JP2019053951A - Electrode material for lithium ion secondary battery, electrode for lithium ion secondary battery, and lithium ion secondary battery - Google Patents

Abstract

To provide an electrode material having high electron conductivity and excellent lithium ion diffusivity, an electrode for a lithium ion secondary battery including the same, and a lithium ion secondary battery including the same.SOLUTION: The electrode material for lithium ion secondary batteries has an electrode active material having a melting point of 25°C or higher and carries an organic compound soluble in an electrolyte for a lithium ion secondary battery. Green compact density at a time of 51 MPa application is 2.3 g/cmor less.SELECTED DRAWING: None

Description

  The present invention relates to an electrode material for a lithium ion secondary battery, an electrode for a lithium ion secondary battery, and a lithium ion secondary battery.

In recent years, non-aqueous electrolyte secondary batteries such as lithium ion secondary batteries have been proposed and put into practical use as batteries that are expected to be reduced in size, weight, capacity, and output.
This lithium ion secondary battery is composed of a positive electrode and a negative electrode having a property capable of reversibly removing and inserting lithium ions, and a non-aqueous electrolyte.

As a negative electrode material for a lithium ion secondary battery, as a negative electrode active material, generally, a carbon-based material or a lithium-containing lithium titanate (Li ₄ Ti ₅ O ₁₂ ) or the like having a property capable of reversibly inserting and removing lithium ions Metal oxide is used.
As a positive electrode material for a lithium ion secondary battery, a layered oxide lithium cobaltate (LCO), a ternary layered oxide (NCM) in which a part of cobalt is substituted with manganese and nickel, and manganese are used as a positive electrode active material. Li-containing metal oxide having a property capable of reversibly removing and inserting lithium ions such as spinel manganese lithium (LMO), lithium iron phosphate (LFP), and lithium iron manganese phosphate (LFMP), which are lithium acid compounds; An electrode material mixture containing a binder or the like is used. And the positive electrode of a lithium ion secondary battery is formed by apply | coating this electrode material mixture on the surface of metal foil called an electrode collector.

  Such a lithium ion secondary battery is lighter and smaller than a conventional secondary battery such as a lead battery, a nickel cadmium battery, or a nickel metal hydride battery, and has high energy. Therefore, the lithium ion secondary battery is used not only as a small power source used for portable electronic devices such as a portable telephone and a notebook personal computer but also as a stationary emergency large power source. In recent years, lithium ion secondary batteries have also been studied as high-output power sources for power storage batteries, motorcycles, electric vehicles, plug-in hybrid vehicles, hybrid vehicles, idling stop systems, electric tools, and the like. High speed charge and discharge characteristics are required for lithium ion secondary batteries used as these high output power sources.

  However, an electrode active material, for example, an electrode material containing a lithium phosphate compound having a property capable of reversibly removing and inserting lithium ions has a problem that electron conductivity is low. Therefore, in order to increase the electron conductivity of the electrode material, the particle surface of the electrode active material is covered with an organic component that is a carbon source, and then the organic component is carbonized to form a carbonaceous film on the particle surface of the electrode active material. In addition, an electrode material in which carbon of the carbonaceous film is interposed as an electron conductive substance is known (for example, see Patent Document 1).

The higher the electron conductivity of the electrode material, the better. When unevenness occurs in the thickness of the carbonaceous film formed on the surface of the electrode active material, a portion having low electron conductivity is locally generated in the positive electrode. Therefore, when a lithium ion secondary battery is used as a stationary emergency large-scale power source, particularly when used at a low temperature, the lithium ion secondary battery has a problem of capacity reduction due to a voltage drop at the end of discharge. Arise. Therefore, by controlling the volume density of the aggregate (electrode material aggregated particles) formed by aggregating the electrode material for the purpose of reducing the uneven thickness of the carbonaceous film supported on the surface of the electrode active material, An electrode material is known in which unevenness in the thickness of a carbonaceous film supported on the surface of an electrode active material is reduced and low temperature characteristics are improved (see, for example, Patent Document 2).
On the other hand, apart from improvements in electrode materials, in lithium ion secondary battery electrodes, the pressure in the direction perpendicular to the surface of the electrode current collector (hereinafter referred to as “pressing pressure”) is applied to the electrode current collector coated with the electrode material mixture layer. It is generally known that the contact point of the conductive auxiliary agent in the electrode material mixture layer is increased to improve the conductivity and ensure the function as an electrode.

JP 2001-015111 A JP 2012-133888 A

  However, when the press pressure is applied to improve the conductivity of the electrode mixture layer, if the press pressure is too low, the number of contact points of the conductive aid in the electrode material mixture layer is insufficient, and high-speed charge / discharge characteristics are exhibited. As a required lithium-ion secondary battery for a high-output power source, the conductivity is insufficient. On the other hand, if the press pressure is too high, plastic deformation of the electrode material agglomerated particles occurs, and the voids in the electrode material agglomerated particles are crushed, thereby reducing the lithium ion conduction path and requiring high-speed charge / discharge characteristics. As a lithium ion secondary battery, there has been a problem that the lithium ion conductivity becomes insufficient.

  The present invention has been made in view of the above circumstances, and has an electrode material with high electron conductivity and excellent lithium ion diffusibility, an electrode for a lithium ion secondary battery including this electrode material, and this It aims at providing the lithium ion secondary battery provided with the electrode for lithium ion secondary batteries.

As a result of intensive studies to solve the above-mentioned problems, the present inventors have made the electrode active material have a melting point of 25 ° C. or higher and carry a soluble organic compound in the electrolyte for a lithium ion secondary battery. Thus, an electrode material having high electron conductivity can be obtained, and the electrode for a lithium ion secondary battery including the electrode material is excellent in lithium ion diffusibility. When the electrode material is used as a battery, the input / output of the battery The inventors have found that characteristics, charge / discharge cycle characteristics, and low temperature characteristics are improved, and have completed the present invention.
The present invention has been completed based on such findings.

That is, the present invention provides the following [1] to [8].
[1] An electrode material in which an electrode active material has a melting point of 25 ° C. or higher and a soluble organic compound supported on an electrolyte for a lithium ion secondary battery, and has a green density of 2 when 51 MPa is applied. An electrode material for a lithium ion secondary battery, wherein the electrode material is ³ g / cm ³ or less.
[2] The electrode active material has the general formula _Li a _A b _D c PO compound represented by ₄ (provided that at least one A is selected from the group consisting of Fe, Mn, Co and Ni, D is Mg, At least one selected from the group consisting of Ca, Sr, Ba, Ti, Zn, B, Al, Ga, In, Si, Ge, Sc, Y and rare earth elements, 0 ≦ a ≦ 1.0, 0 <b ≦ 1.0, 0 ≦ c ≦ 0.4). The electrode material for a lithium ion secondary battery as described in [1] above.
[3] The electrode active material has the general formula _Li a _A b _D c PO compound represented by ₄ (provided that at least one A is selected from the group consisting of Fe, Mn, Co and Ni, D is Mg, At least one selected from the group consisting of Ca, Sr, Ba, Ti, Zn, B, Al, Ga, In, Si, Ge, Sc, Y and rare earth elements, 0 ≦ a ≦ 1.0, 0 <b ≦ a 1.0, 0 ≦ c ≦ 0.4), the general formula _Li a _a b _D c general formula _Li e _C f PO compound represented by the ₄ present on the surface of the compound represented by PO ₄ (provided that, C is at least one selected from Fe and Mn, 0 ≦ e <2, 0 <f <1.5, and a compound different from the compound represented by the general formula Li _{a Ab} D _c PO _4. ) Lithium as described in [1] above, which contains Ion secondary battery electrode material.
[4] The electrode material for a lithium ion secondary battery according to any one of [1] to [3], wherein the electrode active material is coated with a carbonaceous film.
[5] The lithium ion secondary battery according to any one of [1] to [4], wherein the organic compound is a kind of an organic compound constituting an electrolyte for a lithium ion secondary battery. Electrode material.
[6] The lithium according to [4] or [5] above, comprising an aggregate formed by aggregating the electrode active material coated with the carbonaceous film, and the aggregate is granulated. Electrode material for ion secondary battery.
[7] An electrode for a lithium ion secondary battery comprising an electrode current collector and an electrode mixture layer formed on the electrode current collector, wherein the electrode mixture layer is the above-mentioned [6] The electrode for lithium ion secondary batteries characterized by including the electrode material for lithium ion secondary batteries as described in above.
[8] A lithium ion secondary battery comprising the electrode for a lithium ion secondary battery as described in [7] above.

  According to the present invention, an electrode material having high electron conductivity and excellent lithium ion diffusibility, an electrode for a lithium ion secondary battery containing the electrode material, and an electrode for the lithium ion secondary battery are provided. A lithium ion secondary battery can be provided.

Embodiments of an electrode material for a lithium ion secondary battery, an electrode for a lithium ion secondary battery, and a lithium ion secondary battery of the present invention will be described.
Note that this embodiment is specifically described in order to better understand the gist of the invention, and does not limit the present invention unless otherwise specified.

[Electrode materials for lithium ion secondary batteries]
The electrode material for a lithium ion secondary battery of the present embodiment (hereinafter also simply referred to as an electrode material) is an electrode active material having a melting point of 25 ° C. or higher and a soluble organic compound in an electrolyte for a lithium ion secondary battery. It is an electrode material that is supported, and is characterized in that the green compact density when applying 51 MPa is 2.3 g / cm ³ or less.
According to the electrode material for a lithium ion secondary battery of the present embodiment, when pressing force is applied to the electrode current collector coated with the electrode material mixture layer to improve the conductivity of the electrode, an excessive pressing pressure is applied. Even when applied, the organic compound is contained in the electrode material aggregated particles, so that plastic deformation of the electrode material aggregated particles is suppressed, and the conduction path of lithium ions is maintained without collapsing the voids present in the electrode material aggregated particles. It is. Therefore, both the characteristics of electron conductivity and lithium ion diffusibility can be improved at the same time. In addition, since the organic compound dissolves in the electrolyte for lithium ion secondary batteries after the battery is fabricated, the lithium ion conduction path in the electrode is further maintained, so that both the electronic conductivity and the lithium ion diffusivity are maintained. The characteristics can be further improved.

(Electrode active material)
The electrode active material used in this embodiment is a compound represented by the general formula Li _{a Ab} D _c PO ₄ (where A is at least one selected from the group consisting of Fe, Mn, Co and Ni, and D is At least one selected from the group consisting of Mg, Ca, Sr, Ba, Ti, Zn, B, Al, Ga, In, Si, Ge, Sc, Y and rare earth elements, 0 ≦ a ≦ 1.0, 0 <B ≦ 1.0, 0 ≦ c ≦ 0.4) is preferable from the viewpoint of high discharge capacity and high energy density.

Here, about A, Fe, Mn, and Co are preferable, and Fe is more preferable.
Regarding D, Mg, Ca, Sr, Ba, Ti, Zn, and Al are preferable, and Mg is more preferable. When the electrode active material particles contain these elements, a positive electrode mixture layer capable of realizing a high discharge potential and high safety can be obtained. Moreover, since the amount of resources is abundant, it is preferable as a material to be selected.
The rare earth elements are 15 elements of La, Ce, Pr, Nd, Pm, Sm, Eu, Gd, Tb, Dy, Ho, Er, Tm, Yb, and Lu which are lanthanum series.

Examples of the compound represented by the general formula Li _{a Ab} D _c PO ₄ (hereinafter sometimes referred to as “compound A”) include LiFePO ₄ , LiMnPO ₄ , LiCoPO ₄ , LiNiPO ₄ , and LiFe _0.5. Mn _0.5 PO ₄ , LiFe _0.4 Mn _0.6 PO ₄ , LiFe _0.3 Mn _0.7 PO ₄ , LiFe _0.2 Mn _0.8 PO ₄ , LiFe _0.1 Mn _0.9 PO ₄ LiFe _0.265 Co _0.005 Mg _0.03 Mn _0.7 PO _{4 and the} like.

Further, the electrode active material, the general formula _Li a _A b _D and c PO compound represented by _4, the general formula _Li a _A b _D formula present at the surface of the compound represented by c PO _{4 Li} e C Compound represented by _f PO ₄ (wherein C is at least one selected from Fe and Mn, 0 ≦ e <2, 0 <f <1.5, represented by the general formula Li _{a Ab} D _c PO ₄ It is preferable to contain a compound different from the compound to be obtained.

Examples of the compound represented by the general formula Li _e C _f PO ₄ (hereinafter sometimes referred to as “compound B”) include, for example, LiFePO ₄ , Li ₂ FePO ₄ , LiMnPO ₄ , Li ₂ MnPO ₄ , and LiFe _{0. .5} Mn _0.5 PO ₄ , LiFe _0.4 Mn _0.6 PO ₄ , LiFe _0.3 Mn _0.7 PO ₄ , LiFe _0.2 Mn _0.8 PO ₄ , LiFe _0.1 Mn _0.9 PO ₄ , Li ₂ Fe _0.5 Mn _0.5 PO ₄ , Li ₂ Fe _0.4 Mn _0.6 PO ₄ , Li ₂ Fe _0.3 Mn _0.7 PO ₄ , Li ₂ Fe _0.2 Mn _{0 .8} PO ₄ , Li ₂ Fe _0.1 Mn _0.9 PO _{4 and the} like. However, Compound B is a compound different from Compound A.

When the electrode active material includes compound A and compound B existing on the surface of compound A, for example, compound A is a carbonaceous film on the surface of an electrode active material such as LiMnPO ₄ , LiCoPO ₄ , LiNiPO _4. Even in a material that is difficult to form, a compound B can form a carbonaceous film on the surface of the electrode active material. That is, when the electrode active material includes Compound A and Compound B, the carbonaceous film is formed on the surface of Compound A, the surface of Compound B, or the surfaces of Compound A and Compound B.

  When the electrode active material includes Compound A and Compound B, the ratio of Compound A to Compound B is preferably 99.9: 0.1 to 90.0: 10.0 in terms of molar ratio. It is more preferable that it is 5: 0.5-95.0: 5.0.

  The size of the electrode active material is not particularly limited, but the average primary particle size is preferably 0.01 μm or more and 5 μm or less, and more preferably 0.04 μm or more and 3 μm or less. When the average primary particle diameter is within the above range, the surface of the electrode active material crystal grains can be easily uniformly coated with a carbonaceous film, and the discharge capacity can be substantially increased in high-speed charge / discharge, and sufficient charge / discharge performance Can be realized. If the average primary particle diameter is less than 0.01 μm, it is difficult to uniformly coat the surface of the electrode active material crystal grains with a carbonaceous film, and the electrode active material was not uniformly coated with carbon during high-speed charge / discharge. Reaction resistance related to lithium insertion / extraction from the crystal grain surface region is increased. In particular, when charging / discharging is performed at high speed, the battery voltage reaches the upper and lower limit voltage during charging / discharging before lithium insertion / extraction in a region with high reaction resistance is completed. As a result, the discharge capacity is substantially reduced, making it difficult to achieve sufficient charge / discharge performance. On the other hand, when the average primary particle diameter exceeds 5 μm, the lithium diffusion resistance in the electrode active material crystal grains becomes so large that it becomes a rate-limiting factor for the charge / discharge reaction. In particular, when charging / discharging is performed at high speed, the battery voltage reaches the upper and lower limit voltage during charging / discharging before lithium insertion / extraction in a region with high reaction resistance is completed. As a result, the discharge capacity is substantially reduced, making it difficult to achieve sufficient charge / discharge performance.

  Here, the average particle diameter is a volume average particle diameter. The average primary particle diameter of the primary particles of the electrode active material of the present embodiment is determined by a scanning electron microscope (SEM) image, and the average value of the major axis diameters of 100 primary particles is defined as the average primary particle diameter. did.

  The crystal grain means a particle composed of a single crystallite, that is, a single crystal particle. When most of the electrode active material or the electrode material is composed of an aggregate of single crystal particles, the crystal grains are equal to the primary particles, and the crystallite diameter is equal to the primary particle diameter.

  The crystallite diameter can be calculated from the result of X-ray diffraction measurement (X-ray Diffraction: XRD) using the Rietveld method (Rietveld method) or Scherrer's equation. However, for particles with a crystallite diameter exceeding 0.2 μm, the calculation accuracy of the crystallite diameter based on the X-ray diffraction measurement results is low, so for convenience, the average primary particle diameter and the crystallite diameter based on the scanning electron microscope image Are assumed to be equal.

(Method for producing electrode active material or electrode active material precursor)
As the method for manufacturing a precursor of the electrode active material or the electrode active material used in the present embodiment, for example, the general formula _Li a _A b _D c PO compound represented by ₄ (where, A is Fe, Mn, Co and Ni D is selected from the group consisting of Mg, Ca, Sr, Ba, Ti, Zn, B, Al, Ga, In, Si, Ge, Sc, Y and rare earth elements. A method for producing an electrode active material comprising at least one kind, 0 ≦ a ≦ 1.0, 0 <b ≦ 1.0, 0 ≦ c ≦ 0.4), or a precursor thereof, and a general formula Li _a A _b D _c A compound represented by PO ₄ (compound A) and a compound represented by the general formula Li _e C _f PO ₄ existing on the surface thereof (where C is at least one selected from Fe and Mn, 0 ≦ e <2 , 0 <f <1.5) (Compound B ), And a method for producing a precursor thereof.

  As a precursor of the electrode active material, it becomes an electrode active material comprising Compound A or an electrode active material comprising Compound A and Compound B in the final step in the method for producing an electrode material for a lithium ion secondary battery described later. If it is a thing, it will not specifically limit.

As a method for producing Compound A, conventional methods such as a solid phase method, a liquid phase method, and a gas phase method are used.
Specifically, the method for producing compound A includes a step of hydrothermally synthesizing a slurry-like mixture prepared by mixing a Li source, an Fe source, a P source, and water using a pressure-resistant sealed container. And a step of washing the obtained precipitate with water to obtain a compound. Thereby, an electrode active material or its precursor is obtained.

Examples of the Li source include lithium salts such as lithium acetate (LiCH ₃ COO) and lithium chloride (LiCl), lithium hydroxide (LiOH), and the like.
Examples of the Fe source include divalent compounds such as iron (II) chloride (FeCl ₂ ), iron (II) acetate (Fe (CH ₃ COO) ₂ ), and iron (II) sulfate (FeSO ₄ ). .
Examples of the P source include phosphoric acid (H ₃ PO ₄ ), ammonium dihydrogen phosphate (NH ₄ H ₂ PO ₄ ), diammonium hydrogen phosphate ((NH ₄ ) ₂ HPO ₄ ), and the like.

Compound A obtained by the above production method may be crystalline particles or amorphous particles, or may be mixed crystal particles in which crystalline particles and amorphous particles coexist.
Here, the reason why the compound A may be amorphous particles is that the amorphous compound A is, for example, in a non-oxidizing atmosphere of 500 ° C. or more and 1000 ° C. or less when an electrode material described later is manufactured. This is because it heats and crystallizes.

When the electrode active material contains compound A and compound B, conventional methods such as a solid phase method, a liquid phase method, and a gas phase method are used as a method for producing compound B.
Specifically, the compound B is produced by mixing a slurry mixture prepared by mixing a Li source, an Fe source, a P source, and water with a compound A and drying it. A step of firing the powder. Thereby, the electrode active material or its precursor containing the compound A and the compound B which exists on the surface is obtained.

Examples of the Li source include lithium salts such as lithium acetate (LiCH ₃ COO) and lithium chloride (LiCl), lithium hydroxide (LiOH), and the like.
Examples of the Fe source include divalent compounds such as iron (II) chloride (FeCl ₂ ), iron (II) acetate (Fe (CH ₃ COO) ₂ ), and iron (II) sulfate (FeSO ₄ ). .
Examples of the P source include phosphoric acid (H ₃ PO ₄ ), ammonium dihydrogen phosphate (NH ₄ H ₂ PO ₄ ), diammonium hydrogen phosphate ((NH ₄ ) ₂ HPO ₄ ), and the like.

Compound B obtained by the above production method may be crystalline particles or amorphous particles, or may be mixed crystal particles in which crystalline particles and amorphous particles coexist.
Here, the reason why the compound B may be amorphous particles is that the amorphous compound B is, for example, in a non-oxidizing atmosphere of 500 ° C. or more and 1000 ° C. or less when an electrode material described later is manufactured. This is because it heats and crystallizes.

Moreover, when an electrode active material contains the compound A and the compound B which exists on the surface, an electrode active material is manufactured as follows.
In the particle size distribution of Compound A or Compound A precursor and Compound B or Compound B precursor, and the particle size distribution of Compound A or Compound A precursor, the ratio of D90 to D10 of this particle size distribution (D90 / D10) Is a slurry mixture in which the ratio of D90 to D10 (D90 / D10) of the particle size distribution is 7 or more and 25 or less in the particle size distribution of the compound B or the precursor of the compound B. By firing, an electrode active material is obtained. Further, in a slurry mixture containing Compound A and Compound B, the ratio of D90 to D10 in the particle size distribution of Compound A and Compound B (D90 / D10) may be adjusted to 5 or more and 30 or less.
In addition, D10 is a particle diameter in which the cumulative volume percentage in the volume particle size distribution of the electrode active material is 10% by volume, and D90 is a particle diameter in which the cumulative volume percentage in the volume particle size distribution of the electrode active material is 90% by volume.

  The shape of the electrode active material produced as described above is not particularly limited, but is selected from the group consisting of a spherical shape, a substantially spherical shape, a bowl shape, a rice grain shape, a cylindrical shape, a substantially cylindrical shape, a rectangular parallelepiped shape, and a substantially rectangular parallelepiped shape. It is preferably at least one kind, more preferably spherical, and particularly preferably spherical. If the shape of the electrode active material is a true sphere, an electrode material in which the electrode active material forms secondary particles easily forms spherical secondary particles.

Here, the reason why the shape of the electrode active material is preferably spherical is that the amount of solvent when preparing an electrode material mixture by mixing an electrode material, a binder resin (binder), and a solvent is reduced. This is because the electrode material mixture can be easily applied to the electrode current collector.
Further, when the shape of the electrode active material is spherical, the surface area of the electrode active material is minimized, and the amount of binder resin (binder) added to the electrode material mixture can be minimized. As a result, the internal resistance of the obtained electrode can be reduced.
Furthermore, when the electrode active material is spherical, it becomes easy to close-pack the electrode material when the electrode material mixture is applied to the electrode current collector, so that the amount of the electrode material filled per unit volume increases. Therefore, the electrode density can be increased, and as a result, the capacity of the lithium ion secondary battery can be increased.

The electrode material for a lithium ion secondary battery according to the present embodiment includes crystal grains composed of the electrode active material (particles composed only of a compound represented by the general formula Li _{a Ab} D _c PO ₄ and / or the general formula Li _a A _b particles composed of a compound represented by D D _c PO ₄ and a compound represented by the general formula Li _e C _f PO ₄ ) or primary particles (particles composed only of a compound represented by the general formula Li _{a Ab} D _c PO ₄ ; and / or the general formula _Li a _a b becomes and _D c carrying carbon on the surface of the PO compounds of the general formula _Li e _C f PO particles comprising a compound represented by the ₄ represented by _4), and between the grains Alternatively, an electrode active material coated with a carbonaceous film having carbon interposed between primary particles is coated with an organic compound having a melting point of 25 ° C. or higher and soluble in an electrolyte for a lithium ion secondary battery. It is preferable formed by lifting.

  The size of the electrode active material coated with the carbonaceous film is not particularly limited, but the average primary particle diameter is preferably 0.05 μm or more and 10 μm or less, more preferably 0.06 μm or more and 3 μm or less. preferable. When the average primary particle diameter is within the above range, the surface of the electrode active material crystal grains can be easily uniformly coated with a carbonaceous film, and the discharge capacity can be substantially increased in high-speed charge / discharge, and sufficient charge / discharge performance is achieved. Can be realized. If the average primary particle diameter is less than 0.05 μm, it is difficult to uniformly coat the surface of the electrode active material crystal grains with a carbonaceous film, and the electrode is not uniformly coated with carbon during high-speed charge / discharge. The reaction resistance related to lithium insertion / extraction in the active material crystal grain surface region is increased. In particular, when charging / discharging is performed at high speed, the battery voltage reaches the upper and lower limit voltage during charging / discharging before lithium insertion / extraction in a region with high reaction resistance is completed. As a result, the discharge capacity is substantially reduced, making it difficult to achieve sufficient charge / discharge performance. On the other hand, when the average primary particle diameter exceeds 10 μm, the lithium diffusion resistance in the electrode active material crystal grains becomes so large that it becomes a rate-limiting factor for the charge / discharge reaction. In particular, when charging / discharging is performed at high speed, the battery voltage reaches the upper and lower limit voltage during charging / discharging before lithium insertion / extraction in a region with high reaction resistance is completed. As a result, the discharge capacity is substantially reduced, making it difficult to achieve sufficient charge / discharge performance.

  Here, the average particle diameter is a volume average particle diameter. The average primary particle diameter of the electrode active material coated with the carbonaceous film of the present embodiment is determined by a scanning electron microscope image, as in the case of the electrode active material.

The shape of the electrode active material coated with the carbonaceous film is not particularly limited, but is selected from the group consisting of a spherical shape, a substantially spherical shape, a bowl shape, a rice grain shape, a cylindrical shape, a substantially cylindrical shape, a rectangular parallelepiped shape, and a substantially rectangular parallelepiped shape. It is preferable that there is at least one. That is, the shapes of the electrode active materials covered with the carbonaceous film may all be the same, or two or more types may be mixed.
Here, the shape of the electrode active material coated with the carbonaceous film is at least one selected from the group consisting of a spherical shape, a substantially spherical shape, a bowl shape, a rice grain shape, a cylindrical shape, a substantially cylindrical shape, a rectangular parallelepiped shape, and a substantially rectangular parallelepiped shape. The reason why it is preferable to be a seed is that when an electrode active material coated with a carbonaceous film, a binder resin (binder), and a conductive additive are mixed to form an electrode for a lithium ion secondary battery. This is because it is easy to adjust the electrode density.

  In addition, when preparing an electrode material composed of substantially spherical secondary particles by collecting primary particles of an electrode active material coated with a plurality of carbonaceous films, the shape of the electrode active material coated with the carbonaceous film is changed. The reason why it is preferable to use at least one selected from the group consisting of a spherical shape, a substantially spherical shape, a bowl shape, a rice grain shape, a cylindrical shape, a substantially cylindrical shape, a rectangular parallelepiped shape, and a substantially rectangular parallelepiped shape is that the filling property of secondary particles is high. Because it is possible to do. Moreover, the amount of solvent when preparing an electrode material mixture by mixing an electrode material, a binder resin (binder), a conductive additive, and a solvent can be reduced. In addition, the electrode material mixture can be easily applied to the electrode current collector.

  The average particle diameter (average secondary particle diameter) of the secondary particles of the electrode active material coated with the carbonaceous film is preferably 0.3 μm or more and 60 μm or less, and is 0.5 μm or more and 50 μm or less. Is more preferably 1 μm or more and 30 μm or less. When the average secondary particle diameter is 0.3 μm or more, sufficient adhesion strength between the electrode current collector and the electrode active material coated with the carbonaceous film can be obtained, and the amount of the binder resin is excessive. Can prevent and increase battery capacity. In addition, when the average secondary particle diameter is 60 μm or less, it is possible to make it difficult for a coarse and dense distribution of the electrode material to occur in the electrode when the electrode for a lithium ion secondary battery is formed. Thereby, it can prevent that a difference arises in the degradation rate of an electrode material in the microscopic area | region of an electrode.

  Here, the average secondary particle diameter of the electrode active material coated with the carbonaceous film means the number average particle diameter of the secondary particles of the electrode active material coated with the carbonaceous film. The average secondary particle diameter of the electrode active material coated with the carbonaceous film can be measured using a laser diffraction scattering type particle size distribution measuring device or the like.

The organic compound supported on the electrode active material (hereinafter sometimes referred to as “organic compound I”) has a melting point of 25 ° C. or higher and is soluble in an electrolyte for a lithium ion secondary battery. Although it is not limited, it is preferable that it is 1 type of the organic compound which comprises the electrolyte solution for lithium ion secondary batteries, for example, ethylene carbonate, a sulfolane, a sulfolane derivative, ethyl methyl sulfone etc. are mentioned. Among these, ethylene carbonate is preferably used.
Here, the “electrolyte for a lithium ion secondary battery” refers to an electrolyte having lithium ion conductivity. As an electrolyte for a lithium ion secondary battery, for example, ethylene carbonate (ethylene carbonate; EC) and ethyl methyl carbonate (ethyl methyl carbonate; EMC) are mixed so that the volume ratio is 0 to 1: 1. In the obtained mixed solvent, lithium hexafluorophosphate (LiPF ₆ ), for example, a non-aqueous electrolyte or ethylene carbonate (ethylene carbonate; EC) dissolved in a concentration of 1 mol / dm ³ and diethyl carbonate (Diethyl carbonate; DEC) is mixed at a volume ratio of 0 to 1: 1, and lithium hexafluorophosphate (LiPF ₆ ) is added to the obtained mixed solvent, for example, at a concentration of 1 to 1.5. Examples thereof include a non-aqueous electrolyte dissolved so as to be mol / dm ³ .

  When the organic compound I is soluble in the electrolytic solution for a lithium ion secondary battery, when the battery containing the electrode material of this embodiment is immersed in the electrolytic solution to produce a battery, the organic compound in the electrode material I dissolves in the electrolyte. As a result, a space serving as a lithium ion conduction path is formed at the location where the organic compound I of the electrode material is present, and both the characteristics of electron conductivity and lithium ion diffusivity can be improved at the same time.

  In the electrode material of the present embodiment, the content of the organic compound I is preferably 5% by mass or more and 90% by mass or less, preferably 10% by mass or more and 85% by mass or less, based on the weight of the electrode active material described above. More preferably, it is more preferably 20% by mass or more and 80% by mass or less, further preferably 35% by mass or more and 70% by mass or less, and more preferably 40% by mass or more and 65% by mass or less. It is even more preferable. By making content of the organic compound I into the said range, the lithium ion conductivity of a lithium ion secondary battery can be improved. If the content of the organic compound I exceeds 85% by mass, the organic compound I cannot be completely dissolved in the amount of the electrolyte used in the lithium ion secondary battery, so that it is supported on the electrode material when assembled as a battery. The organic compound I is not completely dissolved in the electrolytic solution, and the organic compound I that remains undissolved when driving as a lithium ion secondary battery blocks the lithium ion conduction path, thereby inhibiting the lithium ion conductivity and increasing the internal resistance of the battery. This is not preferable because there is a possibility. Further, when the content of the organic compound I is less than 10% by mass, the plastic deformation of the electrode material aggregated particles is remarkable when the press mixture is applied to improve the conductivity of the electrode mixture layer. When the voids are crushed, the lithium ion conduction path is reduced, and the lithium ion secondary battery for a high power supply requiring high-speed charge / discharge characteristics is not preferable because the lithium ion conductivity becomes insufficient.

The electrode material of the present embodiment is preferably formed by supporting the organic compound I on an aggregate formed by aggregating an electrode active material coated with a carbonaceous film (carbon-coated electrode active material aggregate). The volume density of the carbon-coated electrode active material aggregate carrying the organic compound I (hereinafter also simply referred to as an aggregate) is the volume density when the aggregate carrying the organic compound I is assumed to be solid. It is preferable that it is 60 volume% or more and 95 volume% or less.
Here, the aggregate formed by supporting the solid organic compound I is an aggregate having no voids, and the density of the aggregate formed by supporting the solid organic compound I is the electrode material. It is assumed to be equal to the theoretical density of.

  In addition, the aggregate formed by aggregating the electrode active material coated with the carbonaceous film means that the electrode active materials coated with the carbonaceous film are aggregated in a point contact state, and a contact portion between the electrode active materials. Is an agglomerate in the form of a neck having a small cross-sectional area and firmly connected. As described above, the contact portion between the electrode active materials has a cervical shape with a small cross-sectional area, so that a channel-like (network-like) void is three-dimensionally expanded in the aggregate.

In addition, when the volume density of the aggregate is 60% by volume or more of the volume density assuming that the aggregate formed by supporting the organic compound I is solid, the aggregate formed by supporting the organic compound I By densifying, the strength of the aggregate formed by supporting the organic compound I increases. For example, when an electrode material mixture is prepared by mixing an electrode material, a binder resin (binder), a conductive additive, and a solvent, an aggregate formed by supporting the organic compound I is unlikely to collapse. As a result, an increase in the viscosity of the electrode material mixture is suppressed and fluidity is maintained. Thereby, while being able to improve the applicability | paintability of an electrode material mixture, the improvement of the filling property of the electrode active material in the coating film which consists of an electrode material mixture can also be aimed at. When the aggregate formed by supporting the organic compound I collapses when preparing the electrode material mixture, the blending amount of the binder resin for binding the electrode active materials increases. Therefore, the viscosity of the electrode material mixture increases, the solid content concentration in the electrode material mixture decreases, and the ratio of the electrode material to the electrode film formed using the electrode material mixture decreases.
In addition, when the volume density of the aggregate is 95% by volume or less of the volume density when the aggregate formed by supporting the organic compound I is assumed to be solid, the organic compound I is lithium when the battery is manufactured. Dissolving in an ion secondary battery electrolyte is preferable because a lithium ion conduction path is formed in the aggregate to a degree sufficient to drive the battery.

  The electrode material of this embodiment, when used as an electrode material of a lithium ion secondary battery, is a compound that constitutes at least an electrode active material in order to uniformly carry out a reaction related to the de-insertion of Li ions over the entire surface of the electrode material It is preferable that 80% or more of the surface of A is coated with a carbonaceous film, and it is more preferable that at least 90% of the surface of the compound A constituting the electrode active material is coated with a carbonaceous film. When the coverage of the carbonaceous film on the surface of the compound A constituting the electrode active material is 80% or more, the coating effect of the carbonaceous film is sufficiently obtained. On the other hand, when the coverage of the carbonaceous film is less than 80%, when the deionization reaction of Li ions is performed on the surface of the electrode material, it is involved in the deionization of Li ions at a location where the carbonaceous film is not formed. Increases reaction resistance.

  When the electrode active material of this embodiment contains the compound A and the compound B which exists on the surface, the surface of the compound A and the surface of the compound B may be coat | covered with the carbonaceous film. In this case, at least 80% or more of the surface of the compound A constituting the electrode active material is preferably coated with a carbonaceous film, and at least 90% or more of the surface of the compound A constituting the electrode active material is covered with the carbonaceous film. More preferably, it is coated with. Further, it is preferable that 50% or more of the surface of the compound B constituting the electrode active material is coated with a carbonaceous film, and 70% or more of the surface of the compound B constituting the electrode active material is coated with a carbonaceous film. More preferably.

  In addition, the coverage of the carbonaceous film on the surface of the electrode material of the present embodiment is determined by using a transmission electron microscope (Transmission Electron Microscope, TEM), an energy dispersive X-ray analyzer (Energy Dispersive X-ray microanalyzer, EDX), or the like. Can be measured.

In the electrode material of the present embodiment, the carbon amount in the carbonaceous film is 0.6% by mass or more and 3.5% by mass with respect to the mass percentage of the electrode active material (when the total amount of the carbonaceous film is 100% by mass). % Is preferably 0.8% by mass or more and 2.5% by mass or less, more preferably 1.1% by mass or more and 1.7% by mass or less.
If the amount of carbon is 0.6% by mass or more, the coverage of the carbonaceous film on the surface of the electrode material exceeds 80%. Therefore, when a lithium ion secondary battery is formed, the discharge capacity at a high-speed charge / discharge rate is high. Become. As a result, the lithium ion secondary battery can achieve sufficient charge / discharge rate performance. On the other hand, when the carbon content is 3.5% by mass or less, the charge transfer resistance due to steric hindrance does not increase when Li ions diffuse in the carbonaceous film. As a result, the internal resistance of the lithium ion secondary battery does not increase, and the voltage drop at the high-speed charge / discharge rate of the lithium ion secondary battery does not occur.

The average thickness of the carbonaceous film in the electrode material is preferably 1.0 nm or more and 7.0 nm or less, and more preferably 3.0 nm or more and 5.0 nm or less.
Here, the reason why the average value of the thickness of the carbonaceous film is limited to the above range is that if the average value of the thickness of the carbonaceous film is 1.0 nm or more, the charge transfer resistance in the carbonaceous film is high. Never become. As a result, the internal resistance of the lithium ion secondary battery does not increase, and the voltage drop at the high-speed charge / discharge rate of the lithium ion secondary battery does not occur. On the other hand, if the average thickness of the carbonaceous film is 7.0 nm or less, the charge transfer resistance due to steric hindrance does not increase when Li ions diffuse in the carbonaceous film. As a result, the internal resistance of the lithium ion secondary battery does not increase, and the voltage drop at the high-speed charge / discharge rate of the lithium ion secondary battery does not occur.

The specific surface area of the electrode material is preferably 5 m ² / g or more and 20 m ² / g or less, and more preferably 9 m ² / g or more and 13 m ² / g or less.
If the specific surface area is 5 m ² / g or more, the average value of the thickness of the carbonaceous film is 7.0 nm or less when the carbon content in the carbonaceous film is 2.0 mass%. On the other hand, if the specific surface area is 20 m ² / g or less, the carbon content in the carbonaceous film is 0.6% by mass or more, and the average thickness of the carbonaceous film is 1.0 nm or more.

The density of the carbonaceous film, calculated by the carbon content constituting the carbonaceous film, is preferably 0.3 g / cm ³ or more and 1.5 g / cm ³ or less, 0.4 g / cm ³ or more and 1. More preferably, it is 0 g / cm ³ or less. The density of the carbonaceous film calculated by the carbon content constituting the carbonaceous film is the mass per unit volume of the carbonaceous film, assuming that the carbonaceous film is composed of only carbon.
When the density of the carbonaceous film is 0.3 g / cm ³ or more, the carbonaceous film exhibits sufficient electron conductivity. On the other hand, if the density of the carbonaceous film is 1.5 g / cm ³ or less, the content of microcrystals of graphite having a layered structure in the carbonaceous film is small, so when Li ions diffuse in the carbonaceous film. No steric hindrance due to graphite microcrystals. Thereby, the charge transfer resistance is not increased. As a result, the internal resistance of the lithium ion secondary battery does not increase, and the voltage drop at the high-speed charge / discharge rate of the lithium ion secondary battery does not occur.

The mass of carbon constituting the carbonaceous film is preferably 50% by mass or more and more preferably 60% by mass or more of the entire mass (100% by mass) of the carbonaceous film.
The carbonaceous film is generated by thermal decomposition of a carbonaceous source that is a precursor of carbon, and contains elements such as hydrogen and oxygen in addition to carbon. When the firing temperature at the time of producing the electrode material is 500 ° C. or less, the mass of carbon in the entire mass of the carbonaceous film is less than 50% by mass, and the charge transfer resistance of the carbonaceous film is increased. As a result, the internal resistance of the lithium ion secondary battery increases, and the voltage drop at the high speed charge / discharge rate becomes significant.

  The electrode material for a lithium ion secondary battery according to the present embodiment supports the organic compound I on an aggregate (carbon-coated electrode active material aggregate) formed by aggregating the electrode active material coated with the carbonaceous film described above. By becoming, it becomes easy to hold | maintain the coupling | bonding of the electrode active materials through a carbonaceous film even after pressing an electrode, Therefore It is excellent in electronic conductivity. Moreover, it is excellent in the diffusibility of Li ion inside an electrode material.

(Method for producing electrode material for lithium ion secondary battery)
As a manufacturing method of the electrode material for lithium ion secondary batteries of this embodiment, the electrode active material or the precursor of an electrode active material obtained by the manufacturing method of the above-mentioned electrode active material or the precursor of an electrode active material, for example And a step of preparing a slurry containing a carbonaceous film precursor [carbonaceous source (hereinafter also referred to as organic compound II)] (hereinafter referred to as “slurry preparation step”), and spraying and drying the slurry. A step of producing a granulated body (hereinafter referred to as a “granulated body producing step”) and a step of heat-treating the granulated body in a non-oxidizing atmosphere of 500 ° C. or more and 1000 ° C. or less. (Hereinafter referred to as “heat treatment step”) and a step of supporting the organic compound I on the carbon-coated electrode active material aggregate obtained in the above step (hereinafter referred to as “organic compound I supporting step”).
Hereinafter, the manufacturing method of the electrode material of this embodiment is demonstrated in detail.

(Slurry preparation process)
In the slurry preparation step, the above-described compound A, or compound A and compound B, and organic compound II are dissolved or dispersed in water to prepare a uniform slurry.
In the slurry preparation step, it is preferable to add a dispersant when dissolving or dispersing Compound A, Compound A and Compound B, and Organic Compound II in water.

  As a method of dissolving or dispersing Compound A, Compound A and Compound B, and Organic Compound II in water in the slurry preparation step, Compound A, Compound A and Compound B are dispersed in water, and Organic Compound If II is the method of melt | dissolving or disperse | distributing in water, it will not specifically limit. As such a method, for example, a method using a medium stirring type dispersion device that stirs medium particles at high speed, such as a planetary ball mill, a vibration ball mill, a bead mill, a paint shaker, or an attritor, is preferably used.

  In the slurry preparation step, when compound A, compound A and compound B, and organic compound II are dissolved or dispersed in water, primary particles of compound A or compound A and compound B are dispersed in water. Thereafter, it is preferable to dissolve the organic compound II in the water containing the compound A or the compound A and the compound B. In this way, the primary particles of Compound A or the surfaces of the primary particles of Compound A and Compound B are coated with organic compound II. As a result, the primary particles of Compound A or the primary particles of Compound A and Compound B are coated. In the meantime, carbon derived from the organic compound II is uniformly interposed.

  Further, in the slurry preparation step, in the particle size distribution of Compound A or Compound A and Compound B in the slurry, the ratio of D90 to D10 of the particle size distribution (D90 / D10) is 5 or more and 30 or less. It is preferable to appropriately adjust the dispersion conditions, for example, the concentration of Compound A in the slurry, or the concentration of Compound A and Compound B, the concentration of the organic compound in the slurry, the stirring time of the slurry, and the like.

  Examples of the organic compound II that is a carbonaceous source include polyvinyl alcohol, polyvinyl pyrrolidone, cellulose, starch, gelatin, carboxymethyl cellulose, methyl cellulose, hydroxymethyl cellulose, hydroxyethyl cellulose, polyacrylic acid, polystyrene sulfonic acid, polyacrylamide, and polyvinyl acetate. Glucose, fructose, galactose, mannose, maltose, sucrose, lactose, glycogen, pectin, alginic acid, glucomannan, chitin, hyaluronic acid, chondroitin, agarose, polyether, polyhydric alcohols and the like.

In the electrode material of the present embodiment, when the electrode active material contains only compound A, the compounding ratio of compound A and organic compound II is based on 100 parts by mass of compound A when the total amount of organic compound II is converted to carbon content. It is preferably 0.6 parts by mass or more and 3.5 parts by mass or less, more preferably 1.1 parts by mass or more and 1.7 parts by mass or less.
Moreover, in the electrode material of this embodiment, when an electrode active material contains the compound A and the compound B, the compounding ratio of the compound A and the compound B and the organic compound II converted the total amount of the organic compound II into the carbon amount. When the total amount of Compound A and Compound B is 100 parts by mass, it is preferably 0.6 parts by mass or more and 3.5 parts by mass or less, and 1.1 parts by mass or more and 1.7 parts by mass or less. Is more preferable.

  In the electrode material of the present embodiment, if the compounding ratio in which the total amount of the organic compound II is converted to the carbon amount is 0.6 parts by mass or more, the coverage of the carbonaceous film formed on the surface of the electrode active material is 80%. Therefore, when a lithium ion secondary battery is formed, the discharge capacity at a high speed charge / discharge rate is increased. As a result, sufficient charge / discharge rate performance of the lithium ion secondary battery can be realized. On the other hand, if the compounding ratio in which the total amount of the organic compound II is converted to the carbon amount is 3.5 parts by mass or less, the average value of the thickness of the carbonaceous film in the electrode material is 7 nm or less, and Li ions are contained in the carbonaceous film. When diffusing, charge transfer resistance due to steric hindrance does not increase. As a result, the internal resistance of the lithium ion secondary battery does not increase, and the voltage drop at the high-speed charge / discharge rate of the lithium ion secondary battery does not occur.

(Granulated body production process)
In the granule preparation step, the slurry obtained in the slurry preparation step is sprayed in a high-temperature atmosphere, for example, in the atmosphere of 70 ° C. or more and 250 ° C. or less, and dried to produce a granule.

In the granule preparation process, conditions for drying the slurry, for example, slurry concentration, gas-liquid amount (amount of slurry and amount of gas used when spraying slurry), nozzle shape, drying temperature, etc. are adjusted as appropriate. By doing so, it is possible to control the particle size distribution of the primary particles contained in the obtained electrode material.
In addition, you may grind | pulverize the obtained granulated body before and after the heat processing process mentioned later. The method for pulverizing the granulated body is not particularly limited, but for example, a method using an airflow pulverizer is preferably used.

(Heat treatment process)
In the heat treatment step, a carbon-coated electrode active material aggregate is obtained by firing the granule obtained in the granule preparation step in a non-oxidizing atmosphere, preferably at 500 ° C. or more and 1000 ° C. or less. As a calcination temperature, 600 degreeC or more and 900 degrees C or less are more preferable. In the heat treatment step, it is preferable that the granule obtained in the granule preparation step is fired within the above temperature range for 0.1 hour or more and 40 hours or less.

  When the firing temperature is 500 ° C. or higher, the decomposition reaction of the organic compound II contained in the granule proceeds sufficiently, and the carbonization of the organic compound II becomes sufficient. As a result, a high-resistance organic substance decomposition product is not generated in the obtained carbon-coated electrode active material aggregate. On the other hand, if the firing temperature is 1000 ° C. or lower, the lithium in the compound A, or the compound A and the compound B will not evaporate. Grain growth is not promoted. As a result, the discharge capacity at the high speed charge / discharge rate is increased, and sufficient charge / discharge rate performance of the lithium ion secondary battery can be realized.

As the non-oxidizing atmosphere, an inert atmosphere such as nitrogen (N ₂ ) or argon (Ar), or a reducing gas containing a reducing gas such as hydrocarbon gas or hydrogen (H ₂ ) when further oxidation is to be suppressed. An atmosphere is preferably used. In addition, for the purpose of removing organic components evaporated in the non-oxidizing atmosphere at the time of firing, air, oxygen (O ₂ ), fluorine (F ₂ ), nitrogen monoxide (NO), carbon monoxide in an inert atmosphere. Combustible gas such as (CO), methane (CH ₄ ), acetylene (C ₂ H ₂ ) or combustible gas may be introduced.

  In the heat treatment step, it is included in the carbon-coated electrode active material aggregate obtained by appropriately adjusting the conditions for firing the granulated body, for example, the heating rate, the maximum holding temperature, the holding time of the maximum holding temperature, etc. It is possible to control the particle size distribution of the primary particles.

(Organic compound I supporting step)
In the organic compound I supporting step, the organic compound I is supported on the carbon-coated electrode active material aggregate obtained in the heat treatment step.
Examples of the organic compound I include the compounds listed above.
As a method for supporting the organic compound I, for example, a predetermined amount of the organic compound I powder is added to the carbon-coated electrode active material aggregate, and then heated to 25 ° C. or more to thereby add the organic compound I to the carbon-coated electrode active material aggregate. Or a carbon-coated electrode active material aggregate, an organic compound I, and a solvent in which the organic compound I is soluble are mixed and sufficiently stirred and mixed to dissolve the organic compound I in the solvent. After the solvent in which Compound I is dissolved is uniformly distributed in the carbon-coated electrode active material aggregate, the solvent is dried, and the organic compound I is contained inside the carbon-coated electrode active material aggregate, and the carbon-coated electrode active material A method of concentrating the organic compound I on the surface of the aggregate, a method of simply mixing the carbon-coated electrode active material aggregate and the organic compound I powder, or dissolving the organic compound I in the carbon-coated electrode active material aggregate Tena The solvent may be used a method of a predetermined amount sprayed, and the like.

  The compounding amount of the organic compound I is preferably 5% by mass or more and 90% by mass or less, more preferably 10% by mass or more and 85% by mass or less, and more preferably 20% by mass with respect to the above-mentioned electrode active material weight. % Or more and 80% by mass or less, more preferably 35% by mass or more and 70% by mass or less, and further preferably 40% by mass or more and 65% by mass or less. By setting the blending amount of the organic compound I within the above range, the lithium ion conductivity of the lithium ion secondary battery can be increased.

The green compact density, which is the pellet density when a pressure of 51 MPa is applied, of the electrode material of the present embodiment thus obtained is 2.3 g / cm ³ or less, preferably 2.2 g / cm ³ or less. More preferably, it can be 2.1 g / cm ³ or less. When the green compact density is 2.3 g / cm ³ or less, voids in the electrode material aggregated particles are not crushed when a press pressure is applied to the electrode material mixture layer. When the number of contact points of the conductive auxiliary agent becomes sufficient and a lithium ion secondary battery is formed, the discharge capacity at a high-speed charge / discharge rate increases. As a result, sufficient charge / discharge rate performance of the lithium ion secondary battery can be realized.
The green compact density can be measured using a powder resistance measurement system (for example, trade name: MCP-PD51 type, manufactured by Mitsubishi Chemical Analytech Co., Ltd.).

[Electrode for lithium ion secondary battery]
The electrode for a lithium ion secondary battery of the present embodiment (hereinafter sometimes simply referred to as “electrode”) includes the electrode material for the lithium ion secondary battery of the present embodiment. More specifically, the electrode of the present embodiment includes an electrode current collector made of a metal foil, and an electrode mixture layer formed on the electrode current collector. The electrode material for lithium ion secondary batteries is contained. That is, the electrode of this embodiment is formed by forming an electrode mixture layer on one main surface of the electrode current collector using the electrode material for a lithium ion secondary battery of this embodiment.

  Since the electrode for the lithium ion secondary battery of the present embodiment includes the electrode material for the lithium ion secondary battery of the present embodiment, the lithium ion secondary battery using the electrode for the lithium ion secondary battery of the present embodiment is Excellent input / output characteristics and charge / discharge rate performance at room temperature.

(Method for producing electrode for lithium ion secondary battery)
The manufacturing method of the electrode for lithium ion secondary batteries of this embodiment is a method which can form an electrode mixture layer on one main surface of an electrode current collector using the electrode material for lithium ion secondary batteries of this embodiment. If there is no particular limitation. As a manufacturing method of the electrode of this embodiment, the following method is mentioned, for example.
First, an electrode material mixture is prepared by mixing the electrode material for a lithium ion secondary battery of the present embodiment, a binder resin (binder), and a solvent. Under the present circumstances, you may add conductive support agents, such as carbon black, to the electrode material mixture in this embodiment as needed.

[Binder resin]
Binder resins, that is, binders include, for example, polyvinylidene fluoride (PVdF), polyethylene, polypropylene, polyethylene terephthalate, polymethyl methacrylate, vinyl acetate copolymer, styrene / butadiene latex, acrylic latex, acrylonitrile, Examples thereof include butadiene latex, fluorine latex, and silicon latex. These may use only 1 type and may mix and use 2 or more types.

  The content of the binder resin in the electrode material mixture is 2% by mass or more and 10% by mass when the total mass of the electrode material for the lithium ion secondary battery, the binder resin, and the conductive additive of this embodiment is 100% by mass. % Or less, more preferably 4% by mass or more and 8% by mass or less. When the content of the binder resin is 2% by mass or more, when the electrode mixture layer is formed using the electrode material mixture containing the electrode material for the lithium ion secondary battery in the present embodiment, the electrode mixture layer and The binding property of the electrode current collector becomes sufficient, and the electrode mixture layer does not crack or fall off during the rolling of the electrode mixture layer. In addition, the electrode mixture layer does not peel from the electrode current collector during the charge / discharge process of the battery, and the battery capacity and charge / discharge rate do not decrease. On the other hand, when the content of the binder resin is 10% by mass or less, the internal resistance of the electrode material does not increase, and the battery capacity at the high-speed charge / discharge rate of the lithium ion secondary battery does not decrease.

[Conductive aid]
Although it does not specifically limit as a conductive support agent, For example, fibers, such as particulate carbon of acetylene black (AB), ketjen black, furnace black, a vapor growth carbon fiber (VGCF; Vapor Growth Carbon Fiber), and a carbon nanotube And carbon. These may use only 1 type and may mix and use 2 or more types.

  The content of the conductive auxiliary in the electrode material mixture is 2% by mass or more and 10% by mass when the total mass of the electrode material for the lithium ion secondary battery, the binder and the conductive auxiliary of the present embodiment is 100% by mass. % Or less, more preferably 4% by mass or more and 8% by mass or less. If the content of the conductive auxiliary is 2% by mass or more, when the electrode mixture layer is formed using the electrode material mixture containing the electrode material for the lithium ion secondary battery in this embodiment, the electron conductivity is The battery capacity and the charge / discharge rate are improved. On the other hand, if the content of the conductive additive is 10% by mass or less, the electrode material occupied in the electrode mixture layer is relatively increased, and the battery capacity of the lithium ion secondary battery per unit volume is improved.

〔solvent〕
The solvent used for the electrode material mixture containing the electrode material for a lithium ion secondary battery of the present embodiment is appropriately selected according to the properties of the binder resin. By appropriately selecting the solvent, the electrode material mixture can be easily applied to an object to be coated such as an electrode current collector.
Examples of the solvent include water, methanol, ethanol, 1-propanol, 2-propanol (isopropyl alcohol: IPA), butanol, pentanol, hexanol, octanol, and diacetone alcohol; ethyl acetate, butyl acetate, lactic acid Esters such as ethyl, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate and γ-butyrolactone; diethyl ether, ethylene glycol monomethyl ether (methyl cellosolve), ethylene glycol monoethyl ether (ethyl cellosolve), ethylene glycol Monobutyl ether (butyl cellosolve), diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, etc. Ethers; Ketones such as acetone, methyl ethyl ketone (MEK), methyl isobutyl ketone (MIBK), acetylacetone and cyclohexanone; Amides such as dimethylformamide, N, N-dimethylacetoacetamide and N-methyl-2-pyrrolidone (NMP) And glycols such as ethylene glycol, diethylene glycol and propylene glycol. These solvents may be used alone or in a combination of two or more.

  The content of the solvent in the electrode material mixture is 50% by mass or more and 70% by mass when the total mass of the electrode material for the lithium ion secondary battery, the binder, and the solvent of this embodiment is 100% by mass. Or less, more preferably 55% by mass or more and 65% by mass or less. When the content of the solvent in the electrode material mixture is within the above range, an electrode material mixture having excellent electrode forming properties and excellent battery characteristics can be obtained.

  The method of mixing the electrode material for a lithium ion secondary battery, the binder resin, the conductive additive, and the solvent of the present embodiment is not particularly limited as long as these components can be mixed uniformly. Examples thereof include a mixing method using a kneading machine such as a ball mill, a sand mill, a planetary (planetary) mixer, a paint shaker, and a homogenizer.

The electrode material mixture is applied to one main surface of the electrode current collector to form a coating film, and then the coating film is dried, from the mixture of the lithium ion secondary battery electrode material and binder resin of the present embodiment. An electrode current collector having a coating film formed on one main surface is obtained.
Thereafter, the coating film is pressure-bonded and dried to obtain an electrode for a lithium ion secondary battery having an electrode current collector and an electrode mixture layer formed on one main surface thereof.

[Lithium ion secondary battery]
The lithium ion secondary battery of the present embodiment includes a positive electrode, a negative electrode, and a nonaqueous electrolyte (electrolytic solution), and the positive electrode is the electrode for the lithium ion secondary battery of the present embodiment. Specifically, the lithium ion secondary battery of this embodiment includes the lithium ion secondary battery electrode of this embodiment as a positive electrode, a negative electrode, a separator, and a nonaqueous electrolyte.
In the lithium ion secondary battery of this embodiment, the negative electrode, the nonaqueous electrolyte, and the separator are not particularly limited.

(Negative electrode)
As the negative electrode, for example, a metal Li, natural graphite, carbon materials such as hard carbon, include those containing an anode material such as Li alloys and _{Li 4 Ti 5 O 12, Si} (Li 4.4 Si).

(Nonaqueous electrolyte)
As the non-aqueous electrolyte, for example, ethylene carbonate (ethylene carbonate; EC) and ethyl methyl carbonate (ethyl methyl carbonate; EMC) are mixed so that the volume ratio is 0 to 1: 1, and the resulting mixture is obtained. lithium hexafluorophosphate (LiPF ₆₎ in a solvent, for example, those dissolved at a concentration of 1 mol / dm ^3.

(Separator)
As the separator, for example, porous propylene can be used. A solid electrolyte may be used instead of the nonaqueous electrolyte and the separator.

  Since the lithium ion secondary battery of the present embodiment includes the electrode for the lithium ion secondary battery of the present embodiment as the positive electrode, high-speed charge / discharge is possible.

EXAMPLES Next, although an Example demonstrates this invention concretely, this invention is not limited at all by these examples. For example, in this embodiment, metal Li is used as the negative electrode in order to reflect the behavior of the electrode material itself in the data. However, a negative electrode material such as a carbon material, a Li alloy, or Li ₄ Ti ₅ O ₁₂ may be used. . A solid electrolyte may be used instead of the electrolytic solution and the separator.

Example 1
(1) Synthesis of electrode material for lithium ion secondary battery In 2 L (liter) of water, 6 mol of lithium hydroxide (LiOH), 2 mol of iron (II) acetate (Fe (CH ₃ COO) ₂ ), 2 mol of Phosphoric acid (H ₃ PO ₄ ) and 0.100 mol of lithium sulfate (Li ₂ SO ₄ ) were added and mixed so that the total amount was 4 L to prepare a uniform slurry mixture.
Subsequently, this mixture was accommodated in a pressure-resistant airtight container having a capacity of 8 L, and hydrothermal synthesis was performed at 170 ° C. for 1 hour to produce a precipitate.
Next, the obtained precipitate was washed with water to obtain a cake-like electrode active material.
Next, 150 g of this cake-like electrode active material, 15 g of lactose as organic compound II are dispersed and dissolved in 200 g of water, and 500 g of zirconia balls having a diameter of 0.1 mm as medium particles are put into a ball mill, The rotation speed and stirring time of the ball mill were adjusted so that the ratio (D90 / D10) of D90 to D10 in the particle size distribution of the electrode active material therein was 30, and the dispersion treatment was performed. This obtained the slurry containing an electrode active material (slurry preparation process).

Next, the obtained slurry was sprayed into an air atmosphere at 200 ° C. and dried to obtain a dried product (granulated body preparation step).
Next, the obtained dried product was fired at 700 ° C. for 1 hour in a nitrogen atmosphere to obtain a carbon-coated electrode active material aggregate having an average secondary particle size of 20 μm (heat treatment step). After mixing 10% by mass of ethylene carbonate powder as the organic compound I with this aggregate, it was heated at 50 ° C. for 1 hour in a nitrogen atmosphere to confirm that the ethylene carbonate was melted, and then cooled to Example 1 Electrode material for a lithium ion secondary battery (organic compound I supporting step).

(2) Production of Lithium Ion Secondary Battery Electrode The above-mentioned electrode material, polyvinylidene fluoride (PVdF) as a binder resin, and acetylene black (AB) as a conductive assistant, and a mass ratio of 90: 5: 5 Then, N-methyl-2-pyrrolidinone (NMP) was added as a solvent to give fluidity to prepare an electrode material mixture.
Subsequently, this electrode material mixture was applied onto an aluminum (Al) foil having a thickness of 15 μm as an electrode material mass at a basis weight of 8 mg / cm ² and dried to form a coating film. Thereafter, the coating film was pressurized at a linear pressure of 7 tons / 250 mm to produce the lithium ion secondary battery electrode of Example 1.

(3) Production of lithium ion secondary battery A natural graphite negative electrode is arranged as a counter electrode so as to face the electrode for lithium ion secondary battery, and is made of porous polypropylene between the electrode for lithium ion secondary battery and the counter electrode. A separator was disposed to form a battery member.
On the other hand, ethylene carbonate and diethylene carbonate were mixed, and 1 mol / L LiPF ₆ was further added to prepare an electrolyte solution having lithium ion conductivity. In consideration of the amount of ethylene carbonate contained in the electrode material, the volume ratio of ethylene carbonate and diethylene carbonate in the battery was adjusted to 1: 1 when the battery was assembled, and 1 mol / L LiPF _{6 was} further added. Was added to prepare an electrolyte solution having lithium ion conductivity.
Next, the battery member was immersed in the electrolyte solution, and a lithium ion secondary battery of Example 1 was produced.

(Example 2)
In 2 L (liter) of water, 6 mol of lithium hydroxide (LiOH), 2 mol of iron (II) acetate (Fe (CH ₃ COO) ₂ ), 2 mol of phosphoric acid (H ₃ PO ₄ ), 0.103 mol Lithium sulfate (Li ₂ SO ₄ ) was added and mixed so that the total amount was 4 L to prepare a uniform slurry mixture.
Subsequently, this mixture was accommodated in a pressure-resistant airtight container having a capacity of 8 L, and hydrothermal synthesis was performed at 170 ° C. for 1 hour to produce a precipitate.
Next, the obtained precipitate was washed with water to obtain a cake-like electrode active material.
Next, 150 g of this cake-like electrode active material, 11 g of lactose as organic compound II were dispersed and dissolved in 200 g of water, and 500 g of zirconia balls having a diameter of 0.1 mm as medium particles were put into a ball mill. The ball mill rotation speed and stirring time were adjusted so that the ratio (D90 / D10) of D90 to D10 in the particle size distribution of the electrode active material in the slurry was 30, and the dispersion treatment was performed. Thereby, the slurry containing an electrode active material was obtained.
Next, the obtained slurry was sprayed into an air atmosphere at 200 ° C. and dried to obtain a dried product.
Next, the obtained dried product was fired at 700 ° C. for 1 hour in a nitrogen atmosphere to obtain a carbon-coated electrode active material aggregate having an average secondary particle size of 14 μm. After mixing 20 mass% of ethylene carbonate powder as the organic compound I with this aggregate, heating at 50 ° C. for 1 hour in a nitrogen atmosphere to confirm that the ethylene carbonate was melted, and then cooling to Example 2 Electrode material for a lithium ion secondary battery.
Next, an electrode for a lithium ion secondary battery of Example 2 was produced in the same manner as in Example 1 except that the electrode material for a lithium ion secondary battery of Example 2 was used. In addition, a lithium ion secondary battery of Example 2 was produced in the same manner as in Example 1 using the obtained electrode for a lithium ion secondary battery.

(Example 3)
In 2 L (liter) of water, 6 mol of lithium hydroxide (LiOH), 2 mol of iron (II) acetate (Fe (CH ₃ COO) ₂ ), 2 mol of phosphoric acid (H ₃ PO ₄ ), 0.103 mol Lithium sulfate (Li ₂ SO ₄ ) was added and mixed so that the total amount was 4 L to prepare a uniform slurry mixture.
Subsequently, this mixture was accommodated in a pressure-resistant airtight container having a capacity of 8 L, and hydrothermal synthesis was performed at 170 ° C. for 1 hour to produce a precipitate.
Next, the obtained precipitate was washed with water to obtain a cake-like electrode active material.
Next, 150 g of this cake-like electrode active material, 7 g of lactose as organic compound II was dispersed and dissolved in 200 g of water, and 500 g of zirconia balls having a diameter of 0.1 mm as medium particles were put into a ball mill. The ball mill rotation speed and stirring time were adjusted so that the ratio (D90 / D10) of D90 to D10 in the particle size distribution of the electrode active material in the slurry was 30, and the dispersion treatment was performed. Thereby, the slurry containing an electrode active material was obtained.
Next, the obtained slurry was sprayed into an air atmosphere at 200 ° C. and dried to obtain a dried product.
Next, the obtained dried product was fired at 700 ° C. for 1 hour in a nitrogen atmosphere to obtain a carbon-coated electrode active material aggregate having an average secondary particle size of 8 μm. After mixing 30% by mass of the ethylene carbonate powder as the organic compound I with this aggregate, the mixture was heated at 50 ° C. for 1 hour in a nitrogen atmosphere to confirm that the ethylene carbonate was melted, and then cooled to obtain Example 3 Electrode material for a lithium ion secondary battery.
Next, an electrode for a lithium ion secondary battery of Example 3 was produced in the same manner as in Example 1 except that the electrode material for a lithium ion secondary battery of Example 3 was used. In addition, a lithium ion secondary battery of Example 3 was produced in the same manner as in Example 1 by using the obtained electrode for a lithium ion secondary battery.

Example 4
In 2 L (liter) of water, 6 mol of lithium hydroxide (LiOH), 2 mol of iron (II) acetate (Fe (CH ₃ COO) ₂ ), 2 mol of phosphoric acid (H ₃ PO ₄ ), 0.103 mol Lithium sulfate (Li ₂ SO ₄ ) was added and mixed so that the total amount was 4 L to prepare a uniform slurry mixture.
Subsequently, this mixture was accommodated in a pressure-resistant airtight container having a capacity of 8 L, and hydrothermal synthesis was performed at 170 ° C. for 1 hour to produce a precipitate.
Next, the obtained precipitate was washed with water to obtain a cake-like electrode active material.
Next, 150 g of this cake-like electrode active material, 7 g of lactose as organic compound II was dispersed and dissolved in 200 g of water, and 500 g of zirconia balls having a diameter of 0.1 mm as medium particles were put into a ball mill. The ball mill rotation speed and stirring time were adjusted so that the ratio (D90 / D10) of D90 to D10 in the particle size distribution of the electrode active material in the slurry was 30, and the dispersion treatment was performed. Thereby, the slurry containing an electrode active material was obtained.
Next, the obtained slurry was sprayed into an air atmosphere at 200 ° C. and dried to obtain a dried product.
Next, the obtained dried product was fired at 700 ° C. for 1 hour in a nitrogen atmosphere to obtain a carbon-coated electrode active material aggregate having an average secondary particle size of 6 μm. After 40 mass% of ethylene carbonate powder as organic compound I was mixed with this aggregate, it was heated at 50 ° C. for 1 hour in a nitrogen atmosphere to confirm that the ethylene carbonate was melted, and then cooled to Example 4 Electrode material for a lithium ion secondary battery.
Next, an electrode for a lithium ion secondary battery of Example 4 was produced in the same manner as in Example 1 except that the electrode material for a lithium ion secondary battery of Example 4 was used. In addition, a lithium ion secondary battery of Example 4 was produced in the same manner as in Example 1 using the obtained electrode for a lithium ion secondary battery.

(Example 5)
In 2 L (liter) of water, 6 mol of lithium hydroxide (LiOH), 2 mol of iron (II) acetate (Fe (CH ₃ COO) ₂ ), 2 mol of phosphoric acid (H ₃ PO ₄ ), 0.103 mol Lithium sulfate (Li ₂ SO ₄ ) was added and mixed so that the total amount was 4 L to prepare a uniform slurry mixture.
Subsequently, this mixture was accommodated in a pressure-resistant airtight container having a capacity of 8 L, and hydrothermal synthesis was performed at 170 ° C. for 1 hour to produce a precipitate.
Next, the obtained precipitate was washed with water to obtain a cake-like electrode active material.
Next, 150 g of this cake-like electrode active material, 7 g of lactose as organic compound II was dispersed and dissolved in 200 g of water, and 500 g of zirconia balls having a diameter of 0.1 mm as medium particles were put into a ball mill. The ball mill rotation speed and stirring time were adjusted so that the ratio (D90 / D10) of D90 to D10 in the particle size distribution of the electrode active material in the slurry was 30, and the dispersion treatment was performed. Thereby, the slurry containing an electrode active material was obtained.
Next, the obtained slurry was sprayed into an air atmosphere at 200 ° C. and dried to obtain a dried product.
Next, the obtained dried product was fired at 700 ° C. for 1 hour in a nitrogen atmosphere to obtain a carbon-coated electrode active material aggregate having an average secondary particle size of 4 μm. After mixing 50% by mass of ethylene carbonate powder as the organic compound I with this aggregate, the mixture was heated at 50 ° C. for 1 hour in a nitrogen atmosphere to confirm that the ethylene carbonate was melted, and then cooled to Example 5 Electrode material for a lithium ion secondary battery.
Subsequently, the electrode for lithium ion secondary batteries of Example 5 was produced like Example 1 except having used the electrode material for lithium ion secondary batteries of Example 5. FIG. In addition, a lithium ion secondary battery of Example 5 was produced in the same manner as in Example 1 using the obtained electrode for a lithium ion secondary battery.

(Example 6)
In 2 L (liter) of water, 6 mol of lithium hydroxide (LiOH), 2 mol of iron (II) acetate (Fe (CH ₃ COO) ₂ ), 2 mol of phosphoric acid (H ₃ PO ₄ ), 0.103 mol Lithium sulfate (Li ₂ SO ₄ ) was added and mixed so that the total amount was 4 L to prepare a uniform slurry mixture.
Subsequently, this mixture was accommodated in a pressure-resistant airtight container having a capacity of 8 L, and hydrothermal synthesis was performed at 190 ° C. for 1 hour to produce a precipitate.
Next, the obtained precipitate was washed with water to obtain a cake-like electrode active material.
Next, 150 g of this cake-like electrode active material, 7 g of lactose as organic compound II was dispersed and dissolved in 200 g of water, and 500 g of zirconia balls having a diameter of 0.1 mm as medium particles were put into a ball mill. The ball mill rotation speed and stirring time were adjusted so that the ratio (D90 / D10) of D90 to D10 in the particle size distribution of the electrode active material in the slurry was 30, and the dispersion treatment was performed. Thereby, the slurry containing an electrode active material was obtained.
Next, the obtained slurry was sprayed into an air atmosphere at 200 ° C. and dried to obtain a dried product.
Next, the obtained dried product was fired at 700 ° C. for 1 hour in a nitrogen atmosphere to obtain a carbon-coated electrode active material aggregate having an average secondary particle size of 25 μm. After mixing 60 mass% of ethylene carbonate powder as the organic compound I with this aggregate, heating at 50 ° C. for 1 hour in a nitrogen atmosphere to confirm that the ethylene carbonate was melted, and then cooling to Example 6 Electrode material for a lithium ion secondary battery.
Next, an electrode for a lithium ion secondary battery of Example 6 was produced in the same manner as in Example 1 except that the electrode material for a lithium ion secondary battery of Example 6 was used. Further, using the obtained electrode for a lithium ion secondary battery, a lithium ion secondary battery of Example 6 was produced in the same manner as in Example 1.

(Example 7)
In 2 L (liter) of water, 6 mol of lithium hydroxide (LiOH), 2 mol of iron (II) acetate (Fe (CH ₃ COO) ₂ ), 2 mol of phosphoric acid (H ₃ PO ₄ ), 0.103 mol Lithium sulfate (Li ₂ SO ₄ ) was added and mixed so that the total amount was 4 L to prepare a uniform slurry mixture.
Subsequently, this mixture was accommodated in a pressure-resistant sealed container having a capacity of 8 L, and hydrothermally synthesized at 210 ° C. for 1 hour to produce a precipitate.
Next, the obtained precipitate was washed with water to obtain a cake-like electrode active material.
Next, 150 g of this cake-like electrode active material, 7 g of lactose as organic compound II was dispersed and dissolved in 200 g of water, and 500 g of zirconia balls having a diameter of 0.1 mm as medium particles were put into a ball mill. The ball mill rotation speed and stirring time were adjusted so that the ratio (D90 / D10) of D90 to D10 in the particle size distribution of the electrode active material in the slurry was 30, and the dispersion treatment was performed. Thereby, the slurry containing an electrode active material was obtained.
Next, the obtained slurry was sprayed into an air atmosphere at 200 ° C. and dried to obtain a dried product.
Next, the obtained dried product was fired at 700 ° C. for 1 hour in a nitrogen atmosphere to obtain a carbon-coated electrode active material aggregate having an average secondary particle size of 35 μm. After mixing 70 mass% of ethylene carbonate powder as the organic compound I with this aggregate, the mixture was heated at 50 ° C. for 1 hour in a nitrogen atmosphere to confirm that the ethylene carbonate was melted, and then cooled to Example 7 Electrode material for a lithium ion secondary battery.
Next, an electrode for a lithium ion secondary battery of Example 7 was produced in the same manner as in Example 1 except that the electrode material for a lithium ion secondary battery of Example 7 was used. In addition, a lithium ion secondary battery of Example 7 was produced in the same manner as in Example 1 by using the obtained electrode for a lithium ion secondary battery.

(Example 8)
In 2 L (liter) of water, 6 mol of lithium hydroxide (LiOH), 2 mol of iron (II) acetate (Fe (CH ₃ COO) ₂ ), 2 mol of phosphoric acid (H ₃ PO ₄ ), 0.103 mol Lithium sulfate (Li ₂ SO ₄ ) was added and mixed so that the total amount was 4 L to prepare a uniform slurry mixture.
Subsequently, this mixture was accommodated in a pressure-resistant airtight container having a capacity of 8 L, and hydrothermally synthesized at 230 ° C. for 1 hour to produce a precipitate.
Next, the obtained precipitate was washed with water to obtain a cake-like electrode active material.
Next, 150 g of this cake-like electrode active material, 7 g of lactose as organic compound II was dispersed and dissolved in 200 g of water, and 500 g of zirconia balls having a diameter of 0.1 mm as medium particles were put into a ball mill. The ball mill rotation speed and stirring time were adjusted so that the ratio (D90 / D10) of D90 to D10 in the particle size distribution of the electrode active material in the slurry was 30, and the dispersion treatment was performed. Thereby, the slurry containing an electrode active material was obtained.
Next, the obtained slurry was sprayed into an air atmosphere at 200 ° C. and dried to obtain a dried product.
Next, the obtained dried product was fired at 700 ° C. for 1 hour in a nitrogen atmosphere to obtain a carbon-coated electrode active material aggregate having an average secondary particle size of 50 μm. After 80% by mass of ethylene carbonate powder as organic compound I was mixed with this aggregate, the mixture was heated at 50 ° C. for 1 hour in a nitrogen atmosphere to confirm that the ethylene carbonate was melted, and then cooled to Example 8 Electrode material for a lithium ion secondary battery.
Next, an electrode for a lithium ion secondary battery of Example 8 was produced in the same manner as in Example 1 except that the electrode material for a lithium ion secondary battery of Example 8 was used. In addition, a lithium ion secondary battery of Example 8 was produced in the same manner as in Example 1 by using the obtained electrode for a lithium ion secondary battery.

Example 9
In 2 L (liter) of water, 6 mol of lithium hydroxide (LiOH), 2 mol of iron (II) acetate (Fe (CH ₃ COO) ₂ ), 2 mol of phosphoric acid (H ₃ PO ₄ ), 0.103 mol Lithium sulfate (Li ₂ SO ₄ ) was added and mixed so that the total amount was 4 L to prepare a uniform slurry mixture.
Subsequently, this mixture was accommodated in a pressure-resistant airtight container having a capacity of 8 L, and hydrothermal synthesis was performed at 170 ° C. for 1 hour to produce a precipitate.
Next, the obtained precipitate was washed with water to obtain a cake-like electrode active material.
Next, 150 g of this cake-like electrode active material, 4 g of lactose as organic compound II were dispersed and dissolved in 200 g of water, and 500 g of zirconia balls having a diameter of 0.1 mm as medium particles were put into a ball mill. The ball mill rotation speed and stirring time were adjusted so that the ratio (D90 / D10) of D90 to D10 in the particle size distribution of the electrode active material in the slurry was 30, and the dispersion treatment was performed. Thereby, the slurry containing an electrode active material was obtained.
Next, the obtained slurry was sprayed into an air atmosphere at 200 ° C. and dried to obtain a dried product.
Next, the obtained dried product was fired at 700 ° C. for 1 hour in a nitrogen atmosphere to obtain a carbon-coated electrode active material aggregate having an average secondary particle size of 14 μm. The aggregate was mixed with 20% by mass of sulfolane powder as the organic compound I, heated in a nitrogen atmosphere at 50 ° C. for 1 hour to confirm that the sulfolane was melted, cooled, and cooled to the lithium of Example 9. It was set as the electrode material for ion secondary batteries.
Next, an electrode for a lithium ion secondary battery of Example 9 was produced in the same manner as in Example 1 except that the electrode material for a lithium ion secondary battery of Example 9 was used. Further, a lithium ion secondary battery of Example 9 was produced in the same manner as in Example 1 using the obtained electrode for lithium ion secondary battery.

(Example 10)
In 2 L (liter) of water, 6 mol of lithium hydroxide (LiOH), 2 mol of iron (II) acetate (Fe (CH ₃ COO) ₂ ), 2 mol of phosphoric acid (H ₃ PO ₄ ), 0.103 mol Lithium sulfate (Li ₂ SO ₄ ) was added and mixed so that the total amount was 4 L to prepare a uniform slurry mixture.
Subsequently, this mixture was accommodated in a pressure-resistant airtight container having a capacity of 8 L, and hydrothermal synthesis was performed at 170 ° C. for 1 hour to produce a precipitate.
Next, the obtained precipitate was washed with water to obtain a cake-like electrode active material.
Next, 150 g of this cake-like electrode active material, 7 g of lactose as organic compound II was dispersed and dissolved in 200 g of water, and 500 g of zirconia balls having a diameter of 0.1 mm as medium particles were put into a ball mill. The ball mill rotation speed and stirring time were adjusted so that the ratio (D90 / D10) of D90 to D10 in the particle size distribution of the electrode active material in the slurry was 30, and the dispersion treatment was performed. Thereby, the slurry containing an electrode active material was obtained.
Next, the obtained slurry was sprayed into an air atmosphere at 200 ° C. and dried to obtain a dried product.
Next, the obtained dried product was fired at 700 ° C. for 1 hour in a nitrogen atmosphere to obtain a carbon-coated electrode active material aggregate having an average secondary particle size of 14 μm. This aggregate was mixed with 35% by mass of sulfolane powder as the organic compound I, heated at 50 ° C. for 1 hour in a nitrogen atmosphere to confirm that the sulfolane was melted, cooled, and cooled to the lithium of Example 10. It was set as the electrode material for ion secondary batteries.
Subsequently, the electrode for lithium ion secondary batteries of Example 10 was produced in the same manner as Example 1 except that the electrode material for lithium ion secondary batteries of Example 10 was used. In addition, a lithium ion secondary battery of Example 10 was produced in the same manner as in Example 1 using the obtained electrode for a lithium ion secondary battery.

(Example 11)
In 2 L (liter) of water, 6 mol of lithium hydroxide (LiOH), 2 mol of iron (II) acetate (Fe (CH ₃ COO) ₂ ), 2 mol of phosphoric acid (H ₃ PO ₄ ), 0.103 mol Lithium sulfate (Li ₂ SO ₄ ) was added and mixed so that the total amount was 4 L to prepare a uniform slurry mixture.
Subsequently, this mixture was accommodated in a pressure-resistant airtight container having a capacity of 8 L, and hydrothermal synthesis was performed at 170 ° C. for 1 hour to produce a precipitate.
Next, the obtained precipitate was washed with water to obtain a cake-like electrode active material.
Next, 150 g of this cake-like electrode active material, 9 g of lactose as organic compound II were dispersed and dissolved in 200 g of water, and 500 g of zirconia balls having a diameter of 0.1 mm as medium particles were put into a ball mill. The ball mill rotation speed and stirring time were adjusted so that the ratio (D90 / D10) of D90 to D10 in the particle size distribution of the electrode active material in the slurry was 30, and the dispersion treatment was performed. Thereby, the slurry containing an electrode active material was obtained.
Next, the obtained slurry was sprayed into an air atmosphere at 200 ° C. and dried to obtain a dried product.
Next, the obtained dried product was fired at 700 ° C. for 1 hour in a nitrogen atmosphere to obtain a carbon-coated electrode active material aggregate having an average secondary particle size of 14 μm. After 40 mass% of the sulfolane powder as the organic compound I was mixed with this aggregate, the mixture was heated at 50 ° C. for 1 hour in a nitrogen atmosphere to confirm that the sulfolane was melted, and then cooled, and the lithium of Example 11 was cooled. An electrode material for an ion secondary battery was obtained.
Subsequently, the electrode for lithium ion secondary batteries of Example 11 was produced like Example 1 except having used the electrode material for lithium ion secondary batteries of Example 11. FIG. In addition, a lithium ion secondary battery of Example 11 was produced in the same manner as in Example 1 using the obtained electrode for a lithium ion secondary battery.

(Example 12)
In 2 L (liter) of water, 6 mol of lithium hydroxide (LiOH), 2 mol of iron (II) acetate (Fe (CH ₃ COO) ₂ ), 2 mol of phosphoric acid (H ₃ PO ₄ ), 0.103 mol Lithium sulfate (Li ₂ SO ₄ ) was added and mixed so that the total amount was 4 L to prepare a uniform slurry mixture.
Subsequently, this mixture was accommodated in a pressure-resistant airtight container having a capacity of 8 L, and hydrothermal synthesis was performed at 170 ° C. for 1 hour to produce a precipitate.
Next, the obtained precipitate was washed with water to obtain a cake-like electrode active material.
Next, 150 g of this cake-like electrode active material, 11 g of lactose as organic compound II were dispersed and dissolved in 200 g of water, and 500 g of zirconia balls having a diameter of 0.1 mm as medium particles were put into a ball mill. The ball mill rotation speed and stirring time were adjusted so that the ratio (D90 / D10) of D90 to D10 in the particle size distribution of the electrode active material in the slurry was 30, and the dispersion treatment was performed. Thereby, the slurry containing an electrode active material was obtained.
Next, the obtained slurry was sprayed into an air atmosphere at 200 ° C. and dried to obtain a dried product.
Next, the obtained dried product was fired at 700 ° C. for 1 hour in a nitrogen atmosphere to obtain a carbon-coated electrode active material aggregate having an average secondary particle size of 14 μm. The aggregate was mixed with 65% by mass of sulfolane powder as the organic compound I, heated in a nitrogen atmosphere at 50 ° C. for 1 hour to confirm that the sulfolane was melted, cooled, and cooled to the lithium of Example 12. It was set as the electrode material for ion secondary batteries.
Next, an electrode for a lithium ion secondary battery of Example 12 was produced in the same manner as in Example 1 except that the electrode material for a lithium ion secondary battery of Example 12 was used. In addition, a lithium ion secondary battery of Example 12 was produced in the same manner as in Example 1 by using the obtained electrode for lithium ion secondary battery.

(Example 13)
In 2 L (liter) of water, 6 mol of lithium hydroxide (LiOH), 2 mol of iron (II) acetate (Fe (CH ₃ COO) ₂ ), 2 mol of phosphoric acid (H ₃ PO ₄ ), 0.103 mol Lithium sulfate (Li ₂ SO ₄ ) was added and mixed so that the total amount was 4 L to prepare a uniform slurry mixture.
Subsequently, this mixture was accommodated in a pressure-resistant airtight container having a capacity of 8 L, and hydrothermal synthesis was performed at 170 ° C. for 1 hour to produce a precipitate.
Next, the obtained precipitate was washed with water to obtain a cake-like electrode active material.
Next, 150 g of this cake-like electrode active material, 15 g of lactose as organic compound II is dispersed and dissolved in 200 g of water, and 500 g of zirconia balls having a diameter of 0.1 mm as medium particles are put into a ball mill. The ball mill rotation speed and stirring time were adjusted so that the ratio (D90 / D10) of D90 to D10 in the particle size distribution of the electrode active material in the slurry was 30, and the dispersion treatment was performed. Thereby, the slurry containing an electrode active material was obtained.
Next, the obtained slurry was sprayed into an air atmosphere at 200 ° C. and dried to obtain a dried product.
Next, the obtained dried product was fired at 700 ° C. for 1 hour in a nitrogen atmosphere to obtain a carbon-coated electrode active material aggregate having an average secondary particle size of 14 μm. The aggregate was mixed with 70% by mass of sulfolane powder as the organic compound I, and then heated at 50 ° C. for 1 hour in a nitrogen atmosphere to confirm that the sulfolane was melted. It was set as the electrode material for ion secondary batteries.
Next, an electrode for a lithium ion secondary battery of Example 13 was produced in the same manner as in Example 1 except that the electrode material for a lithium ion secondary battery of Example 13 was used. Further, a lithium ion secondary battery of Example 13 was produced in the same manner as in Example 1 using the obtained electrode for a lithium ion secondary battery.

(Example 14)
In 2 L (liter) of water, 6 mol of lithium hydroxide (LiOH), 2 mol of iron (II) acetate (Fe (CH ₃ COO) ₂ ), 2 mol of phosphoric acid (H ₃ PO ₄ ), 0.103 mol Lithium sulfate (Li ₂ SO ₄ ) was added and mixed so that the total amount was 4 L to prepare a uniform slurry mixture.
Subsequently, this mixture was accommodated in a pressure-resistant airtight container having a capacity of 8 L, and hydrothermal synthesis was performed at 170 ° C. for 1 hour to produce a precipitate.
Next, the obtained precipitate was washed with water to obtain a cake-like electrode active material.
Next, 150 g of this cake-like electrode active material, 21 g of lactose as organic compound II was dispersed and dissolved in 200 g of water, and 500 g of zirconia balls having a diameter of 0.1 mm as medium particles were put into a ball mill. The ball mill rotation speed and stirring time were adjusted so that the ratio (D90 / D10) of D90 to D10 in the particle size distribution of the electrode active material in the slurry was 30, and the dispersion treatment was performed. Thereby, the slurry containing an electrode active material was obtained.
Next, the obtained slurry was sprayed into an air atmosphere at 200 ° C. and dried to obtain a dried product.
Next, the obtained dried product was fired at 700 ° C. for 1 hour in a nitrogen atmosphere to obtain a carbon-coated electrode active material aggregate having an average secondary particle size of 14 μm. After 85 mass% of the sulfolane powder as the organic compound I was mixed with this aggregate, the mixture was heated at 50 ° C. for 1 hour in a nitrogen atmosphere to confirm that the sulfolane was melted, and then cooled to cool the lithium of Example 14. It was set as the electrode material for ion secondary batteries.
Next, an electrode for a lithium ion secondary battery of Example 14 was produced in the same manner as in Example 1 except that the electrode material for a lithium ion secondary battery of Example 14 was used. In addition, a lithium ion secondary battery of Example 14 was produced in the same manner as in Example 1 by using the obtained electrode for a lithium ion secondary battery.

(Example 15)
In 2 L (liter) of water, 6 mol of lithium hydroxide (LiOH), 2 mol of iron (II) acetate (Fe (CH ₃ COO) ₂ ), 2 mol of phosphoric acid (H ₃ PO ₄ ), 0.103 mol Lithium sulfate (Li ₂ SO ₄ ) was added and mixed so that the total amount was 4 L to prepare a uniform slurry mixture.
Subsequently, this mixture was accommodated in a pressure-resistant airtight container having a capacity of 8 L, and hydrothermal synthesis was performed at 170 ° C. for 1 hour to produce a precipitate.
Next, the obtained precipitate was washed with water to obtain a cake-like electrode active material.
Next, 150 g of this cake-like electrode active material, 4 g of lactose as organic compound II were dispersed and dissolved in 200 g of water, and 500 g of zirconia balls having a diameter of 0.1 mm as medium particles were put into a ball mill. The ball mill rotation speed and stirring time were adjusted so that the ratio (D90 / D10) of D90 to D10 in the particle size distribution of the electrode active material in the slurry was 30, and the dispersion treatment was performed. Thereby, the slurry containing an electrode active material was obtained.
Next, the obtained slurry was sprayed into an air atmosphere at 200 ° C. and dried to obtain a dried product.
Next, the obtained dried product was fired at 700 ° C. for 1 hour in a nitrogen atmosphere to obtain a carbon-coated electrode active material aggregate having an average secondary particle size of 14 μm. This aggregate was mixed with 20% by mass of ethyl methyl sulfone powder as organic compound I, and then heated at 50 ° C. for 1 hour in a nitrogen atmosphere to confirm that ethyl methyl sulfone had melted, and then cooled and carried out. The lithium ion secondary battery electrode material of Example 15 was obtained.
Next, an electrode for a lithium ion secondary battery of Example 15 was produced in the same manner as in Example 1 except that the electrode material for a lithium ion secondary battery of Example 15 was used. Further, a lithium ion secondary battery of Example 15 was produced in the same manner as in Example 1 using the obtained electrode for a lithium ion secondary battery.

(Example 16)
In 2 L (liter) of water, 6 mol of lithium hydroxide (LiOH), 2 mol of iron (II) acetate (Fe (CH ₃ COO) ₂ ), 2 mol of phosphoric acid (H ₃ PO ₄ ), 0.103 mol Lithium sulfate (Li ₂ SO ₄ ) was added and mixed so that the total amount was 4 L to prepare a uniform slurry mixture.
Subsequently, this mixture was accommodated in a pressure-resistant airtight container having a capacity of 8 L, and hydrothermal synthesis was performed at 170 ° C. for 1 hour to produce a precipitate.
Next, the obtained precipitate was washed with water to obtain a cake-like electrode active material.
Next, 150 g of this cake-like electrode active material, 7 g of lactose as organic compound II was dispersed and dissolved in 200 g of water, and 500 g of zirconia balls having a diameter of 0.1 mm as medium particles were put into a ball mill. The ball mill rotation speed and stirring time were adjusted so that the ratio (D90 / D10) of D90 to D10 in the particle size distribution of the electrode active material in the slurry was 30, and the dispersion treatment was performed. Thereby, the slurry containing an electrode active material was obtained.
Next, the obtained slurry was sprayed into an air atmosphere at 200 ° C. and dried to obtain a dried product.
Next, the obtained dried product was fired at 700 ° C. for 1 hour in a nitrogen atmosphere to obtain a carbon-coated electrode active material aggregate having an average secondary particle size of 14 μm. This aggregate was mixed with 35% by mass of ethyl methyl sulfone powder as organic compound I, and then heated at 50 ° C. for 1 hour in a nitrogen atmosphere to confirm that ethyl methyl sulfone had melted, and then cooled and carried out. The electrode material for lithium ion secondary batteries of Example 16 was obtained.
Next, an electrode for a lithium ion secondary battery of Example 16 was produced in the same manner as in Example 1 except that the electrode material for a lithium ion secondary battery of Example 16 was used. In addition, a lithium ion secondary battery of Example 16 was produced in the same manner as in Example 1 using the obtained electrode for a lithium ion secondary battery.

(Example 17)
In 2 L (liter) of water, 6 mol of lithium hydroxide (LiOH), 2 mol of iron (II) acetate (Fe (CH ₃ COO) ₂ ), 2 mol of phosphoric acid (H ₃ PO ₄ ), 0.103 mol Lithium sulfate (Li ₂ SO ₄ ) was added and mixed so that the total amount was 4 L to prepare a uniform slurry mixture.
Subsequently, this mixture was accommodated in a pressure-resistant airtight container having a capacity of 8 L, and hydrothermal synthesis was performed at 170 ° C. for 1 hour to produce a precipitate.
Next, the obtained precipitate was washed with water to obtain a cake-like electrode active material.
Next, 150 g of this cake-like electrode active material, 9 g of lactose as organic compound II were dispersed and dissolved in 200 g of water, and 500 g of zirconia balls having a diameter of 0.1 mm as medium particles were put into a ball mill. The ball mill rotation speed and stirring time were adjusted so that the ratio (D90 / D10) of D90 to D10 in the particle size distribution of the electrode active material in the slurry was 30, and the dispersion treatment was performed. Thereby, the slurry containing an electrode active material was obtained.
Next, the obtained slurry was sprayed into an air atmosphere at 200 ° C. and dried to obtain a dried product.
Next, the obtained dried product was fired at 700 ° C. for 1 hour in a nitrogen atmosphere to obtain a carbon-coated electrode active material aggregate having an average secondary particle size of 14 μm. After 40 mass% of ethylmethylsulfone powder as organic compound I was mixed with this aggregate, the mixture was heated at 50 ° C. for 1 hour in a nitrogen atmosphere to confirm that ethylmethylsulfone was melted, and then cooled and carried out. The lithium ion secondary battery electrode material of Example 17 was obtained.
Subsequently, the electrode for lithium ion secondary batteries of Example 17 was produced like Example 1 except having used the electrode material for lithium ion secondary batteries of Example 17. FIG. Further, using the obtained electrode for a lithium ion secondary battery, a lithium ion secondary battery of Example 17 was produced in the same manner as in Example 1.

(Example 18)
In 2 L (liter) of water, 6 mol of lithium hydroxide (LiOH), 2 mol of iron (II) acetate (Fe (CH ₃ COO) ₂ ), 2 mol of phosphoric acid (H ₃ PO ₄ ), 0.103 mol Lithium sulfate (Li ₂ SO ₄ ) was added and mixed so that the total amount was 4 L to prepare a uniform slurry mixture.
Subsequently, this mixture was accommodated in a pressure-resistant airtight container having a capacity of 8 L, and hydrothermal synthesis was performed at 170 ° C. for 1 hour to produce a precipitate.
Next, the obtained precipitate was washed with water to obtain a cake-like electrode active material.
Next, 150 g of this cake-like electrode active material, 11 g of lactose as organic compound II were dispersed and dissolved in 200 g of water, and 500 g of zirconia balls having a diameter of 0.1 mm as medium particles were put into a ball mill. The ball mill rotation speed and stirring time were adjusted so that the ratio (D90 / D10) of D90 to D10 in the particle size distribution of the electrode active material in the slurry was 30, and the dispersion treatment was performed. Thereby, the slurry containing an electrode active material was obtained.
Next, the obtained slurry was sprayed into an air atmosphere at 200 ° C. and dried to obtain a dried product.
Next, the obtained dried product was fired at 700 ° C. for 1 hour in a nitrogen atmosphere to obtain a carbon-coated electrode active material aggregate having an average secondary particle size of 14 μm. After mixing 65% by mass of ethylmethylsulfone powder as organic compound I with this agglomerate, heating at 50 ° C. for 1 hour in a nitrogen atmosphere to confirm that ethylmethylsulfone was melted, cooling and carrying out The electrode material for lithium ion secondary batteries of Example 18 was used.
Subsequently, the electrode for lithium ion secondary batteries of Example 18 was produced like Example 1 except having used the electrode material for lithium ion secondary batteries of Example 18. FIG. Further, using the obtained electrode for a lithium ion secondary battery, a lithium ion secondary battery of Example 18 was produced in the same manner as in Example 1.

(Example 19)
In 2 L (liter) of water, 6 mol of lithium hydroxide (LiOH), 2 mol of iron (II) acetate (Fe (CH ₃ COO) ₂ ), 2 mol of phosphoric acid (H ₃ PO ₄ ), 0.103 mol Lithium sulfate (Li ₂ SO ₄ ) was added and mixed so that the total amount was 4 L to prepare a uniform slurry mixture.
Subsequently, this mixture was accommodated in a pressure-resistant airtight container having a capacity of 8 L, and hydrothermal synthesis was performed at 170 ° C. for 1 hour to produce a precipitate.
Next, the obtained precipitate was washed with water to obtain a cake-like electrode active material.
Next, 150 g of this cake-like electrode active material, 15 g of lactose as organic compound II is dispersed and dissolved in 200 g of water, and 500 g of zirconia balls having a diameter of 0.1 mm as medium particles are put into a ball mill. The ball mill rotation speed and stirring time were adjusted so that the ratio (D90 / D10) of D90 to D10 in the particle size distribution of the electrode active material in the slurry was 30, and the dispersion treatment was performed. Thereby, the slurry containing an electrode active material was obtained.
Next, the obtained slurry was sprayed into an air atmosphere at 200 ° C. and dried to obtain a dried product.
Next, the obtained dried product was fired at 700 ° C. for 1 hour in a nitrogen atmosphere to obtain a carbon-coated electrode active material aggregate having an average secondary particle size of 14 μm. After 70 mass% of ethyl methyl sulfone powder as organic compound I was mixed with this aggregate, it was heated at 50 ° C. for 1 hour in a nitrogen atmosphere to confirm that ethyl methyl sulfone was melted, and then cooled and carried out. The electrode material for lithium ion secondary batteries of Example 19 was obtained.
Next, an electrode for a lithium ion secondary battery of Example 19 was produced in the same manner as in Example 1 except that the electrode material for a lithium ion secondary battery of Example 19 was used. In addition, a lithium ion secondary battery of Example 19 was produced in the same manner as in Example 1 by using the obtained electrode for a lithium ion secondary battery.

(Example 20)
In 2 L (liter) of water, 6 mol of lithium hydroxide (LiOH), 2 mol of iron (II) acetate (Fe (CH ₃ COO) ₂ ), 2 mol of phosphoric acid (H ₃ PO ₄ ), 0.103 mol Lithium sulfate (Li ₂ SO ₄ ) was added and mixed so that the total amount was 4 L to prepare a uniform slurry mixture.
Subsequently, this mixture was accommodated in a pressure-resistant airtight container having a capacity of 8 L, and hydrothermal synthesis was performed at 170 ° C. for 1 hour to produce a precipitate.
Next, the obtained precipitate was washed with water to obtain a cake-like electrode active material.
Next, 150 g of this cake-like electrode active material, 21 g of lactose as organic compound II was dispersed and dissolved in 200 g of water, and 500 g of zirconia balls having a diameter of 0.1 mm as medium particles were put into a ball mill. The ball mill rotation speed and stirring time were adjusted so that the ratio (D90 / D10) of D90 to D10 in the particle size distribution of the electrode active material in the slurry was 30, and the dispersion treatment was performed. Thereby, the slurry containing an electrode active material was obtained.
Next, the obtained slurry was sprayed into an air atmosphere at 200 ° C. and dried to obtain a dried product.
Next, the obtained dried product was fired at 700 ° C. for 1 hour in a nitrogen atmosphere to obtain a carbon-coated electrode active material aggregate having an average secondary particle size of 14 μm. After 85 mass% of ethylmethylsulfone powder as organic compound I was mixed with this aggregate, it was heated at 50 ° C for 1 hour in a nitrogen atmosphere to confirm that ethylmethylsulfone was melted, and then cooled and carried out. The lithium ion secondary battery electrode material of Example 20 was obtained.
Next, an electrode for a lithium ion secondary battery of Example 20 was produced in the same manner as in Example 1 except that the electrode material for a lithium ion secondary battery of Example 20 was used. Further, using the obtained electrode for a lithium ion secondary battery, a lithium ion secondary battery of Example 20 was produced in the same manner as in Example 1.

(Example 21)
In 2 L (liter) of water, 6 mol of lithium hydroxide (LiOH), 0.53 mol of iron (II) acetate (Fe (CH ₃ COO) ₂ ), and 0.01 mol of cobalt (II) acetate (Co (CH ₃ COO) ₂ ), 0.06 mol of magnesium acetate (Mg (CH ₃ COO) ₂ ), 1.4 mol of manganese (II) acetate (Mn (CH ₃ COO) ₂ ), 2 mol of phosphoric acid (H ₃ PO ₄ ) and 0.123 mol of lithium sulfate (Li ₂ SO ₄ ) were added and mixed so that the total amount was 4 L to prepare a uniform slurry mixture.
Next, this mixture was placed in a pressure-resistant airtight container having a capacity of 8 L, and hydrothermally synthesized at 140 ° C. for 1 hour to produce a precipitate.
Next, the obtained precipitate was washed with water to obtain a cake-like electrode active material.
Next, 0.1 mol of lithium hydroxide (LiOH), 0.1 mol of iron (II) acetate (Fe (CH ₃ COO) ₂ ), and 0.1 mol of phosphoric acid (H) were added to the cake-like electrode active material. ₃ PO ₄ ) and 1.92 × 10 ⁻⁵ mol of lithium sulfate (Li ₂ SO ₄ ) are added, mixed so that the total amount becomes 2 L, dried, and averaged on the surface of the electrode active material. LiFePO ₄ 0.1 mol with a primary particle diameter of 5 nm was uniformly supported and dried to obtain a mixture containing an electrode active material.
Next, 150 g of this mixture, 4 g of lactose as the organic compound II, dispersed in 200 g of water and an aqueous lactose solution and 500 g of zirconia balls having a diameter of 0.1 mm as medium particles are put into a ball mill, and the electrode activity in the slurry is increased. The ball mill rotational speed and the stirring time were adjusted so that the ratio (D90 / D10) of D90 to D10 in the particle size distribution of the substance was 30, and the dispersion treatment was performed. Thereby, the slurry containing an electrode active material was obtained.
Next, the obtained slurry was sprayed into an air atmosphere at 200 ° C. and dried to obtain a dried product.
Next, the obtained dried product was fired at 700 ° C. for 1 hour in a nitrogen atmosphere to obtain a carbon-coated electrode active material aggregate having an average secondary particle size of 20 μm. After mixing 20 mass% of ethylene carbonate powder as the organic compound I with this aggregate, heating at 50 ° C. for 1 hour in a nitrogen atmosphere to confirm that the ethylene carbonate was melted, and then cooling to Example 21 Electrode material for a lithium ion secondary battery.
Next, an electrode for a lithium ion secondary battery of Example 21 was produced in the same manner as in Example 1 except that the electrode material for a lithium ion secondary battery of Example 21 was used. In addition, a lithium ion secondary battery of Example 21 was produced in the same manner as in Example 1 using the obtained electrode for a lithium ion secondary battery.

(Example 22)
In 2 L (liter) of water, 6 mol of lithium hydroxide (LiOH), 0.53 mol of iron (II) acetate (Fe (CH ₃ COO) ₂ ), and 0.01 mol of cobalt (II) acetate (Co (CH ₃ COO) ₂ ), 0.06 mol of magnesium acetate (Mg (CH ₃ COO) ₂ ), 1.4 mol of manganese (II) acetate (Mn (CH ₃ COO) ₂ ), 2 mol of phosphoric acid (H ₃ PO ₄ ) and 0.123 mol of lithium sulfate (Li ₂ SO ₄ ) were added and mixed so that the total amount was 4 L to prepare a uniform slurry mixture.
Next, this mixture was placed in a pressure-resistant airtight container having a capacity of 8 L, and hydrothermally synthesized at 140 ° C. for 1 hour to produce a precipitate.
Next, the obtained precipitate was washed with water to obtain a cake-like electrode active material.
Next, 0.1 mol of lithium hydroxide (LiOH), 0.1 mol of iron (II) acetate (Fe (CH ₃ COO) ₂ ), and 0.1 mol of phosphoric acid (H) were added to the cake-like electrode active material. ₃ PO ₄ ) and 1.92 × 10 ⁻⁵ mol of lithium sulfate (Li ₂ SO ₄ ) are added, mixed so that the total amount becomes 2 L, dried, and averaged on the surface of the electrode active material. LiFePO ₄ 0.1 mol with a primary particle diameter of 5 nm was uniformly supported and dried to obtain a mixture containing an electrode active material.
Next, 150 g of this mixture, 7 g of lactose as the organic compound II, dispersed in and dissolved in 200 g of water, an aqueous lactose solution and 500 g of zirconia balls having a diameter of 0.1 mm as medium particles were put into a ball mill, and the electrode activity in the slurry was The ball mill rotational speed and the stirring time were adjusted so that the ratio (D90 / D10) of D90 to D10 in the particle size distribution of the substance was 30, and the dispersion treatment was performed. Thereby, the slurry containing an electrode active material was obtained.
Next, the obtained slurry was sprayed into an air atmosphere at 200 ° C. and dried to obtain a dried product.
Next, the obtained dried product was fired at 700 ° C. for 1 hour in a nitrogen atmosphere to obtain a carbon-coated electrode active material aggregate having an average secondary particle size of 20 μm. After mixing 35 mass% of ethylene carbonate powder as the organic compound I with this aggregate, the mixture was heated at 50 ° C. for 1 hour in a nitrogen atmosphere to confirm that the ethylene carbonate was melted, and then cooled to Example 22 Electrode material for a lithium ion secondary battery.
Next, an electrode for a lithium ion secondary battery of Example 22 was produced in the same manner as in Example 1 except that the electrode material for a lithium ion secondary battery of Example 22 was used. In addition, a lithium ion secondary battery of Example 22 was produced in the same manner as in Example 1 using the obtained electrode for a lithium ion secondary battery.

(Example 23)
In 2 L (liter) of water, 6 mol of lithium hydroxide (LiOH), 0.53 mol of iron (II) acetate (Fe (CH ₃ COO) ₂ ), and 0.01 mol of cobalt (II) acetate (Co (CH ₃ COO) ₂ ), 0.06 mol of magnesium acetate (Mg (CH ₃ COO) ₂ ), 1.4 mol of manganese (II) acetate (Mn (CH ₃ COO) ₂ ), 2 mol of phosphoric acid (H ₃ PO ₄ ) and 0.123 mol of lithium sulfate (Li ₂ SO ₄ ) were added and mixed so that the total amount was 4 L to prepare a uniform slurry mixture.
Next, this mixture was placed in a pressure-resistant airtight container having a capacity of 8 L, and hydrothermally synthesized at 140 ° C. for 1 hour to produce a precipitate.
Next, the obtained precipitate was washed with water to obtain a cake-like electrode active material.
Next, 0.1 mol of lithium hydroxide (LiOH), 0.1 mol of iron (II) acetate (Fe (CH ₃ COO) ₂ ), and 0.1 mol of phosphoric acid (H) were added to the cake-like electrode active material. ₃ PO ₄ ) and 1.92 × 10 ⁻⁵ mol of lithium sulfate (Li ₂ SO ₄ ) are added, mixed so that the total amount becomes 2 L, dried, and averaged on the surface of the electrode active material. LiFePO ₄ 0.1 mol with a primary particle diameter of 5 nm was uniformly supported and dried to obtain a mixture containing an electrode active material.
Next, 150 g of this mixture, 9 g of lactose as the organic compound II, dispersed in and dissolved in 200 g of water, and 500 g of zirconia balls having a diameter of 0.1 mm as medium particles were put into a ball mill, and the electrode activity in the slurry was The ball mill rotational speed and the stirring time were adjusted so that the ratio (D90 / D10) of D90 to D10 in the particle size distribution of the substance was 30, and the dispersion treatment was performed. Thereby, the slurry containing an electrode active material was obtained.
Next, the obtained slurry was sprayed into an air atmosphere at 200 ° C. and dried to obtain a dried product.
Next, the obtained dried product was fired at 700 ° C. for 1 hour in a nitrogen atmosphere to obtain a carbon-coated electrode active material aggregate having an average secondary particle size of 20 μm. This aggregate was mixed with 40% by mass of ethylene carbonate powder as the organic compound I, and then heated at 50 ° C. for 1 hour in a nitrogen atmosphere to confirm that the ethylene carbonate was melted. Electrode material for a lithium ion secondary battery.
Subsequently, the electrode for lithium ion secondary batteries of Example 23 was produced like Example 1 except having used the electrode material for lithium ion secondary batteries of Example 23. FIG. In addition, a lithium ion secondary battery of Example 23 was produced in the same manner as in Example 1 by using the obtained electrode for a lithium ion secondary battery.

(Example 24)
In 2 L (liter) of water, 6 mol of lithium hydroxide (LiOH), 0.53 mol of iron (II) acetate (Fe (CH ₃ COO) ₂ ), and 0.01 mol of cobalt (II) acetate (Co (CH ₃ COO) ₂ ), 0.06 mol of magnesium acetate (Mg (CH ₃ COO) ₂ ), 1.4 mol of manganese (II) acetate (Mn (CH ₃ COO) ₂ ), 2 mol of phosphoric acid (H ₃ PO ₄ ) and 0.123 mol of lithium sulfate (Li ₂ SO ₄ ) were added and mixed so that the total amount was 4 L to prepare a uniform slurry mixture.
Next, this mixture was placed in a pressure-resistant airtight container having a capacity of 8 L, and hydrothermally synthesized at 140 ° C. for 1 hour to produce a precipitate.
Next, the obtained precipitate was washed with water to obtain a cake-like electrode active material.
Next, 0.1 mol of lithium hydroxide (LiOH), 0.1 mol of iron (II) acetate (Fe (CH ₃ COO) ₂ ), and 0.1 mol of phosphoric acid (H) were added to the cake-like electrode active material. ₃ PO ₄ ) and 1.92 × 10 ⁻⁵ mol of lithium sulfate (Li ₂ SO ₄ ) are added, mixed so that the total amount becomes 2 L, dried, and averaged on the surface of the electrode active material. LiFePO ₄ 0.1 mol with a primary particle diameter of 5 nm was uniformly supported and dried to obtain a mixture containing an electrode active material.
Next, 150 g of this mixture, 13 g of lactose as the organic compound II, dispersed in 200 g of water and an aqueous lactose solution and 500 g of zirconia balls having a diameter of 0.1 mm as medium particles were put into a ball mill, and the electrode activity in the slurry was The ball mill rotational speed and the stirring time were adjusted so that the ratio (D90 / D10) of D90 to D10 in the particle size distribution of the substance was 30, and the dispersion treatment was performed. Thereby, the slurry containing an electrode active material was obtained.
Next, the obtained slurry was sprayed into an air atmosphere at 200 ° C. and dried to obtain a dried product.
Next, the obtained dried product was fired at 700 ° C. for 1 hour in a nitrogen atmosphere to obtain a carbon-coated electrode active material aggregate having an average secondary particle size of 20 μm. After mixing 65 mass% of ethylene carbonate powder as the organic compound I with this aggregate, the mixture was heated at 50 ° C. for 1 hour in a nitrogen atmosphere to confirm that the ethylene carbonate was melted, and then cooled to Example 24. Electrode material for a lithium ion secondary battery.
Next, an electrode for a lithium ion secondary battery of Example 24 was produced in the same manner as in Example 1 except that the electrode material for a lithium ion secondary battery of Example 24 was used. In addition, a lithium ion secondary battery of Example 24 was produced in the same manner as in Example 1 using the obtained electrode for a lithium ion secondary battery.

(Example 25)
In 2 L (liter) of water, 6 mol of lithium hydroxide (LiOH), 0.53 mol of iron (II) acetate (Fe (CH ₃ COO) ₂ ), and 0.01 mol of cobalt (II) acetate (Co (CH ₃ COO) ₂ ), 0.06 mol of magnesium acetate (Mg (CH ₃ COO) ₂ ), 1.4 mol of manganese (II) acetate (Mn (CH ₃ COO) ₂ ), 2 mol of phosphoric acid (H ₃ PO ₄ ) and 0.123 mol of lithium sulfate (Li ₂ SO ₄ ) were added and mixed so that the total amount was 4 L to prepare a uniform slurry mixture.
Next, this mixture was placed in a pressure-resistant airtight container having a capacity of 8 L, and hydrothermally synthesized at 140 ° C. for 1 hour to produce a precipitate.
Next, the obtained precipitate was washed with water to obtain a cake-like electrode active material.
Next, 0.1 mol of lithium hydroxide (LiOH), 0.1 mol of iron (II) acetate (Fe (CH ₃ COO) ₂ ), and 0.1 mol of phosphoric acid (H) were added to the cake-like electrode active material. ₃ PO ₄ ) and 1.92 × 10 ⁻⁵ mol of lithium sulfate (Li ₂ SO ₄ ) are added, mixed so that the total amount becomes 2 L, dried, and averaged on the surface of the electrode active material. LiFePO ₄ 0.1 mol with a primary particle diameter of 5 nm was uniformly supported and dried to obtain a mixture containing an electrode active material.
Next, 150 g of this mixture and 17 g of lactose as the organic compound II are dispersed and dissolved in 200 g of water, and 500 g of zirconia balls having a diameter of 0.1 mm as medium particles are put into a ball mill, and the electrode activity in the slurry is increased. The ball mill rotational speed and the stirring time were adjusted so that the ratio (D90 / D10) of D90 to D10 in the particle size distribution of the substance was 30, and the dispersion treatment was performed. Thereby, the slurry containing an electrode active material was obtained.
Next, the obtained slurry was sprayed into an air atmosphere at 200 ° C. and dried to obtain a dried product.
Next, the obtained dried product was fired at 700 ° C. for 1 hour in a nitrogen atmosphere to obtain a carbon-coated electrode active material aggregate having an average secondary particle size of 20 μm. After mixing 70 mass% of ethylene carbonate powder as the organic compound I with this aggregate, it was heated at 50 ° C. for 1 hour in a nitrogen atmosphere to confirm that the ethylene carbonate was melted, and then cooled to Example 25. Electrode material for a lithium ion secondary battery.
Subsequently, the electrode for lithium ion secondary batteries of Example 25 was produced like Example 1 except having used the electrode material for lithium ion secondary batteries of Example 25. FIG. In addition, a lithium ion secondary battery of Example 25 was produced in the same manner as in Example 1 using the obtained electrode for a lithium ion secondary battery.

(Example 26)
In 2 L (liter) of water, 6 mol of lithium hydroxide (LiOH), 0.53 mol of iron (II) acetate (Fe (CH ₃ COO) ₂ ), and 0.01 mol of cobalt (II) acetate (Co (CH ₃ COO) ₂ ), 0.06 mol of magnesium acetate (Mg (CH ₃ COO) ₂ ), 1.4 mol of manganese (II) acetate (Mn (CH ₃ COO) ₂ ), 2 mol of phosphoric acid (H ₃ PO ₄ ) and 0.123 mol of lithium sulfate (Li ₂ SO ₄ ) were added and mixed so that the total amount was 4 L to prepare a uniform slurry mixture.
Next, this mixture was placed in a pressure-resistant airtight container having a capacity of 8 L, and hydrothermally synthesized at 140 ° C. for 1 hour to produce a precipitate.
Next, the obtained precipitate was washed with water to obtain a cake-like electrode active material.
Next, 0.1 mol of lithium hydroxide (LiOH), 0.1 mol of iron (II) acetate (Fe (CH ₃ COO) ₂ ), and 0.1 mol of phosphoric acid (H) were added to the cake-like electrode active material. ₃ PO ₄ ) and 1.92 × 10 ⁻⁵ mol of lithium sulfate (Li ₂ SO ₄ ) are added, mixed so that the total amount becomes 2 L, dried, and averaged on the surface of the electrode active material. LiFePO ₄ 0.1 mol with a primary particle diameter of 5 nm was uniformly supported and dried to obtain a mixture containing an electrode active material.
Next, 150 g of this mixture, 20 g of lactose as the organic compound II, dispersed in and dissolved in 200 g of water, an aqueous lactose solution and 500 g of zirconia balls having a diameter of 0.1 mm as medium particles were put into a ball mill, and the electrode activity in the slurry was The ball mill rotational speed and the stirring time were adjusted so that the ratio (D90 / D10) of D90 to D10 in the particle size distribution of the substance was 30, and the dispersion treatment was performed. Thereby, the slurry containing an electrode active material was obtained.
Next, the obtained slurry was sprayed into an air atmosphere at 200 ° C. and dried to obtain a dried product.
Next, the obtained dried product was fired at 700 ° C. for 1 hour in a nitrogen atmosphere to obtain a carbon-coated electrode active material aggregate having an average secondary particle size of 20 μm. After mixing 85 mass% of ethylene carbonate powder as the organic compound I with this aggregate, the mixture was heated at 50 ° C. for 1 hour in a nitrogen atmosphere to confirm that the ethylene carbonate was melted, and then cooled to obtain Example 26. Electrode material for a lithium ion secondary battery.
Next, an electrode for a lithium ion secondary battery of Example 26 was produced in the same manner as in Example 1 except that the electrode material for a lithium ion secondary battery of Example 26 was used. In addition, a lithium ion secondary battery of Example 26 was fabricated in the same manner as in Example 1 using the obtained electrode for a lithium ion secondary battery.

(Example 27)
In 2 L (liter) of water, 6 mol of lithium hydroxide (LiOH), 0.53 mol of iron (II) acetate (Fe (CH ₃ COO) ₂ ), and 0.01 mol of cobalt (II) acetate (Co (CH ₃ COO) ₂ ), 0.06 mol of magnesium acetate (Mg (CH ₃ COO) ₂ ), 1.4 mol of manganese (II) acetate (Mn (CH ₃ COO) ₂ ), 2 mol of phosphoric acid (H ₃ PO ₄ ) and 0.123 mol of lithium sulfate (Li ₂ SO ₄ ) were added and mixed so that the total amount was 4 L to prepare a uniform slurry mixture.
Next, this mixture was placed in a pressure-resistant airtight container having a capacity of 8 L, and hydrothermally synthesized at 140 ° C. for 1 hour to produce a precipitate.
Next, the obtained precipitate was washed with water to obtain a cake-like electrode active material.
Next, 0.1 mol of lithium hydroxide (LiOH), 0.1 mol of iron (II) acetate (Fe (CH ₃ COO) ₂ ), and 0.1 mol of phosphoric acid (H) were added to the cake-like electrode active material. ₃ PO ₄ ) and 1.92 × 10 ⁻⁵ mol of lithium sulfate (Li ₂ SO ₄ ) are added, mixed so that the total amount becomes 2 L, dried, and averaged on the surface of the electrode active material. LiFePO ₄ 0.1 mol with a primary particle diameter of 5 nm was uniformly supported and dried to obtain a mixture containing an electrode active material.
Next, 150 g of this mixture, 4 g of lactose as the organic compound II, dispersed in 200 g of water and an aqueous lactose solution and 500 g of zirconia balls having a diameter of 0.1 mm as medium particles are put into a ball mill, and the electrode activity in the slurry is increased. The ball mill rotational speed and the stirring time were adjusted so that the ratio (D90 / D10) of D90 to D10 in the particle size distribution of the substance was 30, and the dispersion treatment was performed. Thereby, the slurry containing an electrode active material was obtained.
Next, the obtained slurry was sprayed into an air atmosphere at 200 ° C. and dried to obtain a dried product.
Next, the obtained dried product was fired at 700 ° C. for 1 hour in a nitrogen atmosphere to obtain a carbon-coated electrode active material aggregate having an average secondary particle size of 20 μm. The aggregate was mixed with 20% by mass of sulfolane powder as organic compound I, and then heated at 50 ° C. for 1 hour in a nitrogen atmosphere to confirm that the sulfolane was melted. It was set as the electrode material for ion secondary batteries.
Next, an electrode for a lithium ion secondary battery of Example 27 was produced in the same manner as in Example 1 except that the electrode material for a lithium ion secondary battery of Example 27 was used. Further, a lithium ion secondary battery of Example 27 was produced in the same manner as in Example 1 by using the obtained electrode for a lithium ion secondary battery.

(Example 28)
In 2 L (liter) of water, 6 mol of lithium hydroxide (LiOH), 0.53 mol of iron (II) acetate (Fe (CH ₃ COO) ₂ ), and 0.01 mol of cobalt (II) acetate (Co (CH ₃ COO) ₂ ), 0.06 mol of magnesium acetate (Mg (CH ₃ COO) ₂ ), 1.4 mol of manganese (II) acetate (Mn (CH ₃ COO) ₂ ), 2 mol of phosphoric acid (H ₃ PO ₄ ) and 0.123 mol of lithium sulfate (Li ₂ SO ₄ ) were added and mixed so that the total amount was 4 L to prepare a uniform slurry mixture.
Next, this mixture was placed in a pressure-resistant airtight container having a capacity of 8 L, and hydrothermally synthesized at 140 ° C. for 1 hour to produce a precipitate.
Next, the obtained precipitate was washed with water to obtain a cake-like electrode active material.
Next, 0.1 mol of lithium hydroxide (LiOH), 0.1 mol of iron (II) acetate (Fe (CH ₃ COO) ₂ ), and 0.1 mol of phosphoric acid (H) were added to the cake-like electrode active material. ₃ PO ₄ ) and 1.92 × 10 ⁻⁵ mol of lithium sulfate (Li ₂ SO ₄ ) are added, mixed so that the total amount becomes 2 L, dried, and averaged on the surface of the electrode active material. LiFePO ₄ 0.1 mol with a primary particle diameter of 5 nm was uniformly supported and dried to obtain a mixture containing an electrode active material.
Next, 150 g of this mixture, 7 g of lactose as the organic compound II, dispersed in and dissolved in 200 g of water, an aqueous lactose solution and 500 g of zirconia balls having a diameter of 0.1 mm as medium particles were put into a ball mill, and the electrode activity in the slurry was The ball mill rotational speed and the stirring time were adjusted so that the ratio (D90 / D10) of D90 to D10 in the particle size distribution of the substance was 30, and the dispersion treatment was performed. Thereby, the slurry containing an electrode active material was obtained.
Next, the obtained slurry was sprayed into an air atmosphere at 200 ° C. and dried to obtain a dried product.
Next, the obtained dried product was fired at 700 ° C. for 1 hour in a nitrogen atmosphere to obtain a carbon-coated electrode active material aggregate having an average secondary particle size of 20 μm. This aggregate was mixed with 35% by mass of sulfolane powder as the organic compound I, heated in a nitrogen atmosphere at 50 ° C. for 1 hour to confirm that the sulfolane was melted, cooled, and cooled to the lithium of Example 28. It was set as the electrode material for ion secondary batteries.
Next, an electrode for a lithium ion secondary battery of Example 28 was produced in the same manner as in Example 1 except that the electrode material for a lithium ion secondary battery of Example 28 was used. Further, using the obtained electrode for a lithium ion secondary battery, a lithium ion secondary battery of Example 28 was produced in the same manner as in Example 1.

(Example 29)
In 2 L (liter) of water, 6 mol of lithium hydroxide (LiOH), 0.53 mol of iron (II) acetate (Fe (CH ₃ COO) ₂ ), and 0.01 mol of cobalt (II) acetate (Co (CH ₃ COO) ₂ ), 0.06 mol of magnesium acetate (Mg (CH ₃ COO) ₂ ), 1.4 mol of manganese (II) acetate (Mn (CH ₃ COO) ₂ ), 2 mol of phosphoric acid (H ₃ PO ₄ ) and 0.123 mol of lithium sulfate (Li ₂ SO ₄ ) were added and mixed so that the total amount was 4 L to prepare a uniform slurry mixture.
Next, this mixture was placed in a pressure-resistant airtight container having a capacity of 8 L, and hydrothermally synthesized at 140 ° C. for 1 hour to produce a precipitate.
Next, the obtained precipitate was washed with water to obtain a cake-like electrode active material.
Next, 0.1 mol of lithium hydroxide (LiOH), 0.1 mol of iron (II) acetate (Fe (CH ₃ COO) ₂ ), and 0.1 mol of phosphoric acid (H) were added to the cake-like electrode active material. ₃ PO ₄ ) and 1.92 × 10 ⁻⁵ mol of lithium sulfate (Li ₂ SO ₄ ) are added, mixed so that the total amount becomes 2 L, dried, and averaged on the surface of the electrode active material. LiFePO ₄ 0.1 mol with a primary particle diameter of 5 nm was uniformly supported and dried to obtain a mixture containing an electrode active material.
Next, 150 g of this mixture, 9 g of lactose as an organic compound II, dispersed in 200 g of water and an aqueous lactose solution and 500 g of zirconia balls having a diameter of 0.1 mm as medium particles were put into a ball mill, and the electrode activity in the slurry was The ball mill rotational speed and the stirring time were adjusted so that the ratio (D90 / D10) of D90 to D10 in the particle size distribution of the substance was 30, and the dispersion treatment was performed. Thereby, the slurry containing an electrode active material was obtained.
Next, the obtained slurry was sprayed into an air atmosphere at 200 ° C. and dried to obtain a dried product.
Next, the obtained dried product was fired at 700 ° C. for 1 hour in a nitrogen atmosphere to obtain a carbon-coated electrode active material aggregate having an average secondary particle size of 20 μm. After 40 mass% of the sulfolane powder as the organic compound I was mixed with this aggregate, the mixture was heated at 50 ° C. for 1 hour in a nitrogen atmosphere to confirm that the sulfolane was melted, and then cooled and the lithium of Example 29 was cooled. It was set as the electrode material for ion secondary batteries.
Next, an electrode for a lithium ion secondary battery of Example 29 was produced in the same manner as in Example 1 except that the electrode material for a lithium ion secondary battery of Example 29 was used. In addition, a lithium ion secondary battery of Example 29 was produced in the same manner as in Example 1 by using the obtained electrode for lithium ion secondary battery.

(Example 30)
In 2 L (liter) of water, 6 mol of lithium hydroxide (LiOH), 0.53 mol of iron (II) acetate (Fe (CH ₃ COO) ₂ ), and 0.01 mol of cobalt (II) acetate (Co (CH ₃ COO) ₂ ), 0.06 mol of magnesium acetate (Mg (CH ₃ COO) ₂ ), 1.4 mol of manganese (II) acetate (Mn (CH ₃ COO) ₂ ), 2 mol of phosphoric acid (H ₃ PO ₄ ) and 0.123 mol of lithium sulfate (Li ₂ SO ₄ ) were added and mixed so that the total amount was 4 L to prepare a uniform slurry mixture.
Next, this mixture was placed in a pressure-resistant airtight container having a capacity of 8 L, and hydrothermally synthesized at 140 ° C. for 1 hour to produce a precipitate.
Next, the obtained precipitate was washed with water to obtain a cake-like electrode active material.
Next, 0.1 mol of lithium hydroxide (LiOH), 0.1 mol of iron (II) acetate (Fe (CH ₃ COO) ₂ ), and 0.1 mol of phosphoric acid (H) were added to the cake-like electrode active material. ₃ PO ₄ ) and 1.92 × 10 ⁻⁵ mol of lithium sulfate (Li ₂ SO ₄ ) are added, mixed so that the total amount becomes 2 L, dried, and averaged on the surface of the electrode active material. LiFePO ₄ 0.1 mol with a primary particle diameter of 5 nm was uniformly supported and dried to obtain a mixture containing an electrode active material.
Next, 150 g of this mixture, 13 g of lactose as the organic compound II, dispersed in 200 g of water and an aqueous lactose solution and 500 g of zirconia balls having a diameter of 0.1 mm as medium particles were put into a ball mill, and the electrode activity in the slurry was The ball mill rotational speed and the stirring time were adjusted so that the ratio (D90 / D10) of D90 to D10 in the particle size distribution of the substance was 30, and the dispersion treatment was performed. Thereby, the slurry containing an electrode active material was obtained.
Next, the obtained slurry was sprayed into an air atmosphere at 200 ° C. and dried to obtain a dried product.
Next, the obtained dried product was fired at 700 ° C. for 1 hour in a nitrogen atmosphere to obtain a carbon-coated electrode active material aggregate having an average secondary particle size of 20 μm. The aggregate was mixed with 65% by mass of sulfolane powder as the organic compound I, heated in a nitrogen atmosphere at 50 ° C. for 1 hour to confirm that the sulfolane was melted, cooled, and cooled to the lithium of Example 30. It was set as the electrode material for ion secondary batteries.
Next, an electrode for a lithium ion secondary battery of Example 30 was produced in the same manner as in Example 1 except that the electrode material for a lithium ion secondary battery of Example 30 was used. In addition, a lithium ion secondary battery of Example 30 was produced in the same manner as in Example 1 using the obtained electrode for a lithium ion secondary battery.

(Example 31)
In 2 L (liter) of water, 6 mol of lithium hydroxide (LiOH), 0.53 mol of iron (II) acetate (Fe (CH ₃ COO) ₂ ), and 0.01 mol of cobalt (II) acetate (Co (CH ₃ COO) ₂ ), 0.06 mol of magnesium acetate (Mg (CH ₃ COO) ₂ ), 1.4 mol of manganese (II) acetate (Mn (CH ₃ COO) ₂ ), 2 mol of phosphoric acid (H ₃ PO ₄ ) and 0.123 mol of lithium sulfate (Li ₂ SO ₄ ) were added and mixed so that the total amount was 4 L to prepare a uniform slurry mixture.
Next, this mixture was placed in a pressure-resistant airtight container having a capacity of 8 L, and hydrothermally synthesized at 140 ° C. for 1 hour to produce a precipitate.
Next, the obtained precipitate was washed with water to obtain a cake-like electrode active material.
Next, 0.1 mol of lithium hydroxide (LiOH), 0.1 mol of iron (II) acetate (Fe (CH ₃ COO) ₂ ), and 0.1 mol of phosphoric acid (H) were added to the cake-like electrode active material. ₃ PO ₄ ) and 1.92 × 10 ⁻⁵ mol of lithium sulfate (Li ₂ SO ₄ ) are added, mixed so that the total amount becomes 2 L, dried, and averaged on the surface of the electrode active material. LiFePO ₄ 0.1 mol with a primary particle diameter of 5 nm was uniformly supported and dried to obtain a mixture containing an electrode active material.
Next, 150 g of this mixture and 17 g of lactose as the organic compound II are dispersed and dissolved in 200 g of water, and 500 g of zirconia balls having a diameter of 0.1 mm as medium particles are put into a ball mill, and the electrode activity in the slurry is increased. The ball mill rotational speed and the stirring time were adjusted so that the ratio (D90 / D10) of D90 to D10 in the particle size distribution of the substance was 30, and the dispersion treatment was performed. Thereby, the slurry containing an electrode active material was obtained.
Next, the obtained slurry was sprayed into an air atmosphere at 200 ° C. and dried to obtain a dried product.
Next, the obtained dried product was fired at 700 ° C. for 1 hour in a nitrogen atmosphere to obtain a carbon-coated electrode active material aggregate having an average secondary particle size of 20 μm. The aggregate was mixed with 70% by mass of sulfolane powder as the organic compound I, heated in a nitrogen atmosphere at 50 ° C. for 1 hour to confirm that the sulfolane was melted, cooled, and cooled to the lithium of Example 31. It was set as the electrode material for ion secondary batteries.
Next, an electrode for a lithium ion secondary battery of Example 31 was produced in the same manner as in Example 1 except that the electrode material for a lithium ion secondary battery of Example 31 was used. In addition, a lithium ion secondary battery of Example 31 was produced in the same manner as in Example 1 using the obtained electrode for a lithium ion secondary battery.

(Example 32)
In 2 L (liter) of water, 6 mol of lithium hydroxide (LiOH), 0.53 mol of iron (II) acetate (Fe (CH ₃ COO) ₂ ), and 0.01 mol of cobalt (II) acetate (Co (CH ₃ COO) ₂ ), 0.06 mol of magnesium acetate (Mg (CH ₃ COO) ₂ ), 1.4 mol of manganese (II) acetate (Mn (CH ₃ COO) ₂ ), 2 mol of phosphoric acid (H ₃ PO ₄ ) and 0.123 mol of lithium sulfate (Li ₂ SO ₄ ) were added and mixed so that the total amount was 4 L to prepare a uniform slurry mixture.
Next, this mixture was placed in a pressure-resistant airtight container having a capacity of 8 L, and hydrothermally synthesized at 140 ° C. for 1 hour to produce a precipitate.
Next, the obtained precipitate was washed with water to obtain a cake-like electrode active material.
Next, 0.1 mol of lithium hydroxide (LiOH), 0.1 mol of iron (II) acetate (Fe (CH ₃ COO) ₂ ), and 0.1 mol of phosphoric acid (H) were added to the cake-like electrode active material. ₃ PO ₄ ) and 1.92 × 10 ⁻⁵ mol of lithium sulfate (Li ₂ SO ₄ ) are added, mixed so that the total amount becomes 2 L, dried, and averaged on the surface of the electrode active material. LiFePO ₄ 0.1 mol with a primary particle diameter of 5 nm was uniformly supported and dried to obtain a mixture containing an electrode active material.
Next, 150 g of this mixture, 20 g of lactose as the organic compound II, dispersed in and dissolved in 200 g of water, an aqueous lactose solution and 500 g of zirconia balls having a diameter of 0.1 mm as medium particles were put into a ball mill, and the electrode activity in the slurry was The ball mill rotational speed and the stirring time were adjusted so that the ratio (D90 / D10) of D90 to D10 in the particle size distribution of the substance was 30, and the dispersion treatment was performed. Thereby, the slurry containing an electrode active material was obtained.
Next, the obtained slurry was sprayed into an air atmosphere at 200 ° C. and dried to obtain a dried product.
Next, the obtained dried product was fired at 700 ° C. for 1 hour in a nitrogen atmosphere to obtain a carbon-coated electrode active material aggregate having an average secondary particle size of 20 μm. After 85 mass% of the sulfolane powder as the organic compound I was mixed with this aggregate, the mixture was heated at 50 ° C. for 1 hour in a nitrogen atmosphere to confirm that the sulfolane was melted, and then cooled and the lithium of Example 32 was cooled. An electrode material for ion secondary batteries was obtained.
Next, an electrode for a lithium ion secondary battery of Example 32 was produced in the same manner as in Example 1 except that the electrode material for a lithium ion secondary battery of Example 32 was used. In addition, a lithium ion secondary battery of Example 32 was produced in the same manner as in Example 1 by using the obtained electrode for lithium ion secondary battery.

(Example 33)
In 2 L (liter) of water, 6 mol of lithium hydroxide (LiOH), 0.53 mol of iron (II) acetate (Fe (CH ₃ COO) ₂ ), and 0.01 mol of cobalt (II) acetate (Co (CH ₃ COO) ₂ ), 0.06 mol of magnesium acetate (Mg (CH ₃ COO) ₂ ), 1.4 mol of manganese (II) acetate (Mn (CH ₃ COO) ₂ ), 2 mol of phosphoric acid (H ₃ PO ₄ ) and 0.123 mol of lithium sulfate (Li ₂ SO ₄ ) were added and mixed so that the total amount was 4 L to prepare a uniform slurry mixture.
Next, this mixture was placed in a pressure-resistant airtight container having a capacity of 8 L, and hydrothermally synthesized at 140 ° C. for 1 hour to produce a precipitate.
Next, the obtained precipitate was washed with water to obtain a cake-like electrode active material.
Next, 0.1 mol of lithium hydroxide (LiOH), 0.1 mol of iron (II) acetate (Fe (CH ₃ COO) ₂ ), and 0.1 mol of phosphoric acid (H) were added to the cake-like electrode active material. ₃ PO ₄ ) and 1.92 × 10 ⁻⁵ mol of lithium sulfate (Li ₂ SO ₄ ) are added, mixed so that the total amount becomes 2 L, dried, and averaged on the surface of the electrode active material. LiFePO ₄ 0.1 mol with a primary particle diameter of 5 nm was uniformly supported and dried to obtain a mixture containing an electrode active material.
Next, 150 g of this mixture, 4 g of lactose as the organic compound II, dispersed in 200 g of water and an aqueous lactose solution and 500 g of zirconia balls having a diameter of 0.1 mm as medium particles are put into a ball mill, and the electrode activity in the slurry is increased. The ball mill rotational speed and the stirring time were adjusted so that the ratio (D90 / D10) of D90 to D10 in the particle size distribution of the substance was 30, and the dispersion treatment was performed. Thereby, the slurry containing an electrode active material was obtained.
Next, the obtained slurry was sprayed into an air atmosphere at 200 ° C. and dried to obtain a dried product.
Next, the obtained dried product was fired at 700 ° C. for 1 hour in a nitrogen atmosphere to obtain a carbon-coated electrode active material aggregate having an average secondary particle size of 20 μm. This aggregate was mixed with 20% by mass of ethyl methyl sulfone powder as organic compound I, and then heated at 50 ° C. for 1 hour in a nitrogen atmosphere to confirm that ethyl methyl sulfone had melted, and then cooled and carried out. The electrode material for lithium ion secondary batteries of Example 33 was obtained.
Next, an electrode for a lithium ion secondary battery of Example 33 was produced in the same manner as in Example 1 except that the electrode material for a lithium ion secondary battery of Example 33 was used. In addition, a lithium ion secondary battery of Example 33 was produced in the same manner as in Example 1 using the obtained electrode for a lithium ion secondary battery.

(Example 34)
In 2 L (liter) of water, 6 mol of lithium hydroxide (LiOH), 0.53 mol of iron (II) acetate (Fe (CH ₃ COO) ₂ ), and 0.01 mol of cobalt (II) acetate (Co (CH ₃ COO) ₂ ), 0.06 mol of magnesium acetate (Mg (CH ₃ COO) ₂ ), 1.4 mol of manganese (II) acetate (Mn (CH ₃ COO) ₂ ), 2 mol of phosphoric acid (H ₃ PO ₄ ) and 0.123 mol of lithium sulfate (Li ₂ SO ₄ ) were added and mixed so that the total amount was 4 L to prepare a uniform slurry mixture.
Next, this mixture was placed in a pressure-resistant airtight container having a capacity of 8 L, and hydrothermally synthesized at 140 ° C. for 1 hour to produce a precipitate.
Next, the obtained precipitate was washed with water to obtain a cake-like electrode active material.
Next, 0.1 mol of lithium hydroxide (LiOH), 0.1 mol of iron (II) acetate (Fe (CH ₃ COO) ₂ ), and 0.1 mol of phosphoric acid (H) were added to the cake-like electrode active material. ₃ PO ₄ ) and 1.92 × 10 ⁻⁵ mol of lithium sulfate (Li ₂ SO ₄ ) are added, mixed so that the total amount becomes 2 L, dried, and averaged on the surface of the electrode active material. LiFePO ₄ 0.1 mol with a primary particle diameter of 5 nm was uniformly supported and dried to obtain a mixture containing an electrode active material.
Next, 150 g of this mixture, 7 g of lactose as the organic compound II, dispersed in and dissolved in 200 g of water, an aqueous lactose solution and 500 g of zirconia balls having a diameter of 0.1 mm as medium particles were put into a ball mill, and the electrode activity in the slurry was The ball mill rotational speed and the stirring time were adjusted so that the ratio (D90 / D10) of D90 to D10 in the particle size distribution of the substance was 30, and the dispersion treatment was performed. Thereby, the slurry containing an electrode active material was obtained.
Next, the obtained slurry was sprayed into an air atmosphere at 200 ° C. and dried to obtain a dried product.
Next, the obtained dried product was fired at 700 ° C. for 1 hour in a nitrogen atmosphere to obtain a carbon-coated electrode active material aggregate having an average secondary particle size of 20 μm. After mixing 35% by mass of ethylmethylsulfone powder as organic compound I with this aggregate, the mixture was heated at 50 ° C. for 1 hour in a nitrogen atmosphere to confirm that ethylmethylsulfone had melted, and then cooled and carried out. The electrode material for the lithium ion secondary battery of Example 34 was obtained.
Next, an electrode for a lithium ion secondary battery of Example 34 was produced in the same manner as in Example 1 except that the electrode material for a lithium ion secondary battery of Example 34 was used. In addition, a lithium ion secondary battery of Example 34 was produced in the same manner as in Example 1 by using the obtained electrode for lithium ion secondary battery.

(Example 35)
In 2 L (liter) of water, 6 mol of lithium hydroxide (LiOH), 0.53 mol of iron (II) acetate (Fe (CH ₃ COO) ₂ ), and 0.01 mol of cobalt (II) acetate (Co (CH ₃ COO) ₂ ), 0.06 mol of magnesium acetate (Mg (CH ₃ COO) ₂ ), 1.4 mol of manganese (II) acetate (Mn (CH ₃ COO) ₂ ), 2 mol of phosphoric acid (H ₃ PO ₄ ) and 0.123 mol of lithium sulfate (Li ₂ SO ₄ ) were added and mixed so that the total amount was 4 L to prepare a uniform slurry mixture.
Next, this mixture was placed in a pressure-resistant airtight container having a capacity of 8 L, and hydrothermally synthesized at 140 ° C. for 1 hour to produce a precipitate.
Next, the obtained precipitate was washed with water to obtain a cake-like electrode active material.
Next, 0.1 mol of lithium hydroxide (LiOH), 0.1 mol of iron (II) acetate (Fe (CH ₃ COO) ₂ ), and 0.1 mol of phosphoric acid (H) were added to the cake-like electrode active material. ₃ PO ₄ ) and 1.92 × 10 ⁻⁵ mol of lithium sulfate (Li ₂ SO ₄ ) are added, mixed so that the total amount becomes 2 L, dried, and averaged on the surface of the electrode active material. LiFePO ₄ 0.1 mol with a primary particle diameter of 5 nm was uniformly supported and dried to obtain a mixture containing an electrode active material.
Next, 150 g of this mixture, 9 g of lactose as an organic compound II, dispersed in 200 g of water and an aqueous lactose solution and 500 g of zirconia balls having a diameter of 0.1 mm as medium particles were put into a ball mill, and the electrode activity in the slurry was The ball mill rotational speed and the stirring time were adjusted so that the ratio (D90 / D10) of D90 to D10 in the particle size distribution of the substance was 30, and the dispersion treatment was performed. Thereby, the slurry containing an electrode active material was obtained.
Next, the obtained slurry was sprayed into an air atmosphere at 200 ° C. and dried to obtain a dried product.
Next, the obtained dried product was fired at 700 ° C. for 1 hour in a nitrogen atmosphere to obtain a carbon-coated electrode active material aggregate having an average secondary particle size of 20 μm. After 40 mass% of ethylmethylsulfone powder as organic compound I was mixed with this aggregate, the mixture was heated at 50 ° C. for 1 hour in a nitrogen atmosphere to confirm that ethylmethylsulfone was melted, and then cooled and carried out. The electrode material for lithium ion secondary batteries of Example 35 was obtained.
Subsequently, the electrode for lithium ion secondary batteries of Example 35 was produced like Example 1 except having used the electrode material for lithium ion secondary batteries of Example 35. FIG. In addition, a lithium ion secondary battery of Example 35 was produced in the same manner as in Example 1 by using the obtained electrode for a lithium ion secondary battery.

(Example 36)
In 2 L (liter) of water, 6 mol of lithium hydroxide (LiOH), 0.53 mol of iron (II) acetate (Fe (CH ₃ COO) ₂ ), and 0.01 mol of cobalt (II) acetate (Co (CH ₃ COO) ₂ ), 0.06 mol of magnesium acetate (Mg (CH ₃ COO) ₂ ), 1.4 mol of manganese (II) acetate (Mn (CH ₃ COO) ₂ ), 2 mol of phosphoric acid (H ₃ PO ₄ ) and 0.123 mol of lithium sulfate (Li ₂ SO ₄ ) were added and mixed so that the total amount was 4 L to prepare a uniform slurry mixture.
Next, this mixture was placed in a pressure-resistant airtight container having a capacity of 8 L, and hydrothermally synthesized at 140 ° C. for 1 hour to produce a precipitate.
Next, the obtained precipitate was washed with water to obtain a cake-like electrode active material.
Next, 0.1 mol of lithium hydroxide (LiOH), 0.1 mol of iron (II) acetate (Fe (CH ₃ COO) ₂ ), and 0.1 mol of phosphoric acid (H) were added to the cake-like electrode active material. ₃ PO ₄ ) and 1.92 × 10 ⁻⁵ mol of lithium sulfate (Li ₂ SO ₄ ) are added, mixed so that the total amount becomes 2 L, dried, and averaged on the surface of the electrode active material. LiFePO ₄ 0.1 mol with a primary particle diameter of 5 nm was uniformly supported and dried to obtain a mixture containing an electrode active material.
Next, 150 g of this mixture, 13 g of lactose as the organic compound II, dispersed in 200 g of water and an aqueous lactose solution and 500 g of zirconia balls having a diameter of 0.1 mm as medium particles were put into a ball mill, and the electrode activity in the slurry was The ball mill rotational speed and the stirring time were adjusted so that the ratio (D90 / D10) of D90 to D10 in the particle size distribution of the substance was 30, and the dispersion treatment was performed. Thereby, the slurry containing an electrode active material was obtained.
Next, the obtained slurry was sprayed into an air atmosphere at 200 ° C. and dried to obtain a dried product.
Next, the obtained dried product was fired at 700 ° C. for 1 hour in a nitrogen atmosphere to obtain a carbon-coated electrode active material aggregate having an average secondary particle size of 20 μm. After mixing 65% by mass of ethylmethylsulfone powder as organic compound I with this agglomerate, heating at 50 ° C. for 1 hour in a nitrogen atmosphere to confirm that ethylmethylsulfone was melted, cooling and carrying out The electrode material for a lithium ion secondary battery of Example 36 was obtained.
Next, a lithium ion secondary battery electrode of Example 36 was produced in the same manner as in Example 1 except that the lithium ion secondary battery electrode material of Example 36 was used. Further, using the obtained electrode for a lithium ion secondary battery, a lithium ion secondary battery of Example 36 was produced in the same manner as in Example 1.

(Example 37)
In 2 L (liter) of water, 6 mol of lithium hydroxide (LiOH), 0.53 mol of iron (II) acetate (Fe (CH ₃ COO) ₂ ), and 0.01 mol of cobalt (II) acetate (Co (CH ₃ COO) ₂ ), 0.06 mol of magnesium acetate (Mg (CH ₃ COO) ₂ ), 1.4 mol of manganese (II) acetate (Mn (CH ₃ COO) ₂ ), 2 mol of phosphoric acid (H ₃ PO ₄ ) and 0.123 mol of lithium sulfate (Li ₂ SO ₄ ) were added and mixed so that the total amount was 4 L to prepare a uniform slurry mixture.
Next, this mixture was placed in a pressure-resistant airtight container having a capacity of 8 L, and hydrothermally synthesized at 140 ° C. for 1 hour to produce a precipitate.
Next, the obtained precipitate was washed with water to obtain a cake-like electrode active material.
Next, 0.1 mol of lithium hydroxide (LiOH), 0.1 mol of iron (II) acetate (Fe (CH ₃ COO) ₂ ), and 0.1 mol of phosphoric acid (H) were added to the cake-like electrode active material. ₃ PO ₄ ) and 1.92 × 10 ⁻⁵ mol of lithium sulfate (Li ₂ SO ₄ ) are added, mixed so that the total amount becomes 2 L, dried, and averaged on the surface of the electrode active material. LiFePO ₄ 0.1 mol with a primary particle diameter of 5 nm was uniformly supported and dried to obtain a mixture containing an electrode active material.
Next, 150 g of this mixture and 17 g of lactose as the organic compound II are dispersed and dissolved in 200 g of water, and 500 g of zirconia balls having a diameter of 0.1 mm as medium particles are put into a ball mill, and the electrode activity in the slurry is increased. The ball mill rotational speed and the stirring time were adjusted so that the ratio (D90 / D10) of D90 to D10 in the particle size distribution of the substance was 30, and the dispersion treatment was performed. Thereby, the slurry containing an electrode active material was obtained.
Next, the obtained slurry was sprayed into an air atmosphere at 200 ° C. and dried to obtain a dried product.
Next, the obtained dried product was fired at 700 ° C. for 1 hour in a nitrogen atmosphere to obtain a carbon-coated electrode active material aggregate having an average secondary particle size of 20 μm. After 70 mass% of ethyl methyl sulfone powder as organic compound I was mixed with this aggregate, it was heated at 50 ° C. for 1 hour in a nitrogen atmosphere to confirm that ethyl methyl sulfone was melted, and then cooled and carried out. The lithium ion secondary battery electrode material of Example 37 was obtained.
Subsequently, the electrode for lithium ion secondary batteries of Example 37 was produced like Example 1 except having used the electrode material for lithium ion secondary batteries of Example 37. FIG. In addition, a lithium ion secondary battery of Example 37 was produced in the same manner as in Example 1 by using the obtained electrode for a lithium ion secondary battery.

(Example 38)
In 2 L (liter) of water, 6 mol of lithium hydroxide (LiOH), 0.53 mol of iron (II) acetate (Fe (CH ₃ COO) ₂ ), and 0.01 mol of cobalt (II) acetate (Co (CH ₃ COO) ₂ ), 0.06 mol of magnesium acetate (Mg (CH ₃ COO) ₂ ), 1.4 mol of manganese (II) acetate (Mn (CH ₃ COO) ₂ ), 2 mol of phosphoric acid (H ₃ PO ₄ ) and 0.123 mol of lithium sulfate (Li ₂ SO ₄ ) were added and mixed so that the total amount was 4 L to prepare a uniform slurry mixture.
Next, this mixture was placed in a pressure-resistant airtight container having a capacity of 8 L, and hydrothermally synthesized at 140 ° C. for 1 hour to produce a precipitate.
Next, the obtained precipitate was washed with water to obtain a cake-like electrode active material.
Next, 0.1 mol of lithium hydroxide (LiOH), 0.1 mol of iron (II) acetate (Fe (CH ₃ COO) ₂ ), and 0.1 mol of phosphoric acid (H) were added to the cake-like electrode active material. ₃ PO ₄ ) and 1.92 × 10 ⁻⁵ mol of lithium sulfate (Li ₂ SO ₄ ) are added, mixed so that the total amount becomes 2 L, dried, and averaged on the surface of the electrode active material. LiFePO ₄ 0.1 mol with a primary particle diameter of 5 nm was uniformly supported and dried to obtain a mixture containing an electrode active material.
Next, 150 g of this mixture, 20 g of lactose as the organic compound II, dispersed in and dissolved in 200 g of water, an aqueous lactose solution and 500 g of zirconia balls having a diameter of 0.1 mm as medium particles were put into a ball mill, and the electrode activity in the slurry was The ball mill rotational speed and the stirring time were adjusted so that the ratio (D90 / D10) of D90 to D10 in the particle size distribution of the substance was 30, and the dispersion treatment was performed. Thereby, the slurry containing an electrode active material was obtained.
Next, the obtained slurry was sprayed into an air atmosphere at 200 ° C. and dried to obtain a dried product.
Next, the obtained dried product was fired at 700 ° C. for 1 hour in a nitrogen atmosphere to obtain a carbon-coated electrode active material aggregate having an average secondary particle size of 20 μm. After 85 mass% of ethylmethylsulfone powder as organic compound I was mixed with this aggregate, the mixture was heated at 50 ° C. for 1 hour in a nitrogen atmosphere to confirm that ethylmethylsulfone had melted, and then cooled and carried out. The electrode material for a lithium ion secondary battery of Example 38 was obtained.
Next, an electrode for a lithium ion secondary battery of Example 38 was produced in the same manner as in Example 1 except that the electrode material for a lithium ion secondary battery of Example 38 was used. In addition, a lithium ion secondary battery of Example 38 was produced in the same manner as in Example 1 by using the obtained electrode for a lithium ion secondary battery.

(Comparative Example 1)
In 2 L (liter) of water, 6 mol of lithium hydroxide (LiOH), 2 mol of iron (II) acetate (Fe (CH ₃ COO) ₂ ), 2 mol of phosphoric acid (H ₃ PO ₄ ), 0.100 mol Lithium sulfate (Li ₂ SO ₄ ) was added and mixed so that the total amount was 4 L to prepare a uniform slurry mixture.
Subsequently, this mixture was accommodated in a pressure-resistant airtight container having a capacity of 8 L, and hydrothermal synthesis was performed at 170 ° C. for 1 hour to produce a precipitate.
Next, the obtained precipitate was washed with water to obtain a cake-like electrode active material.
Next, 150 g of this electrode active material and 24 g of lactose as an organic compound were dispersed and dissolved in 500 g of water, and 500 g of zirconia balls having a diameter of 0.1 mm as medium particles were put into a ball mill, and the electrode in the slurry The ball mill rotation speed and stirring time were adjusted so that the ratio (D90 / D10) of D90 to D10 in the particle size distribution of the active material was 30, and dispersion treatment was performed. Thereby, the slurry containing an electrode active material was obtained.
Next, the obtained slurry was sprayed into an air atmosphere at 200 ° C. and dried to obtain a dried product.
Next, the obtained dried product was fired at 700 ° C. for 1 hour in a nitrogen atmosphere to obtain an aggregate having an average secondary particle size of 0.2 μm. This aggregate was used as an electrode material for a lithium ion secondary battery of Comparative Example 1.
Next, an electrode for a lithium ion secondary battery of Comparative Example 1 was produced in the same manner as in Example 1 except that the electrode material for a lithium ion secondary battery of Comparative Example 1 was used. Further, a lithium ion secondary battery of Comparative Example 1 was produced in the same manner as in Example 1 using the obtained electrode for lithium ion secondary battery.

(Comparative Example 2)
In 2 L (liter) of water, 6 mol of lithium hydroxide (LiOH), 2 mol of iron (II) acetate (Fe (CH ₃ COO) ₂ ), 2 mol of phosphoric acid (H ₃ PO ₄ ), 0.100 mol Lithium sulfate (Li ₂ SO ₄ ) was added and mixed so that the total amount was 4 L to prepare a uniform slurry mixture.
Subsequently, this mixture was accommodated in a pressure-resistant airtight container having a capacity of 8 L, and hydrothermally synthesized at 280 ° C. for 1 hour to produce a precipitate.
Next, the obtained precipitate was washed with water to obtain a cake-like electrode active material.
Next, 150 g of this electrode active material and 3 g of lactose as an organic compound were dispersed and dissolved in 100 g of water, and 500 g of zirconia balls having a diameter of 0.1 mm as medium particles were put into a ball mill, and the electrode in the slurry The ball mill rotation speed and stirring time were adjusted so that the ratio (D90 / D10) of D90 to D10 in the particle size distribution of the active material was 30, and dispersion treatment was performed. Thereby, the slurry containing an electrode active material was obtained.
Next, the obtained slurry was sprayed into an air atmosphere at 220 ° C. and dried to obtain a dried product.
Next, the obtained dried product was fired at 800 ° C. for 1 hour in a nitrogen atmosphere to obtain an aggregate having an average secondary particle size of 55 μm. This aggregate was used as an electrode material for a lithium ion secondary battery of Comparative Example 2.
Next, a lithium ion secondary battery electrode of Comparative Example 2 was prepared in the same manner as Comparative Example 1 except that the lithium ion secondary battery electrode material of Comparative Example 2 was used. Further, a lithium ion secondary battery of Comparative Example 2 was produced in the same manner as in Comparative Example 1 using the obtained lithium ion secondary battery electrode.

(Comparative Example 3)
In 2 L (liter) of water, 6 mol of lithium hydroxide (LiOH), 0.53 mol of iron (II) acetate (Fe (CH ₃ COO) ₂ ), and 0.01 mol of cobalt (II) acetate (Co (CH ₃ COO) ₂ ), 0.06 mol of magnesium acetate (Mg (CH ₃ COO) ₂ ), 1.4 mol of manganese (II) acetate (Mn (CH ₃ COO) ₂ ), 2 mol of phosphoric acid (H ₃ PO ₄ ) and 0.123 mol of lithium sulfate (Li ₂ SO ₄ ) were added and mixed so that the total amount was 4 L to prepare a uniform slurry mixture.
Next, this mixture was placed in a pressure-resistant airtight container having a capacity of 8 L, and hydrothermally synthesized at 140 ° C. for 1 hour to produce a precipitate.
Next, the obtained precipitate was washed with water to obtain a cake-like electrode active material.
Next, 0.1 mol of lithium hydroxide (LiOH), 0.1 mol of iron (II) acetate (Fe (CH ₃ COO) ₂ ), and 0.1 mol of phosphoric acid (H) were added to the cake-like electrode active material. ₃ PO ₄ ) and 1.92 × 10 ⁻⁵ mol of lithium sulfate (Li ₂ SO ₄ ) are added, mixed so that the total amount becomes 2 L, dried, and averaged on the surface of the electrode active material. LiFePO ₄ 0.1 mol with a primary particle diameter of 5 nm was uniformly supported and dried to obtain a mixture containing an electrode active material.
Next, 150 g of this mixture and 24 g of lactose as an organic compound are dispersed and dissolved in 500 g of water, an aqueous lactose solution and 500 g of zirconia balls having a diameter of 0.1 mm as medium particles are put into a ball mill, and the electrode active material in the slurry The ball mill rotation speed and the stirring time were adjusted so that the ratio of the particle size distribution of D90 to D10 (D90 / D10) was 30, and the dispersion treatment was performed. Thereby, the slurry containing an electrode active material was obtained.
Next, the obtained slurry was sprayed into an air atmosphere at 200 ° C. and dried to obtain a dried product.
Next, the obtained dried product was fired at 700 ° C. for 1 hour in a nitrogen atmosphere to obtain an aggregate having an average secondary particle size of 0.2 μm. This aggregate was used as an electrode material for a lithium ion secondary battery of Comparative Example 3.
Next, an electrode for a lithium ion secondary battery of Comparative Example 3 was produced in the same manner as Comparative Example 1 except that the electrode material for a lithium ion secondary battery of Comparative Example 3 was used. Moreover, the lithium ion secondary battery of the comparative example 3 was produced like the comparative example 1 using the obtained electrode for lithium ion secondary batteries.

(Comparative Example 4)
In 2 L (liter) of water, 6 mol of lithium hydroxide (LiOH), 0.53 mol of iron (II) acetate (Fe (CH ₃ COO) ₂ ), and 0.01 mol of cobalt (II) acetate (Co (CH ₃ COO) ₂ ), 0.06 mol of magnesium acetate (Mg (CH ₃ COO) ₂ ), 1.4 mol of manganese (II) acetate (Mn (CH ₃ COO) ₂ ), 2 mol of phosphoric acid (H ₃ PO ₄ ) and 0.123 mol of lithium sulfate (Li ₂ SO ₄ ) were added and mixed so that the total amount was 4 L to prepare a uniform slurry mixture.
Subsequently, this mixture was accommodated in a pressure-resistant airtight container having a capacity of 8 L, and hydrothermally synthesized at 280 ° C. for 1 hour to produce a precipitate.
Next, the obtained precipitate was washed with water to obtain a cake-like electrode active material.
Next, 0.1 mol of lithium hydroxide (LiOH), 0.1 mol of iron (II) acetate (Fe (CH ₃ COO) ₂ ), and 0.1 mol of phosphoric acid (H) were added to the cake-like electrode active material. ₃ PO ₄ ) and 1.92 × 10 ⁻⁵ mol of lithium sulfate (Li ₂ SO ₄ ) are added, mixed so that the total amount becomes 2 L, dried, and averaged on the surface of the electrode active material. LiFePO ₄ 0.1 mol with a primary particle diameter of 5 nm was uniformly supported and dried to obtain a mixture containing an electrode active material.
Next, 150 g of this mixture and 3 g of lactose as an organic compound were dispersed and dissolved in 100 g of water, and 500 g of zirconia balls having a diameter of 0.1 mm as medium particles were put into a ball mill, and the electrode active material in the slurry The ball mill rotation speed and the stirring time were adjusted so that the ratio of the particle size distribution of D90 to D10 (D90 / D10) was 30, and the dispersion treatment was performed. Thereby, the slurry containing an electrode active material was obtained.
Next, the obtained slurry was sprayed into an air atmosphere at 220 ° C. and dried to obtain a dried product.
Next, the obtained dried product was fired at 800 ° C. for 1 hour in a nitrogen atmosphere to obtain an aggregate having an average secondary particle size of 55 μm. This aggregate was used as an electrode material for a lithium ion secondary battery of Comparative Example 4.
Next, an electrode for a lithium ion secondary battery of Comparative Example 4 was produced in the same manner as Comparative Example 1 except that the electrode material for a lithium ion secondary battery of Comparative Example 4 was used. Further, a lithium ion secondary battery of Comparative Example 4 was produced in the same manner as in Comparative Example 1 using the obtained electrode for lithium ion secondary battery.

[Evaluation of electrode materials]
The obtained electrode material was evaluated by the following method. The results are shown in Table 2-1 and Table 2-2.
(1) Green compact density when 51 MPa is applied Cylindrical shape of a powder resistance measurement system (trade name: MCP-PD51, manufactured by Mitsubishi Chemical Analytech Co., Ltd.) with a predetermined amount of electrode material at room temperature (25 ° C.) The pellet thickness is measured by applying a pressure of 51 MPa using a push rod, and the pellet density at the time of application of 51 MPa from the electrode material weight and the pellet volume, that is, the green compact. The density was determined.

(2) Electrode active material carbon content The carbon content in the carbon-coated electrode active material aggregate obtained in the above-described heat treatment step is the carbon-sulfur analyzer (trade name: EMIA-320V, manufactured by Horiba, Ltd.). It measured using.

(3) Average primary particle diameter of the electrode active material coated with the carbonaceous film The average primary particle diameter of the electrode active material coated with the carbonaceous film is determined by measuring the electrode active material with a scanning electron microscope (SEM; Scanning Electron Microscope). ), 100 electrode active materials were arbitrarily selected from the obtained SEM images, the major axis diameter of each particle was measured, and the average value was calculated from these measured values.

(4) Average secondary particle diameter of the electrode active material coated with the carbonaceous film The average secondary particle diameter of the electrode active material coated with the carbonaceous film is a carbonaceous film in water containing 0.3% by weight of polyvinylpyrrolidone. After the coated electrode active material was dispersed, measurement was performed using a laser diffraction / scattering particle size distribution analyzer (trade name: SALD-2000J, manufactured by Shimadzu Corporation).

(5) The crystallite diameter of the electrode active material The crystallite diameter of the electrode active material was calculated from the X-ray diffraction measurement results obtained using an X-ray diffraction measurement apparatus (trade name: X'Pert, manufactured by PANalytical). Calculated using the formula.

[Evaluation of lithium ion secondary battery]
The obtained lithium ion secondary battery was evaluated by the following method. The results are shown in Table 2-1 and Table 2-2.
(6) Charge / discharge rate performance (input / output characteristics)
After performing a charge / discharge test of a lithium ion secondary battery for 3 cycles, with a constant voltage charge / discharge (1 hour charge and 1 hour discharge) as a cycle at a cut-off voltage of 2V-4.5V and a charge / discharge rate of 1C. After performing 0.1C charge, 0.1C and 5C discharges were performed at temperatures of 25 ° C. and 0 ° C., respectively, to obtain 0.1C discharge capacity and 5C discharge capacity. A value representing the 5C discharge capacity in terms of 100 minutes when the 0.1C discharge capacity was taken as 100 was defined as “charge / discharge rate performance”.

From the results of Tables 2-1 and 2-2, the green density of the electrode materials for lithium ion secondary batteries of Examples 1 to 38 when 51 MPa was applied was 2.3 g / cm ³ or less. . In addition, the charge / discharge rate performance of the LiFePO ₄ electrode active materials of Examples 1 to 20 @ 25 ° C. 5C discharge capacity / 0.1C discharge capacity is 80% or more, and the charge / discharge rate performance @ 0 ° C. 5C discharge capacity / 0.1C discharge Capacity is 60% or more, charge / discharge rate performance of electrode active material including LiFePO ₄ and LiFe _0.265 Co _0.005 Mg _0.03 Mn _0.7 PO ₄ of Examples 21 to 38 at 25 ° C. 5C discharge capacity / 0.1C discharge capacity is 80% or more, charge / discharge rate performance @ 0 ° C 5C discharge capacity / 0.1C discharge capacity is 50% or more, both of 5C discharge capacity at 25 ° C and 0 ° C / 0.1C discharge capacity It was found that the retention rate was high and the rate characteristics were excellent.

  The lithium ion secondary battery using the electrode material for the lithium ion secondary battery according to the present invention can be charged and discharged at a high speed, which greatly improves the reliability of lithium ion secondary batteries including mobile applications. Can contribute.

Claims (8)

An electrode material in which an electrode active material has a melting point of 25 ° C. or higher and a soluble organic compound supported on an electrolyte for a lithium ion secondary battery, and has a green compact density of 2.3 g / min when 51 MPa is applied. An electrode material for a lithium ion secondary battery, wherein the electrode material is cm ³ or less. The electrode active material has the general formula _Li a _A b _D c PO compound represented by ₄ (where, A is at least one selected from the group consisting of Fe, Mn, Co and Ni, D is Mg, Ca, Sr , Ba, Ti, Zn, B, Al, Ga, In, Si, Ge, Sc, Y and at least one selected from the group consisting of rare earth elements, 0 ≦ a ≦ 1.0, 0 <b ≦ 1. The electrode material for a lithium ion secondary battery according to claim 1, wherein 0, 0 ≦ c ≦ 0.4). The electrode active material has the general formula _Li a _A b _D c PO compound represented by ₄ (where, A is at least one selected from the group consisting of Fe, Mn, Co and Ni, D is Mg, Ca, Sr , Ba, Ti, Zn, B, Al, Ga, In, Si, Ge, Sc, Y and at least one selected from the group consisting of rare earth elements, 0 ≦ a ≦ 1.0, 0 <b ≦ 1. 0, 0 ≦ c ≦ 0.4) and a compound represented by the general formula Li _e C _f PO ₄ existing on the surface of the compound represented by the general formula Li _{a Ab} D _c PO ₄ (where C is Fe And at least one selected from Mn, 0 ≦ e <2, 0 <f <1.5, and a compound different from the compound represented by the general formula Li _{a Ab} D _c PO ₄ . The lithium ion according to claim 1, Electrode material for the next battery.   The electrode material for a lithium ion secondary battery according to any one of claims 1 to 3, wherein the electrode active material is coated with a carbonaceous film.   The said organic compound is 1 type of the organic compound which comprises the electrolyte solution for lithium ion secondary batteries, The electrode material for lithium ion secondary batteries in any one of Claims 1-4 characterized by the above-mentioned.   The electrode for a lithium ion secondary battery according to claim 4 or 5, comprising an aggregate obtained by aggregating the electrode active material coated with the carbonaceous film, wherein the aggregate is granulated. material. An electrode for a lithium ion secondary battery comprising: an electrode current collector; and an electrode mixture layer formed on the electrode current collector,
The said electrode mixture layer contains the electrode material for lithium ion secondary batteries of Claim 6, The electrode for lithium ion secondary batteries characterized by the above-mentioned.   A lithium ion secondary battery comprising the electrode for a lithium ion secondary battery according to claim 7.