

(Negative electrode active material)
Examples of the negative electrode active material of the negative electrode include carbon materials, chalcogen compounds (oxides, sulfides, etc.), nitrides, metals, or alloys that can be doped and dedoped with lithium ions at a lower potential than the positive electrode. Be done.

Examples of the carbon material that can be used as the negative electrode active material include graphite such as natural graphite and artificial graphite, cokes, carbon black, thermally decomposed carbons, carbon fibers, and calcined organic polymer compounds.

Oxides that can be used as the negative electrode active material include silicon oxides represented by the formula SiO _x (where x is a positive real number) such as SiO ₂ , SiO; the formula TiO _x such as TiO ₂ and TiO (here). , X is a positive real number) titanium oxide; V ₂ O ₅ , VO _2, etc. Formula VO _x (where x is a positive real number) vanadium oxide; Fe ₃ O ₄ , Fe ₂ O ₃ , FeO, etc. Iron oxide represented by the formula FeO _x (where x is a positive real number); SnO ₂ , SnO, etc. formula SnO _x (where x is a positive real number) Tin oxide; Oxide of tungsten represented by the general formula WO _x (where x is a positive real number) such as WO ₃ and WO ₂ ; Li ₄ Ti ₅ O ₁₂ and Li VO ₂ and other lithium and titanium Alternatively, a composite metal oxide containing vanadium; can be mentioned.

Sulfides that can be used as the negative electrode active material include Ti ₂ S ₃ , TiS ₂ , TiS, and other titanium sulfides represented by the formula TiS _x (where x is a positive real number); V ₃ S ₄ , VS. _2. VS, etc. The sulfide of vanadium represented by the formula VS _x (where x is a positive real number); Fe ₃ S ₄ , FeS ₂ , FeS, etc. formula FeS _x (where x is a positive real number) Iron sulfide represented by; Mo ₂ S ₃ , MoS _2, etc. Formula MoS _x (where x is a positive real number) Molybdenum sulfide represented by the formula MoS _x (where x is a positive real number); SnS _2, SnS, etc. formula SnS _x (here, here) Tin sulfide represented by x is a positive real number); WS _{2 and the} like formula WS _x (where x is a positive real number) and represented by tungsten sulfide; Sb ₂ S _{3 and the} like formula SbS _x (here) in, x is antimony represented by a positive real _{number); Se 5 S 3, SeS} 2, SeS formula SeS _x (wherein such, sulfide selenium x is represented by a positive real number); the Can be mentioned.

The nitrides that can be used as the negative electrode active material include Li ₃ N and Li _3-x A _x N (where A is either or both of Ni and Co, and 0 <x <3). Such as lithium-containing nitrides can be mentioned.

These carbon materials, oxides, sulfides, and nitrides may be used alone or in combination of two or more. Further, these carbon materials, oxides, sulfides and nitrides may be either crystalline or amorphous.

Examples of the metal that can be used as the negative electrode active material include lithium metal, silicon metal, and tin metal.

Alloys that can be used as the negative electrode active material include lithium alloys such as Li-Al, Li-Ni, Li-Si, Li-Sn, and Li-Sn-Ni; silicon alloys such as Si-Zn; Sn-Mn, Sn. Also mentioned are tin alloys such as −Co, Sn—Ni, Sn—Cu, Sn—La; alloys such as Cu ₂ Sb, La ₃ Ni ₂ Sn ₇ ;

These metals and alloys are mainly used alone as electrodes after being processed into a foil, for example.

Among the above negative electrode active materials, the potential of the negative electrode hardly changes from the uncharged state to the fully charged state during charging (potential flatness is good), the average discharge potential is low, and the capacity retention rate when repeatedly charged and discharged is high. A carbon material containing graphite as a main component, such as natural graphite or artificial graphite, is preferably used because of its high value (good cycle characteristics). The shape of the carbon material may be, for example, a flaky shape such as natural graphite, a spherical shape such as mesocarbon microbeads, a fibrous shape such as graphitized carbon fiber, or an agglomerate of fine powder.

The negative electrode mixture may contain a binder, if necessary. Examples of the binder include thermoplastic resins, and specific examples thereof include PVdF, thermoplastic polyimide, carboxymethyl cellulose, polyethylene and polypropylene.

(Negative electrode current collector)
Examples of the negative electrode current collector included in the negative electrode include a band-shaped member made of a metal material such as Cu, Ni, or stainless steel as a forming material. Among them, Cu is used as a forming material and processed into a thin film because it is difficult to form an alloy with lithium and it is easy to process.

As a method of supporting the negative electrode mixture on such a negative electrode current collector, as in the case of the positive electrode, a method by pressure molding, a paste using a solvent or the like, coating on the negative electrode current collector, drying and pressing. A method of crimping can be mentioned.

(Separator)
As the separator contained in the lithium secondary battery, for example, a material having a form such as a porous film, a non-woven fabric, or a woven fabric made of a material such as a polyolefin resin such as polyethylene or polypropylene, a fluororesin, or a nitrogen-containing aromatic polymer is used. Can be used. Further, two or more kinds of these materials may be used to form a separator, or these materials may be laminated to form a separator.

In the present embodiment, the separator has an air permeation resistance of 50 seconds / 100 cc or more and 300 seconds / 100 cc according to the Garley method defined by JIS P 8117 in order to allow the electrolyte to permeate well when the battery is used (during charging / discharging). It is preferably 50 seconds / 100 cc or more, and more preferably 200 seconds / 100 cc or less.

The porosity of the separator is preferably 30% by volume or more and 80% by volume or less, and more preferably 40% by volume or more and 70% by volume or less. The separator may be a stack of separators having different porosity.

(Electrolytic solution)
The electrolytic solution contained in the lithium secondary battery contains an electrolyte and an organic solvent.

The electrolytes contained in the electrolytic solution include LiClO ₄ , LiPF ₆ , LiAsF ₆ , LiSbF ₆ , LiBF ₄ , LiCF ₃ SO ₃ , LiN (SO ₂ CF ₃ ) ₂ , LiN (SO ₂ C ₂ F ₅ ) ₂ , LiN. (SO ₂ CF ₃ ) (COCF ₃ ), Li (C ₄ F ₉ SO ₃ ), LiC (SO ₂ CF ₃ ) ₃ , Li ₂ B ₁₀ Cl ₁₀ , LiBOB (where BOB is bis (oxalato) boronate) ), LiFSI (where FSI stands for bis (fluorosulfonyl) image), lower aliphatic carboxylic acid lithium salts, lithium salts such as LiAlCl _4, and mixtures of two or more of these. May be used. Among them, the electrolyte is at least selected from the group consisting of LiPF ₆ , LiAsF ₆ , LiSbF ₆ , LiBF ₄ , LiCF ₃ SO ₃ , LiN (SO ₂ CF ₃ ) ₂ and LiC (SO ₂ CF ₃ ) ₃ containing fluorine. It is preferable to use one containing one type.

Examples of the organic solvent contained in the electrolytic solution include propylene carbonate, ethylene carbonate, dimethyl carbonate, diethyl carbonate, ethyl methyl carbonate, 4-trifluoromethyl-1,3-dioxolan-2-one, 1,2-di. Carbonates such as (methoxycarbonyloxy) ethane; 1,2-dimethoxyethane, 1,3-dimethoxypropane, pentafluoropropylmethyl ether, 2,2,3,3-tetrafluoropropyldifluoromethyl ether, tetrahydrofuran, 2- Ethers such as methyl tetrahydrofuran; esters such as methyl formate, methyl acetate, γ-butyrolactone; nitriles such as acetonitrile and butyronitrile; amides such as N, N-dimethylformamide, N, N-dimethylacetamide; 3-methyl Carbamates such as -2-oxazolidone; sulfur-containing compounds such as sulfolane, dimethylsulfoxide, 1,3-propanesartone, or those in which a fluoro group is further introduced into an organic solvent (1 of the hydrogen atoms of the organic solvent). The above is replaced with a fluorine atom).

As the organic solvent, it is preferable to use a mixture of two or more of these. Of these, a mixed solvent containing carbonates is preferable, and a mixed solvent of cyclic carbonate and acyclic carbonate and a mixed solvent of cyclic carbonate and ethers are more preferable. As the mixed solvent of the cyclic carbonate and the acyclic carbonate, a mixed solvent containing ethylene carbonate, dimethyl carbonate and ethyl methyl carbonate is preferable. An electrolytic solution using such a mixed solvent has a wide operating temperature range, is not easily deteriorated even when charged and discharged at a high current rate, is not easily deteriorated even when used for a long time, and is made of natural graphite as an active material of a negative electrode. It has many features that it is resistant to decomposition even when a graphite material such as artificial graphite is used.

Further, as the electrolytic solution, it is preferable to use an electrolytic solution containing a lithium salt containing fluorine such as LiPF ₆ and an organic solvent having a fluorine substituent because the safety of the obtained lithium secondary battery is enhanced. A mixed solvent containing ethers having a fluorine substituent such as pentafluoropropylmethyl ether and 2,2,3,3-tetrafluoropropyldifluoromethyl ether and dimethyl carbonate has a capacity even when charged and discharged at a high current rate. It is more preferable because of its high maintenance rate.

A solid electrolyte may be used instead of the above electrolyte. As the solid electrolyte, for example, an organic polymer electrolyte such as a polyethylene oxide-based polymer compound, a polymer compound containing at least one of a polyorganosiloxane chain or a polyoxyalkylene chain can be used. Further, a so-called gel type compound in which a non-aqueous electrolytic solution is retained in a polymer compound can also be used. In addition, Li ₂ S-SiS ₂ , Li ₂ S-GeS ₂ , Li ₂ S-P ₂ S ₅ , Li ₂ S-B ₂ S ₃ , Li ₂ S-SiS ₂ -Li ₃ PO ₄ , Li ₂ S-SiS _{2 -Li 2 SO 4, Li 2} S-GeS 2 -P 2 S 5 inorganic solid electrolytes containing a sulfide, and the like, may be used a mixture of two or more thereof. By using these solid electrolytes, the safety of the lithium secondary battery may be further enhanced.

Further, in the lithium secondary battery, when a solid electrolyte is used, the solid electrolyte may serve as a separator, and in that case, the separator may not be required.

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

<Scanning electron microscope-energy dispersive X-ray (EDX) spectroscopic measurement>
The cumulative frequency distribution curve of R on the surface of the lithium metal composite oxide powder was determined by using a scanning electron microscope-energy dispersive X-ray (EDX) spectroscopy (JSM-7900F) manufactured by JEOL Ltd.
Here, R is the ratio (O / (Ni + X)) of the amount of substance (O) of oxygen to the total amount of substance (Ni + X) of Ni and the element X.

≪How to find the cumulative frequency distribution curve of R≫
EDX plane analysis for each primary particle of the lithium metal composite oxide was carried out for 50 particles, and R on the surface of each particle was calculated from the obtained EDX spectrum. The accelerating voltage at this time was 1100 V. Further, a cumulative frequency distribution curve is created from the calculated ratio R of 50 particles, and the value of R at the point where the cumulative frequency from the smaller side of R is 90% is R (90), and the value of R at the point where R is 10%. The value was R (10), and the value of R at the point where the value was 50% was R (50).
Specifically, an SEM image of the lithium metal composite oxide powder was obtained with a field of view of 5000 times. Ten particles were randomly selected from the particles contained in the field of view. This operation was performed in 5 fields of view, and analysis of 50 particles was performed.

<Powder X-ray diffraction measurement>
The powder X-ray diffraction measurement was performed using an X-ray diffractometer (Ultima IV manufactured by Rigaku Co., Ltd.). Lithium metal composite compound powder is filled in a dedicated substrate and measured using a Cu-Kα source under the conditions of diffraction angle 2θ = 10 ° to 90 °, sampling width 0.02 °, and scan speed 4 ° / min. A powder X-ray diffraction pattern was obtained.

<Measurement of cumulative particle size>
0.1 g of the lithium metal composite oxide powder was put into 50 ml of a 0.2 mass% sodium hexametaphosphate aqueous solution to obtain a dispersion liquid in which the lithium metal composite oxide powder was dispersed. Next, the particle size distribution of the obtained dispersion was measured using a Microtrack MT3300EXII (laser diffraction scattering particle size distribution measuring device) manufactured by Microtrack Bell Co., Ltd., and a volume-based cumulative particle size distribution curve was obtained. Then, in the obtained cumulative particle size distribution curve, the value of the particle size at the point where the cumulative volume from the fine particle side is 90% when the whole is 100% is 90% cumulative volume particle size (D ₉₀ ) (μm). ), The value of the particle size at the point where the cumulative volume is 50% is 50% cumulative volume particle size (D ₅₀ ) (μm), and the value of the particle size at the point where the cumulative volume is 10% is 10% cumulative volume particle size (D). ₁₀ ) Obtained as (μm).

<Composition analysis>
The composition analysis of the lithium metal composite oxide powder produced by the method described below is carried out by dissolving the obtained lithium metal composite oxide powder in hydrochloric acid and then inductively coupled plasma emission spectrometry (SI Nanotechnology Co., Ltd.). , SPS3000).

<Measurement of excess lithium contained in lithium metal composite oxide powder>
20 g of lithium metal composite oxide powder and 100 g of pure water were placed in a 100 ml beaker and stirred for 5 minutes. After stirring, the lithium metal composite oxide powder was filtered, 0.1 mol / L hydrochloric acid was added dropwise to 60 g of the remaining filtrate, and the pH of the filtrate was measured with a pH meter. The titration amount of hydrochloric acid at pH = 8.3 ± 0.1 is Aml, and the titration amount of hydrochloric acid at pH = 4.5 ± 0.1 is Bml. From the following formula, in the lithium metal composite oxide powder. The concentrations of lithium carbonate and lithium hydroxide remaining in the water were calculated. In the formula below, the molecular weights of lithium carbonate and lithium hydroxide were calculated with each atomic weight as H; 1.000, Li; 6.941, C; 12, O; 16.
The amount of surplus lithium was determined from the amounts of lithium carbonate and lithium hydroxide.
Lithium carbonate concentration (mass%) = {0.1 × (BA) / 1000} × {73.882 / (20 × 60/100)} × 100
Lithium hydroxide concentration (mass%) = {0.1 × (2A-B) / 1000} × {23.941 / (20 × 60/100)} × 100

<Observation of single particles>
Scanning electron microscopy of the lithium metal composite oxide powder was carried out, and the presence of single particles independent of the primary particles or secondary particles was confirmed.

≪Measurement of self-discharge rate≫
The self-discharge rate was measured by the following method.
A lithium secondary battery (coin-type cell) was produced using the lithium metal composite oxide powder obtained by the method described later as a positive electrode active material. The lithium metal composite oxide powder obtained by the method described later, the conductive material (acetylene black), and the binder (PVdF) are added and kneaded so as to have a composition of 92: 5: 3 (mass ratio). A paste-like positive electrode mixture was prepared. N-methyl-2-pyrrolidone was used as an organic solvent when preparing the positive electrode mixture.

The obtained positive electrode mixture was applied to an Al foil having a thickness of 40 μm as a current collector and vacuum dried at 150 ° C. for 8 hours to obtain a positive electrode for a lithium secondary battery. The electrode area of the positive electrode for the lithium secondary battery was 1.65 cm ² .

A lithium secondary battery (coin-type battery R2032; hereinafter, may be referred to as a "coin-type battery") was produced using the obtained positive electrode for a lithium secondary battery. A laminated film separator (a heat-resistant porous layer is laminated on a polypropylene porous film) is placed on the lower lid of a coin cell (manufactured by Hosen Co., Ltd.) for the coin-type battery R2032 with the aluminum foil side facing down. 25 μm)) is placed. 300 μL of the electrolytic solution is injected therein. The electrolytic solution to be used was prepared by dissolving LiPF ₆ in a 30:35:35 (volume ratio) mixture of ethylene carbonate, dimethyl carbonate and ethyl methyl carbonate so as to be 1.0 mol / L.
Next, using metallic lithium as the negative electrode, the negative electrode was placed on the upper side of the laminated film separator, the upper lid was covered with a gasket, and the lithium secondary battery was produced by caulking with a caulking machine.

Furthermore, the test was carried out as follows using the obtained coin-type battery.
The battery was charged at a test temperature of 25 ° C. with a maximum charging voltage of 4.4 V, a charging current of 0.5 CA, and a constant current constant voltage mode until the current value reached 0.05 CA. Then, constant current discharge was performed up to 2.5 V with a discharge current value of 0.5 CA, and the discharge capacity before storage was measured.
Next, after charging at a test temperature of 25 ° C. until the maximum charging voltage is 4.4 V, the charging current is 0.5 CA, and the current value reaches 0.05 CA in the constant current constant voltage mode, the charged coin-type battery is charged at a test temperature of 60 ° C. It was stored for 7 days. After storage, constant current discharge was performed at 25 ° C. up to 2.5 V with a discharge current value of 0.5 CA, and the storage capacity was measured. The self-discharge rate was calculated from the following formula.
Self-discharge rate (%) = (storage capacity / discharge capacity before storage) x 100

<< Example 1 >>
1. 1. Production of Lithium Metal Composite Oxide Powder A1 Water was placed in a reaction vessel equipped with a stirrer and an overflow pipe, and then an aqueous sodium hydroxide solution was added. The liquid temperature in the reaction vessel was maintained at 60 ° C.

The molar ratios of nickel sulfate aqueous solution, cobalt sulfate aqueous solution, manganese sulfate aqueous solution, and zirconium sulfate aqueous solution are Ni: Co: Mn = 0.60: 0.20: 0.20, Zr / (Ni + Co + Mn) = 0.005. The mixture was mixed so as to prepare a mixed raw material solution 1.

Next, the mixed raw material solution 1 and the ammonium sulfate aqueous solution were continuously added as a complexing agent into the reaction vessel under stirring. An aqueous sodium hydroxide solution was added dropwise in an appropriate manner so that the pH of the solution in the reaction vessel became 11.9. A nickel-containing transition metal composite hydroxide is obtained, washed, dehydrated with a centrifuge, washed, dehydrated, isolated and dried at 105 ° C. to obtain a nickel-containing transition metal composite hydroxide as a precursor. I got A1.

The nickel-containing transition metal composite hydroxide A1 and lithium hydroxide monohydrate are weighed and mixed so that the molar ratio is Li / (Ni + Co + Mn) = 1.05, and then 5 at 650 ° C. under an oxygen atmosphere. After firing for hours, the raw material compound A1 was obtained by further firing at 970 ° C. for 5 hours in an oxygen atmosphere.

As a result of the composition analysis of the raw material compound A1, p = 0.023, q = 0.198, and r = 0.199 in the composition formula (II).

The raw material compound A1 and boric acid powder were mixed so as to have a molar ratio of B / (Ni + X) = 0.02 to obtain a raw material mixture A1. The ratio of the amount of substance of B (B / Li) to the amount of substance of Li excluding Li contained in the crystal structure of the raw material compound A1 contained in the raw material mixture A1 was 1.9.

The raw material mixture A1 was heat-treated at 500 ° C. for 5 hours to obtain a lithium metal composite oxide powder A1.

As a result of the composition analysis of the lithium metal composite oxide powder A1, m = 0.015 and n = 0.406 in the composition formula (I), and m1 = 0.015 and n12 = 0 in the composition formula (I) -1. .195, n13 = 0.196, n14 = 0.015. The obtained lithium metal composite oxide powder A1 was used as the positive electrode active material A1 for evaluation using the above-mentioned coin-type battery.

<< Example 2 >>
1. 1. Production of Lithium Metal Composite Oxide Powder A2 After putting water in a reaction vessel equipped with a stirrer and an overflow pipe, an aqueous sodium hydroxide solution was added. The liquid temperature in the reaction vessel was maintained at 60 ° C.

An aqueous solution of nickel sulfate, an aqueous solution of cobalt sulfate, and an aqueous solution of manganese sulfate were mixed so as to have a molar ratio of Ni: Co: Mn = 0.60: 0.20: 0.20 to prepare a mixed raw material solution 2.

Next, the mixed raw material solution 2 and the ammonium sulfate aqueous solution were continuously added as a complexing agent into the reaction vessel under stirring. An aqueous sodium hydroxide solution was added dropwise in an appropriate manner so that the pH of the solution in the reaction vessel became 11.7. A nickel-containing transition metal composite hydroxide is obtained, washed, dehydrated with a centrifuge, washed, dehydrated, isolated and dried at 105 ° C. to obtain a nickel-containing transition metal composite hydroxide as a precursor. I got A2.

The nickel-containing transition metal composite hydroxide A2 and lithium hydroxide monohydrate are weighed and mixed so as to have a molar ratio of Li / (Ni + Co + Mn) = 1.05, and then mixed at 650 ° C. under an oxygen atmosphere. After firing for 5 hours, the raw material compound A2 was obtained by further firing at 955 ° C. for 5 hours in an oxygen atmosphere.

As a result of the composition analysis of the raw material compound A2, p = 0.020, q = 0.200, and r = 0.198 in the composition formula (II).

The raw material compound A2 was put into a Ladyge mixer, the raw material compound A2 was set to 113 ° C., and the coating raw material solution 1-A2 containing B in which boric acid was dissolved in pure water was adjusted to 20 ° C. to B / The coating raw material solution 1-A2 was sprayed and brought into contact with the raw material compound A2 while stirring so that (Ni + X) = 0.02. Further, the content of the solvent was adjusted to 2.7% by mass to obtain a raw material mixture A2. Here, the concentration of B in the coating raw material solution 1-A2 is 0.40 mol / L, and the amount of substance B in the raw material mixture A2 relative to the amount of substance Li excluding Li contained in the crystal structure. The ratio (B / Li) of was 7.8. The Sauter mean diameter D ₃₂ of the spray droplets of the coating raw material solution 1-A2 is 45 μm, and the ratio of the raw material compound A2 to the median diameter DP ₅₀ (DP ₅₀ / D ₃₂ ) is 0.14. It was.

The raw material mixture A2 was heat-treated at 250 ° C. for 5 hours to obtain a lithium metal composite oxide powder A2.

As a result of the composition analysis of the lithium metal composite oxide powder A2, m = 0.010 and n = 0.409 in the composition formula (I), and m1 = 0.010 and n12 = 0 in the composition formula (I) -1. .196, n13 = 0.194, n14 = 0.019. The obtained lithium metal composite oxide powder A2 was used as the positive electrode active material A2, and the above-mentioned coin-type battery was used for evaluation.

<< Example 3 >>
1. 1. Production of Lithium Metal Composite Oxide Powder A3
The raw material compound A2 obtained in Example 2 was heat-treated at 500 ° C. for 5 hours to obtain a lithium metal composite oxide powder A3.

As a result of the composition analysis of the lithium metal composite oxide powder A3, m = 0.010 and n = 0.409 in the composition formula (I), and m1 = 0.010 and n12 = 0 in the composition formula (I) -1. .196, n13 = 0.194, n14 = 0.019. The obtained lithium metal composite oxide powder A4 was used as the positive electrode active material A4, and the above-mentioned coin-type battery was used for evaluation.

<< Example 4 >>
1. 1. Production of Lithium Metal Composite Oxide Powder A4
A coating raw material solution containing boron and lithium is obtained by dissolving boric acid in pure water adjusted to 25 ° C., further adding the raw material compound A2 obtained in Example 2 and dissolving the lithium compound remaining in the raw material compound A2. The raw material compound A2 was immersed in 2-A4. Then, the liquid content of the solvent was adjusted to 15% by mass by filtration to obtain a raw material mixture A4. At this time, the amount of boric acid dissolved in pure water was adjusted so that B / (Ni + X) was 0.01. Here, the amount of the coating raw material solution 2-A4 with respect to the raw material compound A4 is 1.0 times by weight, the concentration of Li contained in the coating raw material solution 2-A4 is 0.026 mol / L, and the raw material mixture A4. The ratio (B / Li) of the amount of substance of B to the amount of substance of Li excluding Li contained in the crystal structure of the raw material compound A2 contained in was 26.

The raw material mixture A4 was heat-treated at 300 ° C. for 5 hours to obtain a lithium metal composite oxide powder A4.

As a result of the composition analysis of the lithium metal composite oxide powder A4, m = 0.017 and n = 0.402 in the composition formula (I), and m1 = 0.017 and n12 = 0 in the composition formula (I) -1. .198, n13 = 0.196, n14 = 0.008. The obtained lithium metal composite oxide powder A4 was used as the positive electrode active material A4, and the above-mentioned coin-type battery was used for evaluation.

<< Example 5 >>
1. 1. Production of Lithium Metal Composite Oxide Powder A5
A coating raw material solution containing boron and lithium is obtained by dissolving boric acid in pure water adjusted to 25 ° C., further adding the raw material compound A2 obtained in Example 2 and dissolving the lithium compound remaining in the raw material compound A2. The raw material compound A2 was immersed in 2-A5. Then, the liquid content of the solvent was adjusted to 15% by mass by filtration to obtain a raw material mixture A5. At this time, the amount of boric acid dissolved in pure water was adjusted so that B / (Ni + X) was 0.001. Here, the amount of the coating raw material solution 2-A5 with respect to the raw material compound A5 is 1.0 times by weight, the concentration of Li contained in the coating raw material solution 2-A5 is 0.026 mol / L, and the raw material mixture A5. The ratio (B / Li) of the amount of substance of B to the amount of substance of Li excluding Li contained in the crystal structure of the raw material compound A2 contained in was 2.6.

The raw material mixture A5 was heat-treated at 300 ° C. for 5 hours to obtain a lithium metal composite oxide powder A5.

As a result of the composition analysis of the lithium metal composite oxide powder A5, m = 0.021 and n = 0.398 in the composition formula (I), and m1 = 0.021 and n12 = 0 in the composition formula (I) -1. It was .200, n13 = 0.197, and n14 = 0.001. The obtained lithium metal composite oxide powder A5 was used as the positive electrode active material A5, and the above-mentioned coin-type battery was used for evaluation.

<< Example 6 >>
1. 1. Production of Lithium Metal Composite Oxide Powder A6
A coating raw material solution containing boron and lithium is obtained by dissolving boric acid in pure water adjusted to 25 ° C., further adding the raw material compound A2 obtained in Example 2 and dissolving the lithium compound remaining in the raw material compound A2. The raw material compound A2 was immersed in 2-A6. Then, the liquid content of the solvent was adjusted to 14% by mass by filtration to obtain a raw material mixture A6. At this time, the amount of boric acid dissolved in pure water was adjusted so that B / (Ni + X) was 0.0001. Here, the amount of the coating raw material solution 2-A6 with respect to the raw material compound A2 is 1.0 times by weight, the concentration of Li contained in the coating raw material solution 2-A6 is 0.026 mol / L, and the raw material mixture A6. The ratio (B / Li) of the amount of substance of B to the amount of substance of Li excluding Li contained in the crystal structure of the raw material compound A2 contained in was 0.26.

The raw material mixture A6 was heat-treated at 300 ° C. for 5 hours to obtain a lithium metal composite oxide powder A6.

As a result of the composition analysis of the lithium metal composite oxide powder A6, m = 0.022 and n = 0.398 in the composition formula (I), and m1 = 0.022 and n12 = 0 in the composition formula (I) -1. .199, n13 = 0.198, n14 = 0.001. The obtained lithium metal composite oxide powder A6 was used as the positive electrode active material A6, and the above-mentioned coin-type battery was used for evaluation.

<< Example 7 >>
1. 1. Production of Lithium Metal Composite Oxide Powder A7
Lithium phosphate is dissolved in pure water adjusted to 25 ° C., the raw material compound A1 obtained in Example 1 is further added, and the lithium compound remaining in the raw material compound A1 and lithium phosphate are dissolved to dissolve phosphorus and lithium. The raw material compound A1 was immersed in the coating raw material solution 2-A7 containing the above. Then, the liquid content of the solvent was adjusted to 15% by mass by filtration to obtain a raw material mixture A7. At this time, the amount of lithium phosphate dissolved in pure water was adjusted so that P / (Ni + X) was 0.01. Here, the amount of the coating raw material solution 2-7 with respect to the raw material compound A7 is 1.0 times by weight, the concentration of Li contained in the coating raw material solution 2-A7 is 0.47 mol / L, and the raw material mixture A7. The ratio (P / Li) of the amount of substance of P to the amount of substance of Li excluding Li contained in the crystal structure of the raw material compound A1 contained in was 1.5.

The raw material mixture A7 was heat-treated at 500 ° C. for 5 hours to obtain a lithium metal composite oxide powder A7.

As a result of the composition analysis of the lithium metal composite oxide powder A7, m = 0.014 and n = 0.404 in the composition formula (I), and m1 = 0.014 and n12 = 0 in the composition formula (I) -1. .196, n13 = 0.198, n14 = 0.010. The obtained lithium metal composite oxide powder A7 was used as the positive electrode active material A7, and the above-mentioned coin-type battery was used for evaluation.

<< Example 8 >>
1. 1. Production of Lithium Metal Composite Oxide Powder A8
Niobium pentoxide is dispersed in pure water adjusted to 25 ° C., and the raw material compound A1 obtained in Example 1 is further added to dissolve the lithium compound remaining in the raw material compound A1 to dissolve the coating raw material containing niobium and lithium. The raw material compound A1 was immersed in the solution 2-A8. Then, the liquid content of the solvent was adjusted to 15% by mass by filtration to obtain a raw material mixture A8. At this time, the amount of lithium phosphate dissolved in pure water was adjusted so that Nb / (Ni + X) was 0.01. Here, the amount of the coating raw material solution 2-A8 with respect to the raw material compound A8 is 1.0 times by weight, and the concentration of Li contained in the coating raw material solution 2-A8 is 0.16.
The ratio of the amount of substance of Nb (Nb / Li) to the amount of substance of Li excluding Li contained in the crystal structure of the raw material compound A1 contained in the raw material mixture A8 was 4.2.

The raw material mixture A8 was heat-treated at 500 ° C. for 5 hours to obtain a lithium metal composite oxide powder A8.

As a result of the composition analysis of the lithium metal composite oxide powder A8, m = 0.015 and n = 0.404 in the composition formula (I), and m1 = 0.015 and n12 = 0 in the composition formula (I) -1. .196, n13 = 0.207, n14 = 0.000. The obtained lithium metal composite oxide powder A8 was used as the positive electrode active material A8 for evaluation using the above-mentioned coin-type battery.

<< Example 9 >>
1. 1. Production of Lithium Metal Composite Oxide Powder A9 Water was placed in a reaction vessel equipped with a stirrer and an overflow pipe, and then an aqueous sodium hydroxide solution was added. The liquid temperature in the reaction vessel was maintained at 60 ° C.

An aqueous solution of nickel sulfate, an aqueous solution of cobalt sulfate, and an aqueous solution of manganese sulfate were mixed so as to have a molar ratio of Ni: Co: Mn = 0.91: 0.07: 0.02 to prepare a mixed raw material solution 9.

Next, the mixed raw material solution 9 and the ammonium sulfate aqueous solution were continuously added as a complexing agent into the reaction vessel under stirring. An aqueous sodium hydroxide solution was added dropwise in an appropriate manner so that the pH of the solution in the reaction vessel became 11.6. A nickel-containing transition metal composite hydroxide is obtained, washed, dehydrated with a centrifuge, washed, dehydrated, isolated and dried at 105 ° C. to obtain a nickel-containing transition metal composite hydroxide as a precursor. I got A9.

The molar ratio of the nickel-containing transition metal composite hydroxide A9, lithium hydroxide monohydrate and potassium sulfate powder was Li / (Ni + Co + Mn) = 1.26, K ₂ SO ₄ / (LiOH + K ₂ SO ₄ ) = 0. The raw material compound A9 was obtained by weighing and mixing so as to have a concentration of .1 (mol / mol) and then firing at 790 ° C. for 10 hours in an oxygen atmosphere.

As a result of the composition analysis of the raw material compound A9, p = 0.015, q = 0.068, and r = 0.020 in the composition formula (II).

A coating raw material solution containing boron and lithium is obtained by dissolving boric acid in pure water prepared by adjusting the raw material compound A9 to 25 ° C., further adding the raw material compound A9, and dissolving the lithium compound remaining in the raw material compound A9. The raw material compound A9 was immersed in 2-A9. Then, the liquid content of the solvent was adjusted to 17% by mass by filtration to obtain a raw material mixture A9. At this time, the amount of boric acid dissolved in pure water was adjusted so that B / (Ni + X) was 0.01. Here, the amount of the coating raw material solution 2-A9 with respect to the raw material compound A4 is 1.0 times by weight, the concentration of Li contained in the coating raw material solution 2-9 is 0.62 mol / L, and the raw material mixture A9. The ratio (B / Li) of the amount of substance of B to the amount of substance of Li excluding Li contained in the crystal structure of the raw material compound A9 contained in was 1.1.

The raw material mixture A9 was heat-treated at 250 ° C. for 5 hours to obtain a lithium metal composite oxide powder A9.

As a result of the composition analysis of the lithium metal composite oxide powder A9, m = 0.010 and n = 0.097 in the composition formula (I), and m1 = 0.010 and n12 = 0 in the composition formula (I) -1. It was 0.067, n13 = 0.020, and n14 = 0.010. The obtained lithium metal composite oxide powder A9 was used as the positive electrode active material A9, and the above-mentioned coin-type battery was used for evaluation.

<< Comparative Example 1 >>
1. 1. Production of Lithium Metal Composite Oxide Powder C1 The molar ratio of the nickel-containing transition metal composite hydroxide A1 and lithium hydroxide monohydrate obtained in Example 1 is Li / (Ni + Co + Mn) = 1.07. After weighing and mixing, the lithium metal composite oxide powder C1 was obtained by firing at 650 ° C. for 5 hours in an oxygen atmosphere and then firing at 970 ° C. for 5 hours in an oxygen atmosphere.

As a result of composition analysis of the lithium metal composite oxide powder C1, m = 0.016 and n = 0.397 in the composition formula (I), and m1 = 0.016 and n12 = 0 in the composition formula (I) -1. .198, n13 = 0.199, n14 = 0.000. The obtained lithium metal composite oxide powder C1 was used as the positive electrode active material C1 for evaluation using the above-mentioned coin-type battery.

≪Comparative example 2≫
1. 1. Production of Lithium Metal Composite Oxide Powder C2 The molar ratio of the nickel-containing transition metal composite hydroxide A1 obtained in Example 1 and lithium hydroxide monohydrate is Li / (Ni + Co + Mn) = 1.05. After weighing and mixing as described above, the raw material compound C2 was obtained by firing at 650 ° C. for 5 hours in an oxygen atmosphere and then firing at 1015 ° C. for 5 hours in an oxygen atmosphere.

As a result of the composition analysis of the raw material compound C2, p = 0.004, q = 0.199, and r = 0.252 in the composition formula (II).

The raw material compound C2 and boric acid powder were mixed so as to have a molar ratio of B / (Ni + X) = 0.02 to obtain a raw material mixture C2. The ratio (B / Li) of the amount of substance of B to the amount of substance of Li excluding Li contained in the crystal structure of the raw material compound C2 contained in the raw material mixture C2 was 2.9.

The raw material mixture C2 was heat-treated at 400 ° C. for 5 hours to obtain a lithium metal composite oxide powder C2.

As a result of the composition analysis of the lithium metal composite oxide powder C2, m = -0.004 and n = 0.460 in the composition formula (I), and m1 = -0.004 and n12 in the composition formula (I) -1. = 0.196, n13 = 0.248, n14 = 0.016. The obtained lithium metal composite oxide powder C2 was used as the positive electrode active material C2, and the above-mentioned coin-type battery was used for evaluation.

≪Comparative example 3≫
1. 1. Production of Lithium Metal Composite Oxide Powder C3 The nickel-containing transition metal composite hydroxide A9 obtained in Example 9, lithium hydroxide monohydrate and potassium sulfate powder were used as a molar ratio of Li / (Ni + Co + Mn) = 1. 10. Weighed and mixed so that K ₂ SO ₄ / (LiOH + K ₂ SO ₄ ) = 0.1 (mol / mol), and then fired at 775 ° C. for 10 hours in an oxygen atmosphere to obtain a fired product C3. It was. The calcined product C3 is added to pure water adjusted to 5 ° C., stirred and dehydrated, rinsed with pure water adjusted to 5 ° C., which is twice the weight of the calcined product C3, isolated, and dried at 150 ° C. Obtained the raw material compound C3.

As a result of the composition analysis of the raw material compound C3, p = 0.015, q = 0.068, and r = 0.020 in the composition formula (II).

The raw material compound C3 and boric acid powder were mixed so as to have a molar ratio of B / (Ni + X) = 0.01 to obtain a raw material mixture C3. The ratio (B / Li) of the amount of substance of B to the amount of substance of Li excluding Li contained in the crystal structure of the raw material compound A2 contained in the raw material mixture A4 was 0.70.

The raw material mixture C3 was heat-treated at 300 ° C. for 5 hours to obtain a lithium metal composite oxide powder C3.

As a result of composition analysis of the lithium metal composite oxide powder C3, m = 0.010 and n = 0.097 in the composition formula (I), and m1 = 0.010 and n12 = 0 in the composition formula (I) -1. It was 0.067, n13 = 0.020, and n14 = 0.010. The obtained lithium metal composite oxide powder C3 was used as the positive electrode active material C3, and the above-mentioned coin-type battery was used for evaluation.

<< Comparative Example 4 >>
1. 1. Production of Lithium Metal Composite Oxide Powder C4
Boric acid was dissolved in pure water to prepare a coating raw material solution 1-C4 containing boron. The raw material compound A2 obtained in Example 2 was adjusted to 20 ° C., and the coating raw material solution 1-C4 was adjusted to 20 ° C., and the coating raw material solution 1-C4 was adjusted so that B / (Ni + X) = 0.02. The raw material compound A2 was added dropwise under running water so as not to be in a sprayed state, and then the solvent was dried by heating in a stationary state to adjust the liquid content of the solvent to 6.9% by mass to obtain a raw material mixture C4. Here, the concentration of B in the coating raw material solution 1-C4 is 0.40 mol / L, which is relative to the amount of substance of Li excluding Li contained in the crystal structure of the raw material compound A2 contained in the raw material mixture C4. , The ratio of the amount of substance of B (B / Li) was 7.8.

The raw material mixture C4 was heat-treated at 180 ° C. for 5 hours to obtain a lithium metal composite oxide powder C4.

As a result of the composition analysis of the lithium metal composite oxide powder C4, m = 0.010 and n = 0.409 in the composition formula (I), and m1 = 0.010 and n12 = 0 in the composition formula (I) -1. .196, n13 = 0.194, n14 = 0.019. The obtained lithium metal composite oxide powder C4 was used as the positive electrode active material C4, and the above-mentioned coin-type battery was used for evaluation.

<< Comparative Example 5 >>
1. 1. Production of Lithium Metal Composite Oxide Powder C5
The raw material mixture C4 of Comparative Example 4 was heat-treated at 250 ° C. for 5 hours to obtain a lithium metal composite oxide powder C5.

As a result of composition analysis of the lithium metal composite oxide powder C5, m = 0.010 and n = 0.409 in the composition formula (I), and m1 = 0.010 and n12 = 0 in the composition formula (I) -1. .196, n13 = 0.194, n14 = 0.019. The obtained lithium metal composite oxide powder C5 was used as the positive electrode active material C5, and the above-mentioned coin-type battery was used for evaluation.

As shown in the above results, it was confirmed that the positive electrode active materials of Examples 1 to 9 to which the present invention was applied had a smaller self-discharge rate than those of Comparative Examples 1 to 5.

Further, when the lithium metal composite oxide powder of Example 1 was observed with a transmission electron microscope, it was confirmed that the coating material was amorphous.

1 ... Separator, 2 ... Positive electrode, 3 ... Negative electrode, 4 ... Electrode group, 5 ... Battery can, 6 ... Electrolyte, 7 ... Top insulator, 8 ... Seal, 10 ... Lithium secondary battery, 21 ... Positive lead, 31 … Negative lead

Claims (27)

It has a layered structure and has at least Li, Ni and element X (element X is Co, Mn, Fe, Cu, Ti, Mg, Ca, Sr, Ba, Al, W, Mo, Nb, Zn, Sn, Zr, Cr. , Ga, Ge, Pd, Ag, Cd, In, V, B, Si, S, F and (one or more elements selected from the group consisting of P)).
In the cumulative frequency distribution curve of R defined below, the value R (90) of the point where the cumulative frequency from the smaller side of R is 90% when the whole is 100% is 1.7 or more and 3 A lithium metal composite oxide powder of .7 or less.
R is the ratio (O / (Ni + X) of the amount of substance (O) of oxygen to the total amount of substance (Ni + X) of nickel and element X in one particle of lithium metal composite oxide contained in the lithium metal composite oxide powder. )).
The amount of substance of nickel, element X and oxygen is determined by energy dispersive X-ray (EDX) spectroscopy with an accelerating voltage of 1100 V for one lithium metal composite oxide particle. In the cumulative frequency distribution curve of R, the value R (10) of R at the point where the cumulative frequency from the smaller side of R is 10% when the whole is 100% is 1.1 or more and 3.3 or less. The lithium metal composite oxide powder according to claim 1. In the cumulative frequency distribution curve of R, the value R (50) of R at the point where the cumulative frequency from the smaller side of R is 50% when the whole is 100% is 1.5 or more and 2.7 or less. The lithium metal composite oxide powder according to claim 1 or 2. The lithium metal composite oxide powder according to any one of claims 1 to 3, which satisfies the following formula (I).
Li [Li _m (Ni _(1-n) X _n ) _1-m ] O ₂ ... (I)
(−0.1 ≦ m ≦ 0.2, 0 <n ≦ 0.7) The lithium metal composite oxide powder according to claim 4, wherein m of the formula (I) is 0 <m ≦ 0.2. The lithium metal composite oxide powder according to any one of claims 1 to 5, which comprises core particles and a coating. The lithium metal composite oxide powder according to claim 6, wherein the coating material contains a lithium-containing composite compound of Li and element M. However, the element M is one or more selected from Al, Zr, B, Si, S, Nb, F and P. The lithium metal composite oxide powder according to any one of claims 1 to 7, further comprising a single particle. The 50% cumulative diameter (D ₅₀ ) is 0.5 μm or more and 10 μm or less in the 10% cumulative diameter (D ₁₀ ), 50% cumulative diameter (D ₅₀ ), and 90% cumulative diameter (D ₉₀ ) obtained from the particle size distribution measurement values. The lithium metal composite oxide powder according to any one of claims 1 to 8, further satisfying the relationship of the following formula (A).
0.3 ≤ (D _90- D ₁₀ ) / D ₅₀ ≤ 3 ... (A) A positive electrode active material for a lithium secondary battery containing the lithium metal composite oxide powder according to any one of claims 1 to 9. A method for producing a lithium metal composite oxide powder, which comprises the following steps (a) to (c) in the following order.
Step (a) A step of mixing a precursor containing at least Ni and a lithium compound containing Li and firing the mixture to obtain a raw material compound.
Step (b) A step of bringing the raw material compound into contact with a coating raw material containing at least one element M selected from the group consisting of Al, B, Si, S, Nb, F and P to obtain a raw material mixture.
Step (c) A step of heat-treating the raw material mixture at a temperature of 200 ° C. or higher to 600 ° C. or lower. The step (b) is a step (b1) of bringing the coating raw material solution 1 containing the element M into contact with the raw material compound to obtain a raw material mixture.
After the step (b1) and before the step (c), the solvent contained in the raw material mixture is removed, and the content of the solvent in the raw material mixture is adjusted to 30% by mass or less (b1-). The method for producing a lithium metal composite oxide powder according to claim 11, further comprising A). The production of the lithium metal composite oxide powder according to claim 12, wherein the step (b1) is a step (b1-1) of spraying and contacting the coating raw material solution 1 with the raw material compound to obtain a raw material mixture. Method. The method for producing a lithium metal composite oxide powder according to claim 12 or 13, wherein in the step (b1), the raw material compound is adjusted to a temperature of −20 ° C. or higher and 300 ° C. or lower and brought into contact with the coating raw material solution 1. .. The method for producing a lithium metal composite oxide powder according to claim 13 or 14, wherein in the step (b1-1), the Sauter mean diameter D ₃₂ of the spray droplets of the coating raw material solution 1 is 10 μm or more and 500 μm or less. .. In the step (b1-1), the ratio (DP ₅₀ / D ₃₂ ) of the median diameter DP ₅₀ of the raw material compound to the Sauter mean diameter D ₃₂ of the sprayed droplets when the coating raw material solution 1 is sprayed is The method for producing a lithium metal composite oxide powder according to any one of claims 13 to 15, which is 0.001 or more and 10 or less. Any one of claims 12 to 16, wherein in the step (b1), the temperature of the coating raw material solution 1 when the coating raw material solution 1 is brought into contact with the raw material compound is −20 ° C. or higher and 300 ° C. or lower. The method for producing a lithium metal composite oxide powder according to the section. The lithium metal composite oxidation according to any one of claims 12 to 17, wherein in the step (b1), the concentration of the element M in the coating raw material solution 1 is 0.001 mol / L or more and 100 mol / L or less. Manufacturing method of material powder. Any of claims 12 to 18, wherein in the step (b1), the ratio (M / Li) of the amount of substance of element M to the amount of substance of lithium contained in the raw material mixture is 0.1 or more and 50 or less. The method for producing a lithium metal composite oxide powder according to item 1.
However, the amount of substance of lithium contained in the raw material mixture is the amount excluding lithium contained in the crystal structure of the raw material compound contained in the raw material mixture. The step (b) is a step (b2) of immersing the raw material compound in the coating raw material solution 2 containing the element M and lithium to obtain a raw material mixture.
After the step (b2) and before the step (c), the solvent contained in the raw material mixture is removed, and the content of the solvent in the raw material mixture is adjusted to 30% by mass or less (b2-). The method for producing a lithium metal composite oxide powder according to claim 11, further comprising A). The method for producing a lithium metal composite oxide powder according to claim 20, wherein in the step (b2), the amount of the coating raw material solution 2 with respect to the raw material compound is 0.1 times or more and 10 times or less on a weight basis. The method for producing a lithium metal composite oxide powder according to claim 20 or 21, wherein the temperature of the coating raw material solution 2 is −20 ° C. or higher and 80 ° C. or lower. The lithium metal composite oxidation according to any one of claims 20 to 22, wherein in the step (b2), the concentration of Li contained in the coating raw material solution 2 is 0.01 mol / L or more and 10 mol / L or less. Method of manufacturing product powder. Any of claims 20 to 23, wherein in the step (b2), the ratio (M / Li) of the amount of substance of element M to the amount of substance of lithium contained in the raw material mixture is 0.1 or more and 50 or less. The method for producing a lithium metal composite oxide powder according to item 1.
However, the amount of substance of lithium contained in the raw material mixture is the amount excluding lithium contained in the crystal structure of the raw material compound contained in the raw material mixture. In the step (b), the ratio (M / Li) of the amount of substance of the element M to the amount of substance of Li excluding Li contained in the crystal structure of the lithium-containing compound contained in the raw material mixture is 0. The method for producing a lithium metal composite oxide powder according to claim 11, wherein the amount is 1 or more and 50 or less.
However, the amount of substance of lithium contained in the raw material mixture is the amount excluding lithium contained in the crystal structure of the raw material compound contained in the raw material mixture. In the step (b), the ratio (M / (Ni + X)) of the element M contained in the coating raw material to the total amount (Ni + X) of the metal elements excluding Li contained in the raw material compound is 0.0001 or more in terms of molar ratio. The method for producing a lithium metal composite oxide powder according to any one of claims 11 to 25, which is 0.05 or less. The method for producing a lithium metal composite oxide powder according to any one of claims 11 to 26, wherein the raw material compound satisfies the following formula (II).
Li (Li _p (Ni _(1-q-r) Co _q X1 _r ) _1-p ) O ₂ ... (II)
(−0.1 ≦ p ≦ 0.2, 0 ≦ q ≦ 0.4, 0 ≦ r ≦ 0.4, 1-q−r ≧ 0.3, X1 is Mn, Fe, Cu, Ti, Mg, One or more elements selected from the group consisting of Ca, Sr, Ba, Al, W, Mo, Nb, Zn, Sn, Zr, Cr, Ga, Ge, Pd, Ag, Cd, In and V.)

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