JP2015135800A - Method of manufacturing positive electrode active material for lithium ion secondary battery, positive electrode for lithium ion secondary battery, and lithium ion secondary battery - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a method of manufacturing a positive electrode active material capable of enhancing the initial discharge capacity and the charge-discharge efficiency of a lithium ion secondary battery.SOLUTION: A method of manufacturing a positive electrode active material for a lithium ion secondary battery mixes compound (A) and compound (B), calcines a mixture thus obtained at 450-700°C under an oxygen-containing atmosphere, and then calcines at 750-1000°C under an oxygen-containing atmosphere, thus obtaining a composite oxide (I) containing any one or both of Li, Ni and Co, and Mn, where the molar quantity of Li is 1.2 times or more of the total molar quantity of Ni, Co and Mn. The compound (A): a carbonate compound having D50 diameter of 3-15 μm, D90 diameter of less than 40 μm, and containing any one or both of Ni and Co. The compound (B): lithium carbonate having D50 diameter of 3-15 μm and D90 diameter of less than 40 μm.

Description

  The present invention relates to a method for producing a positive electrode active material for a lithium ion secondary battery. Moreover, this invention relates to the positive electrode for lithium ion secondary batteries using the positive electrode active material for lithium ion secondary batteries obtained by the said manufacturing method, and a lithium ion secondary battery.

Lithium ion secondary batteries are widely used in portable electronic devices such as mobile phones and notebook computers. Examples of the positive electrode active material for the lithium ion secondary battery include composite oxides of lithium and transition metals such as LiCoO ₂ , LiNiO ₂ , LiNi _0.8 Co _0.2 O ₂ , and LiMn ₂ O ₄ (hereinafter, Also referred to as lithium-containing composite oxide).
In recent years, miniaturization and weight reduction have been demanded as portable electronic devices and in-vehicle lithium ion secondary batteries. Therefore, further improvements in battery characteristics such as discharge capacity per unit mass (hereinafter simply referred to as “discharge capacity”) and charge / discharge efficiency are desired for lithium ion secondary batteries.

In order to improve the discharge capacity, as a positive electrode active material, for example, a lithium-containing composite oxide having a high Li ratio to a transition metal element such as Li _1.2 Ni _0.175 Co _0.10 Mn _0.525 O ₂ ( Hereinafter, it has been proposed to use “Li-rich positive electrode material” (for example, Patent Document 1).
The Li-rich positive electrode material can be obtained, for example, by mixing a coprecipitated compound (a carbonate compound containing a transition metal element) obtained by a carbonate coprecipitation method with a lithium compound such as lithium carbonate and firing.
However, the Li-rich positive electrode material manufactured by the conventional technique is not necessarily sufficient in the initial discharge capacity and the initial charge / discharge efficiency of the lithium ion secondary battery obtained by using this, and improvement is desired.

Special table 2012-511809 gazette

  An object of this invention is to provide the manufacturing method of the positive electrode active material which can improve the initial stage discharge capacity and charging / discharging efficiency of a lithium ion secondary battery. Moreover, an object of this invention is to provide the positive electrode for lithium ion secondary batteries using the positive electrode active material for lithium ion secondary batteries obtained by the said manufacturing method, and a lithium ion secondary battery.

This invention provides the manufacturing method of the positive electrode active material for lithium ion secondary batteries which has the structure of [1]-[10], the positive electrode for lithium ion secondary batteries, and a lithium ion secondary battery.
[1] A composite oxide containing one or both of Ni and Co, Mn and Li, wherein the molar amount of Li is more than 1.2 times the total molar amount of Ni, Co and Mn (I ) Containing a positive electrode active material for a lithium ion secondary battery,
A mixing step of mixing the following compound (A) and the following compound (B);
A first baking step of baking the mixture obtained in the mixing step at 450 to 700 ° C. in an oxygen-containing atmosphere;
And a second firing step of obtaining the composite oxide (I) by firing the fired product obtained in the first firing step at 750 to 1000 ° C. in an oxygen-containing atmosphere. To produce a positive electrode active material for a lithium ion secondary battery.
Compound (A): Volume-based D50 diameter measured by a laser diffraction / scattering particle size distribution analyzer using water as a dispersion medium is 3 to 15 μm, D90 diameter is less than 40 μm, and either Ni or Co Or a carbonate compound containing both and Mn.
Compound (B): Lithium carbonate having a volume-based D50 diameter of 3 to 15 μm and a D90 diameter of less than 40 μm as measured with a laser diffraction / scattering particle size distribution analyzer using 2-propanol as a dispersion medium.
[2] The method for producing a positive electrode active material for a lithium ion secondary battery according to [1], wherein the compound (B) has a D50 diameter of 4 to 11 μm and a D90 diameter of less than 25 μm.
[3] The method for producing a positive electrode active material for a lithium ion secondary battery according to [1] or [2], wherein the D50 diameter of the compound (B) is not more than the D50 diameter of the compound (A).
[4] The method for producing a positive electrode active material for a lithium ion secondary battery according to any one of [1] to [3], wherein the composite oxide (I) is represented by the following general formula (I-1): .
_{Li a Ni x Co y Mn z} Me b O p ... (I-1)
However, Me is at least one element selected from the group consisting of Cr, Fe, Al, Ti, Zr, Mg, Mo, Ru, Nb, V and W, and 1.2 <a <1.6, 0 0.5 ≦ z ≦ 0.8, x + y + z = 1, 0 ≦ b ≦ 0.1, 2.1 <p <2.7.
[5] The method for producing a positive electrode active material for a lithium ion secondary battery according to any one of [1] to [4], wherein the compound (A) is represented by the following general formula (A-1).
Ni _x Co _y Mn _z Me _b CO ₃ (A-1)
However, Me is at least one element selected from the group consisting of Cr, Fe, Al, Ti, Zr, Mg, Mo, Ru, Nb, V and W, and 0.5 ≦ z ≦ 0.8, x + y + z = 1, 0 ≦ b ≦ 0.1.
[6] In the general formula (A-1), x, y, and z are 0.19 ≦ x ≦ 0.22, 0.14 ≦ y ≦ 0.18, and 0.62 ≦ z ≦ 0.67, respectively. The manufacturing method of the positive electrode active material for lithium ion secondary batteries as described in [5].
[7] The positive electrode active material for a lithium ion secondary battery according to any one of [1] to [6], further comprising a step of causing an oxide containing Al to be present on the surface of the composite oxide (I). Production method.
[8] A step of causing a compound containing at least one anion selected from the group consisting of SO ₄ ²⁻ , PO ₄ ³⁻ , and F ⁻ and Li ⁺ to exist on the surface of the composite oxide (I). The manufacturing method of the positive electrode active material for lithium ion secondary batteries in any one of [1]-[7] which has further.
[9] The positive electrode for a lithium ion secondary battery according to any one of [1] to [8], wherein in the mixing step, water is added when the compound (A) and the compound (B) are mixed. A method for producing an active material.
[10] A positive electrode for a lithium ion secondary battery comprising a positive electrode active material for a lithium ion secondary battery produced by the production method according to any one of [1] to [9] and a binder.
[11] A lithium ion secondary battery comprising the lithium ion secondary battery positive electrode according to [10], a negative electrode, and a nonaqueous electrolyte.

According to the method for producing a positive electrode active material for a lithium ion secondary battery of the present invention, the initial discharge capacity (hereinafter also referred to as initial discharge capacity) and the initial charge / discharge efficiency (hereinafter referred to as initial efficiency) of the lithium ion secondary battery. It is also possible to manufacture a positive electrode active material that can be improved.
According to the positive electrode for a lithium ion secondary battery of the present invention, the initial discharge capacity and the initial efficiency of the lithium ion secondary battery can be improved.
The lithium ion secondary battery of the present invention is excellent in initial discharge capacity and initial efficiency.

[Example] It is a graph which shows the discharge curve obtained by the initial stage characteristic evaluation of the lithium secondary battery using the positive electrode active material manufactured in Examples 1-4.

In the present invention, an element symbol (for example, “Li”) indicates an element, and does not indicate a single substance (for example, metal) of the element unless otherwise specified.
In the present invention, the element ratio of the composite oxide is a value in the positive electrode active material before the first charge (also referred to as activation treatment).
In the present invention, the D50 diameter means a particle diameter at a point where the cumulative volume becomes 50% in the cumulative volume distribution curve in which the total volume of the particle size distribution obtained on a volume basis is 100%. Further, the D10 diameter, D90 diameter, and D99 diameter mean the particle diameters at which the cumulative volume becomes 10%, 90%, and 99% in the cumulative volume distribution curve, respectively. The particle size distribution is obtained from a frequency distribution and a cumulative volume distribution curve measured with a laser diffraction / scattering particle size distribution measuring apparatus. The particle diameter is measured by sufficiently dispersing the powder to be measured in a predetermined dispersion medium by ultrasonic treatment or the like, and measuring the particle size distribution (for example, Laser diffraction / scattering particle size distribution measuring apparatus Partica LA manufactured by HORIBA). -950VII, etc.).

<Positive electrode active material for lithium ion secondary battery>
The positive electrode active material for a lithium ion secondary battery obtained by the production method of the present invention (hereinafter referred to as the present production method) contains one or both of Ni and Co, Mn, and Li. The composite oxide (I) has a molar amount exceeding 1.2 times the total molar amount of Ni, Co and Mn.
The positive electrode active material preferably has a composite oxide (I) and a compound other than the composite oxide (I) (hereinafter referred to as a heterogeneous compound). More preferably, the foreign compound is present on the surface of the composite oxide (I). When a positive electrode active material in which a heterogeneous compound is present on the surface of the composite oxide (I) is used, the cycle characteristics (characteristics in which the discharge capacity of the battery does not decrease after repeated charge / discharge) or rate characteristics ( The characteristic that the discharge capacity of the battery does not decrease when discharged at a high discharge rate can be improved.

(Composite oxide (I))
The composite oxide (I) contains one or both of Ni and Co, Mn, and Li. The ratio of the molar amount of Li to the total molar amount (M) of Ni, Co and Mn in the composite oxide (I) (hereinafter also referred to as Li / M ratio) is more than 1.2. The metal element content contained in the composite oxide (I) can be calculated by inductively coupled plasma (ICP) measurement. The Li / M ratio of the positive electrode active material has a great influence on the initial discharge capacity of the lithium ion secondary battery. When the Li / M ratio of the composite oxide (I) exceeds 1.2, the Li / M of the positive electrode active material is increased, and the initial discharge capacity of the lithium ion secondary battery can be sufficiently increased.
The composite oxide (I) preferably contains at least Ni, and particularly preferably contains both Ni and Co, among Ni and Co.
The composite oxide (I) may contain a metal element other than Li, Ni, Co, and Mn (hereinafter referred to as other metal element Me). Examples of the other metal element Me include Cr, Fe, Al, Ti, Zr, Mg, Mo, Ru, Nb, V, and W. In the composite oxide (I), part of oxygen (O) may be substituted with fluorine (F).
As the composition of the composite oxide (I), various known compositions can be employed.

The composite oxide (I) is preferably represented by the following general formula (I-1). The compound represented by the formula (I-1) can increase the discharge capacity of the lithium ion secondary battery.
_{Li a Ni x Co y Mn z} Me b O p ... (I-1)
However, Me is at least one element selected from the group consisting of Cr, Fe, Al, Ti, Zr, Mg, Mo, Ru, Nb, V and W, and 1.2 <a <1.6, 0 0.5 ≦ z ≦ 0.8, x + y + z = 1, 0 ≦ b ≦ 0.1, 2.1 <p <2.7.

In the general formula (I-1), a is preferably 1.3 ≦ a ≦ 1.55, and 1.35 ≦ a ≦ 1.50 in that the capacity of the lithium ion secondary battery can be increased. It is particularly preferred.
x is preferably 0.15 ≦ x ≦ 0.4, and particularly preferably 0.19 ≦ x ≦ 0.22, in that the capacity of the lithium ion secondary battery can be increased.
y is preferably 0 ≦ y ≦ 0.25, and particularly preferably 0.14 ≦ y ≦ 0.18, from the viewpoint that the capacity of the lithium ion secondary battery can be increased.
z is preferably 0.56 ≦ z ≦ 0.76 and particularly preferably 0.62 ≦ z ≦ 0.67 in terms of enhancing the rate characteristics and cycle characteristics of the lithium ion secondary battery.
b is preferably 0 ≦ b ≦ 0.05.
q is preferably 0 ≦ q ≦ 0.05.

As the composite oxide _{(I), Li 1.45 Ni 0.193} Co 0.150 Mn 0.657 O 2.45, Li 1.41 Ni 0.193 Co 0.150 Mn 0.657 O 2.41 , Li _1.28 Ni _0.33 Co _0.04 Mn _0.63 O _2.28 , Li _1.50 Ni _0.25 Mn _0.75 O _2.50 , Li _1.50 Ni _0.225 Co _{0. 05} Mn _0.725 O _2.50 , Li _1.50 Ni _0.20 Co _0.10 Mn _0.70 O _2.50 , Li _1.50 Ni _0.167 Co _0.167 Mn _0.666 O2 _{. 50} , Li _1.40 Ni _0.30 Mn _0.70 O _2.40 , Li _1.50 Ni _0.27 Co _0.06 Mn _0.67 O _2.40 , Li _1.40 Ni _0.24 Co _{0 .12} Mn _{.64 O 2.40, Li 1.30 Ni 0.35} Mn 0.65 O 2.30, Li 1.30 Ni 0.28 Co 0.14 Mn 0.58 O 2.30, Li 1.22 Ni _0.39 Mn _0.61 O _2.22 , Li _1.22 Ni _0.363 Co _0.062 Mn _0.585 O _2.22 are preferred, and Li _1.45 Ni _0.193 Co _0.150 Mn _{0 .657} O _2.45 is particularly preferred.

The complex oxide (I) preferably has a peak attributed to a layered rock salt type crystal structure (space group R-3m) in XRD (X-ray source: CuKα) measurement. It is more preferable to have a peak attributed to the crystal structure of layered Li ₂ MnO ₃ . The peak attributed to the layered Li ₂ MnO ₃ is observed in the range of 2θ = 20 to 25 ° in the XRD spectrum.

The composite oxide (I) is preferably in the form of particles.
The composite oxide (I) preferably has a volume-based D50 diameter measured by a laser diffraction / scattering particle size distribution measuring apparatus using water as a dispersion medium of 2.5 to 14 μm, preferably 3.5 to 10 μm. More preferably, it is particularly preferably 4.5 to 9.5 μm. When the D50 diameter of the composite oxide (I) is not less than the lower limit of the above range, the filling property of the positive electrode active material becomes good, the electrode density can be sufficiently increased, and the discharge capacity of the lithium ion secondary battery is improved. When the D50 diameter of the composite oxide (I) is not more than the upper limit of the above range, the flatness of the positive electrode active material layer formed on the positive electrode current collector (positive electrode surface) is sufficiently high, and the lithium ion secondary battery Cycle characteristics are improved.

Composite oxide (I) has a specific surface area is preferably 1~12m ² / g, more preferably from 2 to 10 m ² / g, particularly preferably 3 to 8 m ² / g. When the specific surface area of the composite oxide (I) is not less than the lower limit of the above range, the discharge capacity and rate characteristics of the lithium ion secondary battery are improved. When the specific surface area of the composite oxide (I) is not more than the upper limit of the above range, the cycle characteristics of the lithium ion secondary battery are improved.
The specific surface area is a value measured by an adsorption BET (Brunauer, Emmet, Teller) method using nitrogen gas.

(Heterogeneous compounds)
The heterogeneous compound contained in the positive electrode active material includes at least one negative compound selected from the group consisting of an oxide containing Al (hereinafter referred to as compound (II)), SO ₄ ²⁻ , PO ₄ ³⁻ , and F ^−. Examples thereof include compounds containing ions and Li ⁺ (hereinafter referred to as compound (III)).

[Compound (II)]
As the compound (II), a cation oxide of Al is preferable, and Al ₂ O ₃ is particularly preferable.
Compound (II) is preferably present on the surface of composite oxide (I). When the positive electrode active material in which the compound (II) is present on the surface of the composite oxide (I) is used for a lithium ion secondary battery, the contact frequency between the composite oxide (I) and the electrolytic solution is reduced. This makes it difficult for a transition metal element such as Mn to elute from the surface of the composite oxide (I) into the electrolytic solution, and facilitates improving the cycle characteristics of the lithium ion secondary battery.
Compound (II) may exist over the whole surface of complex oxide (I), or may exist partially. It is more preferable that the compound (II) exists uniformly over the entire surface of the composite oxide (I) in that the cycle characteristics of the lithium ion secondary battery can be easily improved.

  Compound (II) may be crystalline or amorphous, from the viewpoint of suppressing elution of transition metal elements such as Mn into the electrolyte and enhancing the cycle characteristics of the lithium ion secondary battery, Amorphous is preferred. The compound (II) being amorphous means that a peak attributed to the compound (II) is not observed in the XRD measurement. The reason why the above effect can be obtained when the compound (II) is amorphous is not clear, but the compound (II) is uniformly present on the surface of the composite oxide (I) because it is amorphous. It is thought that it becomes easy.

The presence of compound (II) on the surface of the composite oxide (I) indicates that transmission electron microscope-energy dispersive X-ray spectroscopy analysis (TEM-EDX), X-ray microanalyzer analysis method (EPMA), It can be evaluated by X-ray photoelectron spectroscopy (XPS) or the like.
After cutting out the cross section of the positive electrode active material, the distribution state of the compound (II) can be evaluated by performing element mapping of Al by EPMA or TEM-EDX. In EPMA, it can be confirmed that the compound (II) is present not only in the primary particles close to the surface of the secondary particles in the positive electrode active material, but also in the primary particles inside the secondary particles. In TEM-EDX, it can be confirmed whether Al exists on the surface of a primary particle.
The chemical state of the compound (II) can be evaluated by XPS of the positive electrode active material. For example, if the peak of Al (2p) is in the range of 73.6 eV to 74.4 eV in XPS, it can be confirmed that an oxide containing Al is present.

When the positive electrode active material contains compound (II), the ratio of the molar amount of Al to the total molar amount (M) of Ni, Co and Mn contained in the positive electrode active material (hereinafter also referred to as Al / M ratio) is 0. 0.005 to 0.06 is preferable, 0.01 to 0.05 is more preferable, and 0.015 to 0.04 is particularly preferable. A positive electrode active material having an Al / M ratio within the above range can improve rate characteristics and cycle characteristics of a lithium ion secondary battery.
The amount (mol) of Al contained in the compound (II) present on the surface of the composite oxide (I) is measured by dissolving the positive electrode active material in an acid and performing high frequency inductively coupled plasma (ICP) measurement. . If the amount of Al cannot be determined by ICP measurement, the material used when compound (II) is present on the surface of the composite oxide (I) (for example, the amount of Al in the aqueous solution (II)) Based on the above, the amount of Al is calculated.

[Compound (III)]
Compound (III) is a compound containing at least one anion selected from the group consisting of SO ₄ ²⁻ , PO ₄ ³⁻ , and F ⁻ (hereinafter also referred to as anion (A)) and Li ⁺ . It is.
As the compound (III), Li ₂ SO ₄ , Li ₃ PO ₄ , and LiF are preferable. Among these, LiF is particularly preferable because of excellent cycle characteristics of the lithium ion secondary battery.

The compound (III) is preferably present on the surface of the composite oxide (I). The positive electrode active material in which the compound (III) is present on the surface of the composite oxide (I) can improve the initial efficiency of the lithium ion secondary battery. It exists on the surface of the composite oxide (I) and is used for charging and discharging by immobilizing an excessive amount of Li (also referred to as free Li) with respect to the composition ratio by the anion (A) of the compound (III). This is thought to be because Li easily diffuses in the composite oxide.
Compound (III) may exist over the entire surface of the composite oxide (I) or may exist partially. More preferably, the compound (III) is partially present on the surface of the composite oxide (I).
The compound (III) present on the surface of the composite oxide (I) may be one type or two or more types.

The presence of compound (III) on the surface of the composite oxide (I) is evaluated by TEM-EDX, EPMA, XPS or XRD measurement.
After cutting out the cross section of the positive electrode active material, the distribution state of the compound (III) is evaluated by performing elemental mapping of S, P and F with EPMA or TEM-EDX.
The chemical state of the compound (III) can be evaluated by XPS or XRD. For example, when the positive electrode active material is analyzed by XPS, if the peak of F (1s) is 684.6 eV to 685.4 eV, LiF, and if the peak of P (2p) is in the range of 132.4 eV to 133.4 eV, Li It can be determined that ₃ PO ₄ exists. In the XRD measurement, the presence of each compound can be determined by the presence or absence of a peak attributed to Li ₃ PO ₄ or Li ₂ SO ₄ .

When the positive electrode active material is the compound oxide (I) having the compound (III) present on the surface thereof, the amount of the anion (A) derived from the compound (III) contained in the positive electrode active material is expressed by the following formula: It is preferable that the relative amount (Xa) of the anion (A) determined in (1) is 0.001 to 0.1. When the relative amount (Xa) is 0.001 or more, the charge / discharge efficiency of the lithium ion secondary battery is easily improved. When the relative amount (Xa) is 0.1 or less, the capacity of the lithium ion secondary battery is reduced due to impurity generation. Hateful. The relative amount (Xa) is more preferably 0.003 to 0.07, and particularly preferably 0.005 to 0.05.
The relative amount (Xa) is the respective anions (A ₄ ) of SO ₄ ²⁻ , PO ₄ ³⁻ and F ⁻ contained in the compound (III) with respect to the total molar amount of the alkali metal elements contained in the composite oxide (I). ) Is a value obtained by multiplying the ratio of the molar amount of each) by the absolute value of the valence of each anion (A). In addition, as shown in Formula (1), when the positive electrode active material contains two or more types of anions (A1), (A2)..., The relative amount (Xa) is the total amount of all the positive electrode active materials. It is the total value of the relative amount of anions. That is, for each anion, “relative amount of anion (A1)”, “relative amount of anion (A2)”, and so on, are meant to be in the above-mentioned range.
Relative amount of anion (A) (Xa) = Σ (f _X × v _X ) / f _a (1)
f _X : molar amount of each anion (A) contained in compound (III) v _X : valence of each anion (A) f _a : total molar amount of alkali metal element contained in the positive electrode active material

  The amount (mol) of the anion (A) derived from the compound (III) contained in the positive electrode active material is measured by fluorescent X-ray analysis. If the amount of the anion (A) cannot be determined by fluorescent X-ray analysis, the material used when the compound (III) is present on the surface of the composite oxide (I) (for example, the aqueous solution (III)) The amount of the element is calculated based on the amount of the element.

<Method for producing positive electrode active material for lithium ion secondary battery>
This manufacturing method is a positive electrode for a lithium ion secondary battery containing a composite oxide (I) containing one or both of Ni and Co, Mn, and Li, and having a Li / M ratio of more than 1.2. An active material manufacturing method comprising:
A mixing step of mixing the following compound (A) and the following compound (B);
A first baking step of baking the mixture obtained in the mixing step at 450 to 700 ° C. in an oxygen-containing atmosphere;
A second firing step of obtaining the composite oxide (I) by firing the fired product obtained in the first firing step at 750 to 1000 ° C. in an oxygen-containing atmosphere.
Compound (A): Volume-based D50 diameter measured by a laser diffraction / scattering particle size distribution analyzer using water as a dispersion medium is 3 to 15 μm, D90 diameter is less than 40 μm, and either Ni or Co Or a carbonate compound containing both and Mn.
Compound (B): Lithium carbonate having a volume-based D50 diameter of 3 to 15 μm and a D90 diameter of less than 40 μm as measured with a laser diffraction / scattering particle size distribution analyzer using 2-propanol as a dispersion medium.

(Compound (A))
The compound (A) is a carbonate compound containing one or both of Ni and Co and Mn.
The molar ratio of Ni, Co and Mn in the compound (A) is preferably the same as the molar ratio of Ni, Co and Mn in the composite oxide (I). For example, when producing the composite oxide (I) represented by the general formula (I-1), the compound (A) is preferably represented by the following general formula (A-1).
Ni _x Co _y Mn _z Me _b CO ₃ (A-1)
However, Me is at least one element selected from the group consisting of Cr, Fe, Al, Ti, Zr, Mg, Mo, Ru, Nb, V and W, and 0.5 ≦ z ≦ 0.8, x + y + z = 1, 0 ≦ b ≦ 0.1.
Preferred ranges of x, y, z and b in the general formula (A-1) are the same as the preferred ranges of x, y, z and b in the general formula (I-1).

The compound (A) has a volume-based D50 diameter of 3 to 15 μm and a D90 diameter of less than 40 μm as measured with a laser diffraction / scattering particle size distribution analyzer using water as a dispersion medium. The D50 diameter of the compound (A) is preferably 4 to 11 μm, particularly preferably 5 to 10 μm. The D90 diameter of the compound (A) is preferably less than 30 μm, particularly preferably less than 25 μm.
When the D50 diameter of the compound (A) is 3 to 15 μm and the D90 diameter is less than 40 μm, the D50 diameter of the composite oxide (I) tends to be in the range of 2.5 to 14 μm. Further, when the D50 diameter of the compound (A) is 15 μm or less and the D90 diameter is less than 40 μm, the compound (B) is easily mixed uniformly in the mixing step. When the D50 diameter of the compound (A) is 3 μm or more, the handleability is good.

Compound (A) is the specific surface area is preferably from 50 to 250 m ² / g, more preferably 80~220m ² / g, particularly preferably 100 to 200 m ² / g. When the specific surface area of the compound (A) is in the above range, the specific surface area of the composite oxide (I) can be easily controlled within a preferable range.
The specific surface area of the compound (A) can be measured by the same method as for the composite oxide (I).

Compound (A) is preferably produced by a carbonate coprecipitation method. The carbonate coprecipitation method is a carbonate (coprecipitate) containing a transition metal element by mixing an aqueous solution of a metal salt containing a transition metal element and an aqueous solution containing a carbonate ion source and co-precipitation in the solution. Is a method of precipitating. In the carbonate coprecipitation method, a porous coprecipitate having a high specific surface area is obtained. When this coprecipitate is used as the compound (A), a positive electrode active material exhibiting a high discharge capacity is obtained.
The D50 diameter of the compound (A) is greatly influenced by the composition of the compound (A) deposited by the coprecipitation reaction. For example, the stirring conditions, reaction temperature, concentration and addition rate of the metal salt aqueous solution, reaction time, etc. are adjusted. By doing so, D50 diameter of a compound (A) can be made into a predetermined value. As the stirring power per unit volume increases, the agglomeration of the carbonate is suppressed and the D50 diameter tends to decrease. As the reaction temperature is higher, the aggregation of carbonate is promoted and the D50 diameter tends to increase. As the concentration of the aqueous metal salt solution is higher and the addition rate is faster, the D50 diameter tends to increase in a shorter time. When the reaction time is shortened, the D50 diameter tends to be small. As an example which can make D50 of a compound (A) 3-15 micrometers, the method as described in an Example is mentioned.

Examples of the metal salt containing a transition metal element include nitrates, acetates, chlorides, and sulfates of transition metal elements. Since the material cost is relatively low and excellent battery characteristics are obtained, a transition metal element sulfate is preferable, and a sulfate composed of Ni sulfate, Co sulfate and Mn sulfate is more preferable.
Examples of the sulfate of Ni include nickel (II) sulfate hexahydrate, nickel (II) sulfate heptahydrate, nickel sulfate (II) ammonium hexahydrate, and the like.
Examples of Co sulfate include cobalt (II) sulfate heptahydrate and cobalt (II) ammonium sulfate hexahydrate.
Examples of the sulfate of Mn include manganese sulfate (II) pentahydrate, manganese sulfate (II) ammonium hexahydrate, and the like.

  If necessary, a metal salt containing at least one selected from the group consisting of Cr, Fe, Al, Ti, Zr, Mg, Mo, Ru, Nb, V and W may be added to the reaction solution. Examples of the metal salt include nitrates, acetates, chlorides and sulfates of these metals.

The carbonate ion source is preferably at least one selected from the group consisting of sodium carbonate, sodium bicarbonate, potassium carbonate, and potassium bicarbonate. The carbonate ion source also serves to adjust the pH of the reaction solution. In the carbonate coprecipitation method, the pH of the reaction solution is preferably 7 to 9 and is kept constant at a specific pH.
In order to adjust the solubility of the metal salt containing the transition metal element, an aqueous ammonia solution or an aqueous ammonium sulfate solution may be added to the reaction solution.

The coprecipitate deposited by the carbonate coprecipitation method is preferably separated from the reaction solution by filtration, sedimentation separation, or centrifugation. For filtration or centrifugation, a pressure filter, a vacuum filter, a centrifugal classifier, a filter press, a screw press, a rotary dehydrator, or the like can be used.
It is preferable to carry out a step of washing the coprecipitate after separating the coprecipitate from the reaction solution. By washing, impurity ions such as Na adhering to the coprecipitate can be removed. Examples of the method for washing the coprecipitate include a method of repeating filtration and dispersion in ion-exchanged water.

(Compound (B))
The compound (B) is lithium carbonate having a volume-based D50 diameter of 3 to 15 μm and a D90 diameter of less than 40 μm as measured with a laser diffraction / scattering particle size distribution analyzer using 2-propanol as a dispersion medium. The D50 diameter of the compound (B) is preferably 4 to 11 μm, particularly preferably 5 to 10 μm. The D90 diameter of the compound (B) is preferably less than 25 μm, particularly preferably less than 20 μm.
When the D50 diameter of the compound (B) is 15 μm or less, the reactivity between the compound (B) and the compound (A) increases. When the D90 diameter of the compound (B) is 40 μm or less, when the compound (B) and the compound (A) react with each other, it is difficult to generate a portion having a high Li concentration locally, and the composite oxide (I ) Is easily obtained. When the D50 diameter of the compound (B) is 15 μm or less and the D90 diameter is less than 40 μm, the initial discharge capacity and the initial efficiency of the obtained lithium ion secondary battery having the positive electrode active material are improved.

  In this production method, the D50 diameter of the compound (B) is preferably equal to or less than the D50 diameter of the compound (A) from the viewpoint that the initial discharge capacity and initial efficiency of the lithium ion secondary battery are more excellent, and the compound (B) It is more preferable that the D50 diameter of is smaller than the D50 diameter of the compound (A). When the D50 diameter of the compound (B) is less than or equal to the D50 diameter of the compound (A), the compound (B) is present so as to cover the periphery of the compound (A) when the compound (A) and the compound (B) are mixed. Therefore, it is considered that the reactivity is improved during firing.

(Mixing process)
In the mixing step of this production method, the compound (A) and the compound (B) are mixed.
The mixing ratio of compound (A) and compound (B) in the mixing step is the ratio of the molar amount of Li contained in compound (B) to the total molar amount of Ni, Co and Mn contained in compound (A) ( It is preferable that the mixing ratio is a ratio exceeding 1.2. The mixing ratio is more preferably 1.2 to 1.6, further preferably 1.3 to 1.55, and particularly preferably 1.35 to 1.50. When the mixing ratio is within the above range, the discharge capacity of the lithium ion secondary battery can be increased.
Examples of the method of mixing the compound (A) and the compound (B) include a method using a rocking mixer, a nauta mixer, a spiral mixer, a cutter mill, a V mixer, and the like.

In the mixing step, it is preferable to add water when mixing the compound (A) and the compound (B). Thereby, a compound (A) and a compound (B) can be mixed more uniformly. As a result, battery characteristics, particularly initial characteristics, of the obtained positive electrode active material are improved.
0.15-15 mass% is preferable with respect to the total mass of a compound (A) and a compound (B), and, as for the addition amount of water, 0.3-12 mass% is more preferable.

(First firing step, second firing step)
This manufacturing method includes a first baking step of baking the mixture obtained in the mixing step at a temperature of 450 to 700 ° C. in an oxygen-containing atmosphere, and a fired product obtained in the first baking step. The 2nd baking process baked at the temperature of 750-1000 degreeC in a containing atmosphere is performed.
The positive electrode active material obtained by performing the second baking at a high temperature after the first baking step at a relatively low temperature can increase the discharge capacity of the lithium ion secondary battery and improve the cycle characteristics. The reason is considered as follows. In the first firing step, compound (A) and compound (B) react to form a composite oxide. Next, the crystallinity of the composite oxide is improved in the second firing step, and composite oxide (I) is obtained. By separating the reaction step and the crystallinity improvement step, the dispersion state of Li in the composite oxide (I) becomes uniform. As a result, it is considered that the lithium ion secondary battery having the positive electrode active material containing the composite oxide (I) has improved battery characteristics.

The firing temperature in the first firing step is 450 to 700 ° C, preferably 500 to 650 ° C, particularly preferably 500 to 600 ° C. The firing time in the first firing step is preferably 2 to 12 hours, and more preferably 4 to 10 hours.
The firing temperature in the second firing step is 750 to 1000 ° C, preferably 800 to 950 ° C, particularly preferably 850 to 930 ° C. The firing time in the second firing step is preferably 4 to 24 hours, and more preferably 6 to 20 hours.

The first baking step and the second baking step can be performed using a baking apparatus such as an electric furnace, a continuous baking furnace, and a rotary kiln.
Each of the first baking step and the second baking step is performed in an oxygen-containing atmosphere. Thereby, the transition metal element in the compound (A) is sufficiently oxidized, and the crystallinity tends to be high. The first and second firing steps are preferably performed in an air atmosphere, and particularly preferably performed while supplying air.

(Surface treatment process)
The production method preferably further includes a step (surface treatment step) in which a foreign compound is present on the surface of the composite oxide (I) obtained in the second firing step. The positive electrode active material obtained through the surface treatment step can further improve the cycle characteristics or rate characteristics of the lithium ion secondary battery.
The surface treatment step is preferably a step of allowing compound (II) and / or compound (III) to exist on the surface of composite oxide (I). For example, the following surface treatment step 1 and / or surface treatment step 2 is preferable.
Surface treatment step 1: a step of allowing compound (II) to exist on the surface of the composite oxide (I).
Surface treatment step 2: a step of allowing compound (III) to exist on the surface of the composite oxide (I).

Examples of the method for causing compound (II) and / or compound (III) to exist on the surface of composite oxide (I) in the surface treatment step include a powder mixing method, a gas phase method, a spray coating method, and an immersion method. It is done.
In the powder mixing method, a method in which the compound (II) and / or the compound (III) and the composite oxide (I) are mixed and then heated at a temperature of 300 to 600 ° C. is preferable.
In the gas phase method, the compound (II) and / or the compound (III) is vaporized, and the compound is brought into contact with the surface of the composite oxide (I) and reacted to thereby react the compound on the surface of the composite oxide (I). (II) and / or compound (III) can be present. In the vapor phase method, if necessary, after the contact, heating may be performed at a temperature of 100 to 600 ° C. The atmospheric pressure at the time of contact may be atmospheric pressure, may be pressurized, or may be depressurized.

In the spray coating method, at least one selected from the group consisting of a solution containing Al cations (referred to as solution (II)) and / or anions (A) (SO ₄ ²⁻ , PO ₄ ³⁻ , and F ⁻ ). After spraying a solution containing the anion of the species (solution (III)) onto the composite oxide (I) and heating, the compound (II) and / or the compound is formed on the surface of the composite oxide (I). (III) can be present.
In the immersion method, the composite oxide (I) is immersed in the solution (II) and / or the solution (III), dried or filtered, and then heated, whereby the compound (II) is applied to the surface of the composite oxide (I). ) And / or compound (III) can be present.

  Among the surface treatment methods described above, the step of removing the solvent by filtration or evaporation after contact is unnecessary, and the process is simple. On the surface of the composite oxide (I), the compound (II) and / or the compound (III) The spray coating method or the dipping method is more preferable, and the spray coating method is particularly preferable from the viewpoint of easily forming the film.

In the surface treatment step by the spray coating method or the dipping method, the solution (II) and the solution (III) and the composite oxide (I) are brought into contact with each other as the composite oxide (I), the solution (II) and the solution An embodiment in which (III) is contacted separately and an embodiment in which solution (II) and solution (III) are simultaneously contacted with composite oxide (I) can be mentioned.
Examples of the mode in which the solution (II) and the solution (III) are brought into contact separately include the following three modes. A mode in which the solution (II) is contacted with the composite oxide (I), and then the solution (III) is contacted with the composite oxide (I). A mode in which the solution (III) is brought into contact with the composite oxide (I) and then the solution (II) is brought into contact with the composite oxide (I). A mode in which one solution and the other solution are alternately brought into contact with the composite oxide (I) a plurality of times.
As an embodiment in which the solution (II) and the solution (III) are simultaneously contacted, the composite oxide (I) is simultaneously contacted with the solution (II) and the solution (III), and the solution (II) and the solution (III) are A mode in which the mixed solution is brought into contact with the composite oxide (I) after mixing in advance to obtain a mixed solution, and the like can be mentioned.

  When the solution (II) and the solution (III) are brought into contact with the composite oxide (I) at the same time, the reaction between the cation of Al and the anion (A) easily proceeds. It is particularly preferable that the order in which the solution (III) is contacted after the contact of (II) is made.

The surface treatment step by the spray coating method or the dipping method includes a step of heating after bringing the solution (II) and / or the solution (III) into contact with the composite oxide (I).
Heating in the surface treatment step may be performed after bringing the complex oxide (I) into contact with all the solutions, or may be performed each time after bringing the complex oxide (I) into contact with each solution. . From the viewpoint of productivity, the heating is more preferably performed after contacting the composite oxide (I) with all the solutions.

[Solution (II)]
The solution (II) is a solution containing an Al cation. The solution (II) is preferably a solution in which a water-soluble compound (1) that generates an Al cation in an aqueous solution is dissolved in a solvent.
In the present specification, the solubility in distilled water at 25 ° C. (the mass [g] of the solute dissolved in 100 g of the saturated solution) exceeds 2 is referred to as water solubility.
Examples of the water-soluble compound (1) contained in the solution (II) include inorganic salts such as Al nitrate, sulfate and chloride, acetate, citrate, maleate, formate, lactate, and lactic acid. Examples thereof include organic salts such as salts and oxalates, organic complexes, and ammine complexes. Among these, nitrates, organic acid salts, organic complexes, and ammine complexes are particularly preferable because they are easily decomposed by heat and have high solubility in water.

The solution (II) may contain a water-soluble alcohol and / or polyol as long as the solubility of the compound (1) is not impaired.
Examples of the water-soluble alcohol include methanol, ethanol, 1-propanol, and 2-propanol. Examples of the polyol include ethylene glycol, propylene glycol, diethylene glycol, dipropylene glycol, polyethylene glycol, butanediol, and glycerin.
The range that does not impair the solubility of the compound (1) means that the total mass of the water-soluble alcohol and the polyol is 0 to 20% with respect to the total mass of the solvent.

  The solution (II) may contain a pH adjusting agent in order to adjust the solubility of the compound (1). As the pH adjuster, those that volatilize or decompose when heated in a later step are preferable. For example, an organic acid such as acetic acid, citric acid, lactic acid, formic acid, maleic acid, oxalic acid, or ammonia is preferable. As described above, when a pH adjuster that volatilizes or decomposes is used, it is difficult for impurities to remain, and thus good battery characteristics are easily obtained.

The content of the compound (1) in the solution (II) is preferably 0.5 to 30% and particularly preferably 2 to 20% in terms of Al with respect to the total mass of the solution (II).
If the compound (1) is 0.5% or more, it is preferable because the solvent can be easily removed by heating in the subsequent step. Moreover, if it is 30% or less, the viscosity of solution (II) will become an appropriate range, and it is preferable at the point which is easy to make complex oxide (I) and solution (II) contact uniformly.

  When the solution (II) is brought into contact with the composite oxide (I), the ratio of the molar amount of Al in the solution (II) to the total molar amount of Ni, Co and Mn in the composite oxide (I) (contact ratio) ) Is preferably 0.005 to 0.06. If the contact ratio is within this range, the Al / M ratio can be set within a desired range, and thus the obtained positive electrode active material can improve the rate characteristics and cycle characteristics of the lithium ion secondary battery. The contact ratio is more preferably within the range of 0.01 to 0.05, and particularly preferably within the range of 0.015 to 0.04.

[Solution (III)]
The solution (III) is a solution containing an anion (A) (at least one anion selected from the group consisting of SO ₄ ²⁻ , PO ₄ ³⁻ , and F ⁻ ).
The aqueous solution (III) is preferably a solution in which the water-soluble compound (2) that is dissociated in the aqueous solution to generate an anion is dissolved.

Examples of the compound (2) include acids such as H ₂ SO ₄ , H ₃ PO ₄ , and HF, or ammonium salts, amine salts, lithium salts, sodium salts, potassium salts and the like thereof. Among these, it is preferable to use a salt rather than an acid in terms of handleability and safety. An ammonium salt is particularly preferable in that it is decomposed and removed when heated. Specifically, (NH ₄ ) ₂ SO ₄ , (NH ₄ ) HSO ₄ , (NH ₄ ) ₃ PO ₄ , (NH ₄ ) ₂ HPO ₄ , (NH ₄ ) H ₂ PO ₄ , NH ₄ F and the like are preferable. .

  The solution (III) may contain one or both of a water-soluble alcohol and a polyol, and a pH adjuster, as in the case of the solution (II). Moreover, the content is the same as that of the solution (II).

  The content of the compound (2) in the solution (III) is preferably adjusted to such an amount that the relative amount (Xa) obtained by the above formula (1) is 0.001 to 0.1. Thereby, the positive electrode active material obtained can improve the charging / discharging efficiency of a lithium ion secondary battery. The relative amount (Xa) is more preferably 0.003 to 0.07, and particularly preferably 0.005 to 0.05.

  In the spray coating method or the dipping method, the composite oxide (I) after contacting with the solution (II) and / or the solution (III) is heated. By this heating, volatile impurities such as water and organic components contained in the solution (II) and / or the solution (III) are removed, and the compound (II) is partially or entirely on the surface of the composite oxide (I). And / or a positive electrode active material in which compound (III) is present.

Heating is preferably performed in an oxygen-containing atmosphere. The heating temperature is preferably 250 to 700 ° C, and more preferably 350 to 600 ° C. When the heating temperature is 250 ° C. or higher, compound (II) and / or compound (III) is obtained on the surface of the composite oxide (I). Further, since the volatile impurities such as residual moisture are reduced in the composite oxide (I), it is possible to suppress the deterioration of the cycle characteristics of the lithium ion secondary battery.
Moreover, when making compound (II) amorphous, 250 to 550 degreeC is preferable for heating temperature, and 350 to 500 degreeC is more preferable. When the heating temperature is 550 ° C. or lower, the compound (II) is difficult to crystallize.
The heating time is preferably 0.1 to 24 hours, more preferably 0.5 to 18 hours, and particularly preferably 1 to 12 hours. When the heating time is in the above range, the compound (II) and / or the compound (III) are likely to be favorably formed on the surface of the composite oxide (I).
The pressure at the time of heating is not specifically limited, Normal pressure or pressurization is preferable, and normal pressure is particularly preferable.

<Positive electrode for lithium ion secondary battery>
The positive electrode for lithium ion secondary batteries of the present invention (hereinafter referred to as the present positive electrode) includes a positive electrode active material manufactured by the above-described manufacturing method and a binder.
The configuration of the present positive electrode may be the same as that of a conventional positive electrode except that the positive electrode active material manufactured by the present manufacturing method is used as the positive electrode active material. For example, the positive electrode active material layer containing the positive electrode active material, the conductive material, and the binder is formed on the positive electrode current collector (positive electrode surface).
This positive electrode can be manufactured, for example, by forming a positive electrode active material layer containing the positive electrode active material, the conductive material and the binder on the positive electrode current collector.
The step of forming the positive electrode active material layer can be performed using a known method. For example, a positive electrode active material, a conductive material, and a binder are dissolved or dispersed in a medium to obtain a slurry, or a positive electrode active material, a conductive material, and a binder are kneaded with a medium to obtain a kneaded product. Next, the slurry is applied onto the positive electrode current collector (positive electrode surface), or the kneaded product is rolled onto the positive electrode current collector (positive electrode surface). Thereby, a positive electrode active material layer can be formed.

Examples of the conductive material include carbon black such as acetylene black, graphite, and ketjen black. One type of conductive material may be used, or two or more types may be used.
Examples of the binder include a fluorine resin, a polyolefin, a polymer having an unsaturated bond, and an acrylic acid polymer. Examples of the fluororesin include polyvinylidene fluoride and polytetrafluoroethylene. Examples of the polyolefin include polyethylene and polypropylene. Examples of the polymer having an unsaturated bond include styrene / butadiene rubber, isoprene rubber, and butadiene rubber.
Examples of the positive electrode current collector include an aluminum foil or an aluminum alloy foil.

<Lithium ion secondary battery>
The lithium ion secondary battery of the present invention (hereinafter referred to as the present battery) includes the present positive electrode, a negative electrode, and a nonaqueous electrolyte.
The configuration of the battery may be the same as that of a conventional lithium ion secondary battery except that the positive electrode is used.
The battery typically further includes a separator.

The negative electrode is formed by forming a negative electrode active material layer containing a negative electrode active material on a negative electrode current collector.
The negative electrode can be produced, for example, by preparing a slurry by kneading a negative electrode active material and an organic solvent, and applying the prepared slurry to a negative electrode current collector, drying, and pressing.
As the negative electrode current collector, for example, a metal foil such as a nickel foil or a copper foil can be used.
The negative electrode active material may be any material that can occlude and release lithium ions at a relatively low potential, for example, lithium metal, lithium alloy, carbon material, oxide mainly composed of periodic table 14 or group 15 metal. Carbon compounds, silicon carbide compounds, silicon oxide compounds, titanium sulfide, boron carbide compounds, and the like can be used.

Examples of the carbon material used for the negative electrode active material include non-graphitizable carbon, artificial graphite, natural graphite, pyrolytic carbons, cokes, graphites, glassy carbons, organic polymer compound fired bodies, and carbon fibers. , Activated carbon, carbon blacks and the like. Examples of the cokes include pitch coke, needle coke, and petroleum coke. Examples of the fired organic polymer compound include those obtained by firing and carbonizing a phenol resin, a furan resin, or the like at an appropriate temperature.
Examples of the metal of Group 14 of the periodic table include Si and Sn. Among these, Si is preferable as the metal of Group 14 of the periodic table.
Other materials that can be used as the negative electrode active material include oxides such as iron oxide, ruthenium oxide, molybdenum oxide, tungsten oxide, titanium oxide, and tin oxide, and nitrides such as Li _2.6 Co _0.4 N. It is done.

  Examples of the nonaqueous electrolyte include a nonaqueous electrolytic solution in which an electrolyte salt is dissolved in an organic solvent, an inorganic solid electrolyte, a solid or gel polymer electrolyte in which an electrolyte salt is mixed or dissolved, and the like.

As the electrolyte salt, known ones used in lithium ion secondary batteries can be used, and examples thereof include LiClO ₄ , LiPF ₆ , LiBF ₄ , CF ₃ SO ₃ Li, LiCl, and LiBr.

  As the organic solvent, those known as organic solvents for non-aqueous electrolytes can be employed. For example, propylene carbonate, ethylene carbonate, diethyl carbonate, dimethyl carbonate, 1,2-dimethoxyethane, 1,2-diethoxyethane, γ-butyrolactone, diethyl ether, sulfolane, methyl sulfolane, acetonitrile, acetate ester, butyrate ester, propion Acid ester etc. are mentioned. Among these, from the viewpoint of voltage stability, the organic solvent is preferably a cyclic carbonate such as propylene carbonate, or a chain carbonate such as dimethyl carbonate or diethyl carbonate. One organic solvent may be used, or two or more organic solvents may be used.

Examples of the inorganic solid electrolyte include lithium nitride and lithium iodide.
Examples of the polymer compound used in the solid polymer electrolyte in which the electrolyte salt is mixed or dissolved include polyethylene oxide, polypropylene oxide, polyphosphazene, polyaziridine, polyethylene sulfide, polyvinyl alcohol, polyvinylidene fluoride, polyhexafluoropropylene, And their derivatives, mixtures, and complexes.
Examples of the polymer compound used in the gel polymer electrolyte in which the electrolyte salt is mixed or dissolved include a fluorine polymer compound, polyacrylonitrile, a copolymer of polyacrylonitrile, polyethylene oxide, a copolymer of polyethylene oxide, and the like. Can be mentioned. Examples of the fluorine-based polymer compound include poly (vinylidene fluoride) and poly (vinylidene fluoride-co-hexafluoropropylene).
The matrix of the gel electrolyte is preferably a fluorine-based polymer compound from the viewpoint of stability against redox reaction.

  Examples of the separator include a film made of a microporous polyolefin film typified by polyethylene and polypropylene, polyvinylidene fluoride, and a hexafluoropropylene copolymer.

  The shape of the lithium ion secondary battery is not particularly limited, and shapes such as a coin shape, a sheet shape (film shape), a folded shape, a wound type bottomed cylindrical shape, and a button shape can be appropriately selected according to the application.

  This battery can be manufactured by constituting a lithium ion secondary battery using the present positive electrode, negative electrode, non-aqueous electrolyte, separator and the like. The process which comprises a lithium ion secondary battery can be performed using a well-known method.

Hereinafter, the present invention will be described in detail with reference to examples. However, the present invention is not limited by the following description.
Among Examples 1 to 10 described later, Examples 1 to 3 and 5 to 10 are examples, and Example 4 is a comparative example.
Table 1 shows the D10 diameter, D50 diameter, D90 diameter, and D99 diameter of the lithium carbonate used in each example. Each of these diameters is a value obtained by dispersing each lithium carbonate in 2-propanol and measuring the particle size distribution with a laser diffraction / scattering particle size distribution measuring apparatus (manufactured by Nikkiso Co., Ltd., Microtrac MT3000II).
Table 1 shows the D10 diameter, D50 diameter, D90 diameter, and D99 diameter of the coprecipitates (A1) to (A2) (transition metal-containing carbonate compound) obtained in Synthesis Examples 1 and 2 described later. Each of these diameters is a value obtained by dispersing each coprecipitate in water and measuring the particle size distribution with a laser diffraction / scattering particle size distribution measuring apparatus (manufactured by Nikkiso Co., Ltd., Microtrac MT3000II).

<Synthesis of coprecipitation compound (transition metal-containing carbonate compound)>
(Synthesis Example 1)
Nickel sulfate (II) hexahydrate, cobalt sulfate (II) heptahydrate, manganese sulfate (II) pentahydrate, and Ni: Co: Mn = 20: 15: 65 (molar ratio) The raw material solution was obtained by dissolving in distilled water so that the total concentration of Ni, Co, and Mn was 1.5 mol / L. Ammonium sulfate was dissolved in distilled water to a concentration of 0.75 mol / L to obtain an aqueous ammonium sulfate solution. Sodium carbonate was dissolved in distilled water to a concentration of 1.5 mol / L to obtain an aqueous sodium carbonate solution.

Next, distilled water is put into a 2 L baffled glass reaction vessel and heated to 30 ° C. with a mantle heater, and the solution in the reaction vessel is stirred by a two-stage inclined paddle type stirring blade with a stirring power of 1.5 kW per unit volume. While stirring at / m ³ , the raw material solution was added at a rate of 5.0 g / min and an aqueous ammonium sulfate solution at a rate of 0.5 g / min over 24 hours, and a coprecipitate containing Ni, Co and Mn (containing transition metal) Carbonate compound) was precipitated. During the addition of the raw material solution, an aqueous sodium carbonate solution was added so as to keep the pH in the reaction vessel at 8.0. Further, the liquid was continuously extracted so that the amount of the liquid in the reaction tank did not exceed 2 L.
The obtained coprecipitate was repeatedly washed with pressure filtration and dispersed in distilled water to remove impurity ions. The coprecipitate after washing was dried at 120 ° C. for 15 hours.

After drying, the contents of Ni, Co and Mn contained in the obtained coprecipitate (hereinafter referred to as coprecipitate (A1)) were measured by high frequency inductively coupled plasma (ICP). As a result, the contents of Ni, Co and Mn were 9.6%, 7.5% and 30.7% with respect to the mass of the entire coprecipitate (Ni: Co: Mn = molar ratio). 0.193: 0.150: 0.657).
The D10 diameter, D50 diameter, D90 diameter, and D99 diameter of the coprecipitate (A1) were measured. The results are shown in Table 1.

(Synthesis Example 2)
Nickel sulfate (II) hexahydrate, cobalt sulfate (II) heptahydrate, manganese sulfate (II) pentahydrate were converted into Ni: Co: Mn = 38.6: 8.6: 52. A coprecipitate (hereinafter referred to as a coprecipitate (A2)) was obtained in the same manner as in Synthesis Example 1 except that the ratio was 8 (molar ratio).
The contents of Ni, Co and Mn contained in the coprecipitate (A2) were measured by high frequency inductively coupled plasma (ICP). As a result, the contents of Ni, Co and Mn were 19.1%, 4.3% and 24.6% with respect to the mass of the entire coprecipitate (Ni: Co: Mn = molar ratio). 0.385: 0.086: 0.529).
The D10 diameter, D50 diameter, D90 diameter, and D99 diameter of the coprecipitate (A2) were measured. The results are shown in Table 1.

<Manufacture of complex oxide>
(Example 1)
Ratio of the molar amount of Li contained in lithium carbonate (B1) to the total molar amount of Ni, Co, and Mn contained in the coprecipitate (A1) (mixing) of the coprecipitate (A1) and lithium carbonate (B1) The ratio was 1.45.
The obtained mixture was baked at 580 ° C. for 4 hours under an air atmosphere, and then baked at 850 ° C. for 12 hours under an air atmosphere. Thereby, a composite oxide was obtained. The obtained composite oxide was used as the positive electrode active material of Example 1.
Note that when the composition of the composite oxide was calculated from the contents of Ni, Co, and Mn contained in the coprecipitate (A1) and the amount of lithium carbonate (B1), Li _1.45 Ni _0.193 Co _0. It became ₁₅₀ Mn _0.657 O _2.45 .

(Examples 2 to 4)
A composite oxide was obtained in the same manner as in Example 1 except that lithium carbonate (B2), lithium carbonate (B3), and lithium carbonate (B4) were used instead of lithium carbonate (B1). The obtained composite oxides were used as positive electrode active materials of Examples 2 to 4, respectively.

<Manufacture of complex oxides with different compounds on the surface>
(Example 5)
An aqueous aluminum lactate solution was prepared by adding 3.27 g of distilled water to 6.73 g of a basic aluminum lactate aqueous solution having an Al content relative to the aqueous solution of 8.8% in terms of mass ratio in terms of Al ₂ O ₃ , and mixing them.
While stirring 10 g of the composite oxide obtained in Example 1, 1.6 g of the aluminum lactate aqueous solution was sprayed by a spray coating method to bring the composite oxide into contact with the aluminum lactate aqueous solution. Thereby, a mixture of the composite oxide and the aluminum lactate aqueous solution was obtained.
The resulting mixture was dried at 80 ° C. for 4 hours under an air atmosphere and then heated at 450 ° C. for 5 hours under an air atmosphere. Thereby, particles in which compound (II) was present on part of the surface of the composite oxide particles were obtained. The obtained particles were used as the positive electrode active material of Example 5.
When the Al in the compound (II) contained in the positive electrode active material is calculated from the charged amount, the ratio of the molar amount of Al to the total molar amount of Ni, Co and Mn of the composite oxide (I) (Al / M ratio) Was 0.020.
After embedding the cross section of the positive electrode active material powder with a resin, it was thinned and subjected to TEM-EDX analysis. As a result, it was confirmed that Al was present not on the positive electrode active material but on the surface.
When the XPS measurement of the positive electrode active material powder was performed, the peak position of Al (2p) was 73.8 eV, which was the same as the peak of Al ₂ O ₃ .

(Example 6)
8.39 g of distilled water was added to 1.61 g of ammonium fluoride (NH ₄ F) and mixed to prepare an aqueous ammonium fluoride solution.
After obtaining a mixture of the composite oxide and the aluminum lactate aqueous solution in the same manner as in Example 5, while stirring the mixture, an aqueous ammonium fluoride solution was sprayed by a spray coating method, and the mixture and the aqueous ammonium fluoride solution 1. 28 g was contacted. As a result, a mixture of the composite oxide, the aluminum lactate aqueous solution, and the ammonium fluoride aqueous solution was obtained.
The resulting mixture was dried at 80 ° C. for 4 hours under an air atmosphere and then heated at 450 ° C. for 5 hours under an air atmosphere. As a result, particles containing compound (II) containing Al and compound (III) containing F ⁻ and Li ⁺ on a part of the surface of the composite oxide particles were obtained. The obtained particles were used as the positive electrode active material of Example 6.
When the Al in the compound (II) contained in the positive electrode active material is calculated from the charged amount, the ratio of the molar amount of Al to the total molar amount of Ni, Co and Mn of the composite oxide (I) (Al / M ratio) Was 0.020.
When F in the compound (III) contained in the positive electrode active material was calculated from the charged amount, the relative amount (Xa) of the anion (A) was 0.037.
After embedding the cross section of the positive electrode active material powder with a resin, it was thinned and subjected to TEM-EDX analysis. As a result, it was confirmed that Al was present not on the positive electrode active material but on the surface.
When the XPS measurement of the positive electrode active material powder was performed, the peak position of Al (2p) was 73.8 eV, which was the same as the peak of Al ₂ O ₃ . The peak position of F (1s) was 685.0 eV, which was the same as the peak of LiF.

(Example 7)
Ratio of the molar amount of Li contained in the lithium carbonate (B1) to the total molar amount of Ni, Co and Mn contained in the coprecipitate (A2) and the lithium carbonate (B1) (mixed) The ratio was 1.145.
The obtained mixture was baked at 580 ° C. for 4 hours under an air atmosphere, and then baked at 850 ° C. for 12 hours under an air atmosphere. Thereby, a composite oxide was obtained. The obtained composite oxide was used as the positive electrode active material of Example 7.
Note that when the composition of the composite oxide was calculated from the contents of Ni, Co, and Mn contained in the coprecipitate (A2) and the amount of lithium carbonate (B1), Li _1.145 Ni _0.385 Co _{0. 086} Mn _0.529 O _2.145 .

(Examples 8 to 10)
When mixing the coprecipitate (A2) and lithium carbonate (B1), a composite oxide was obtained in the same manner as in Example 7 except that water was added. The amount of water added was 1% by mass, 5% by mass, and 10% by mass with respect to the total mass of the coprecipitate (A2) and lithium carbonate (B1). The obtained composite oxides were used as the positive electrode active materials of Examples 8 to 10.

<Manufacture of positive electrode sheet>
The positive electrode active material obtained in Examples 1 to 10, acetylene black (conductive material), and a solution containing 12% by mass of polyvinylidene fluoride (binder) (solvent, N-methylpyrrolidone) were mixed. Methylpyrrolidone was added to prepare a slurry. At this time, the positive electrode active material, acetylene black, and polyvinylidene fluoride were in a mass ratio of 80:10:10.
Subsequently, this slurry was applied on one side to a 20 μm thick aluminum foil (positive electrode current collector) using a doctor blade. The gap of the doctor blade was adjusted so that the sheet thickness after rolling was 30 μm. After drying this at 120 degreeC, roll press rolling was performed twice and the positive electrode body sheet | seat was produced.

<Manufacture of lithium secondary batteries>
Using the positive electrode sheet obtained above as a positive electrode, a stainless steel simple sealed cell type lithium secondary battery was assembled in an argon glove box.
Note that a metal lithium foil having a thickness of 500 μm was used for the negative electrode, and a stainless steel plate having a thickness of 1 mm was used for the negative electrode current collector. As the separator, porous polypropylene having a thickness of 25 μm was used. As the electrolytic solution, a LiPF ₆ solution having a concentration of 1 mol / dm ³ was used. As a solvent for the electrolytic solution, a mixed solvent of ethylene carbonate and diethyl carbonate in a volume ratio of 1: 1 was used.

<Evaluation of lithium secondary battery>
About the lithium secondary battery obtained above, initial characteristics (initial discharge capacity, initial efficiency) and cycle characteristics (cycle maintenance ratio) were evaluated by the following procedure. Evaluation was performed at 25 ° C. The results are shown in Table 2.

(Initial characteristics)
The positive electrode active material was charged to 4.6 V with a load current of 20 mA per 1 g of the positive electrode active material, and discharged to 2.0 V with a load current of 20 mA per 1 g of the positive electrode active material. The discharge capacity (mAh / g) and the charge / discharge efficiency (%) at this time were defined as the initial discharge capacity and the initial efficiency, respectively. The discharge curves of Example 1 to Example 4 (vertical axis: voltage (V), horizontal axis: capacity (mAh / g)) are shown in FIG.

(Cycle characteristics)
A charging / discharging cycle of charging to 4.6 V with a load current of 200 mA per 1 g of the positive electrode active material and discharging at a high rate to 2.0 V with a load current of 200 mA per 1 g of the positive electrode active material was repeated 50 times. From the discharge capacity at the second cycle and the discharge capacity at the 50th cycle at this time, the cycle maintenance ratio (%) was obtained by the following formula.
Cycle maintenance ratio = 50th cycle discharge capacity / 2nd cycle discharge capacity × 100

As shown in the results of Examples 1 to 4 in Table 2, Examples 1 to 3 using lithium carbonate having a D50 diameter of 3 to 15 μm and a D90 diameter of less than 40 μm are carbon dioxide having a D50 diameter of more than 15 μm and a D90 diameter of 40 μm or more. The initial discharge capacity and the initial efficiency were higher than in Example 4 using lithium.
Among Examples 1 to 3, the initial discharge capacity and the initial efficiency were particularly high in Examples 1 and 2 in which the D50 diameter of lithium carbonate was not more than the D50 diameter of the coprecipitate (A1). Since almost the same performance was obtained in Example 1 and Example 2, the coprecipitate (A1) and lithium carbonate reacted sufficiently uniformly in the process of synthesizing the composite oxide (I). Conceivable.

When the discharge curves of Examples 1 to 4 shown in FIG. 1 are compared, the discharge curves almost overlap in the region of 3.4 V or higher, but there is a difference in the discharge curves at less than 3.4 V.
The lithium-rich layered positive electrode material is characterized by a large capacity of less than 3.4V. Since a difference was observed in the discharge curves at less than 3.4 V, it is considered that the particle size of lithium carbonate has an influence on the crystal structure peculiar to the lithium-rich layered positive electrode material.

From the results of Example 1 and Example 5 in Table 2, it was confirmed that when the compound (II) was present on the surface of the composite oxide (I), the cycle retention ratio was significantly improved.
Further, from the results of Example 5 and Example 6 in Table 2, it was confirmed that when the compound (III) was present on the surface of the composite oxide (I), particularly high initial efficiency was obtained.

  From Examples 7-10, it can be seen that the initial efficiency increases when a small amount of water is added in the mixing step. This is because the coprecipitate and lithium carbonate were uniformly mixed in the mixing step due to the added water, and as a result, the reaction proceeded uniformly in the firing step, and a positive active material with high initial efficiency was obtained. it is conceivable that.

Claims (11)

A composite oxide (I) containing one or both of Ni and Co, Mn, and Li, wherein the molar amount of Li is more than 1.2 times the total molar amount of Ni, Co, and Mn. A method for producing a positive electrode active material for a lithium ion secondary battery comprising:
A mixing step of mixing the following compound (A) and the following compound (B);
A first baking step of baking the mixture obtained in the mixing step at 450 to 700 ° C. in an oxygen-containing atmosphere;
And a second firing step of obtaining the composite oxide (I) by firing the fired product obtained in the first firing step at 750 to 1000 ° C. in an oxygen-containing atmosphere. To produce a positive electrode active material for a lithium ion secondary battery.
Compound (A): Volume-based D50 diameter measured by a laser diffraction / scattering particle size distribution analyzer using water as a dispersion medium is 3 to 15 μm, D90 diameter is less than 40 μm, and either Ni or Co Or a carbonate compound containing both and Mn.
Compound (B): Lithium carbonate having a volume-based D50 diameter of 3 to 15 μm and a D90 diameter of less than 40 μm as measured with a laser diffraction / scattering particle size distribution analyzer using 2-propanol as a dispersion medium.   The method for producing a positive electrode active material for a lithium ion secondary battery according to claim 1, wherein the compound (B) has a D50 diameter of 4 to 11 µm and a D90 diameter of less than 25 µm.   The manufacturing method of the positive electrode active material for lithium ion secondary batteries of Claim 1 or 2 whose D50 diameter of the said compound (B) is below D50 diameter of the said compound (A). The manufacturing method of the positive electrode active material for lithium ion secondary batteries of any one of Claims 1-3 with which the said complex oxide (I) is represented by the following general formula (I-1).
_{Li a Ni x Co y Mn z} Me b O p ... (I-1)
However, Me is at least one element selected from the group consisting of Cr, Fe, Al, Ti, Zr, Mg, Mo, Ru, Nb, V and W, and 1.2 <a <1.6, 0 0.5 ≦ z ≦ 0.8, x + y + z = 1, 0 ≦ b ≦ 0.1, 2.1 <p <2.7. The manufacturing method of the positive electrode active material for lithium ion secondary batteries of any one of Claims 1-4 with which the said compound (A) is represented with the following general formula (A-1).
Ni _x Co _y Mn _z Me _b CO ₃ (A-1)
However, Me is at least one element selected from the group consisting of Cr, Fe, Al, Ti, Zr, Mg, Mo, Ru, Nb, V and W, and 0.5 ≦ z ≦ 0.8, x + y + z = 1, 0 ≦ b ≦ 0.1.   X, y, z in the general formula (A-1) are 0.19 ≦ x ≦ 0.22, 0.14 ≦ y ≦ 0.18, and 0.62 ≦ z ≦ 0.67, respectively. Item 6. A method for producing a positive electrode active material for a lithium ion secondary battery according to Item 5.   The manufacturing method of the positive electrode active material for lithium ion secondary batteries of any one of Claims 1-6 which further has the process of making the oxide containing Al exist on the surface of the said composite oxide (I). The method further includes the step of causing a compound containing at least one anion selected from the group consisting of SO ₄ ²⁻ , PO ₄ ³⁻ , and F ⁻ and Li ⁺ to exist on the surface of the composite oxide (I). The manufacturing method of the positive electrode active material for lithium ion secondary batteries of any one of Claims 1-7.   In the said mixing process, water is added when mixing the said compound (A) and the said compound (B), The positive electrode active material for lithium ion secondary batteries of any one of Claims 1-8. Production method.   The positive electrode for lithium ion secondary batteries containing the positive electrode active material for lithium ion secondary batteries manufactured by the manufacturing method of any one of Claims 1-9, and a binder.   The lithium ion secondary battery containing the positive electrode for lithium ion secondary batteries of Claim 10, a negative electrode, and a nonaqueous electrolyte.

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