JP2017152114A - Method for manufacturing negative electrode active material for nonaqueous electrolyte secondary battery, and negative electrode active material for nonaqueous electrolyte secondary battery - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a method for manufacturing a negative electrode active material for a nonaqueous electrolyte secondary battery, which allows a secondary battery negative electrode to show a superior discharge capacity, and superior rate and cycle characteristics.SOLUTION: A method for manufacturing a negative electrode active material for a nonaqueous electrolyte secondary battery comprises the steps of: (I) mixing a transition metal composite oxide or a raw material compound to produce the transition metal composite oxide, one or more kinds of an organic acid, saccharide and sodium chloride, and water to obtain a slurry A of which the total addition amount of the organic acid and saccharide is 2-15 pts.mass to 100 pts.mass of the water; (II) drying and then sintering the slurry A under an oxygen atmosphere to obtain transition metal composite oxide particles X with open pores; (III) mixing the resultant transition metal composite oxide particles X with open pores with a carbon material and water to obtain a slurry B and then, stirring and drying the slurry B to obtain a granulated material Y; and (IV) sintering the granulated material Y under a reduction atmosphere or inactive atmosphere.SELECTED DRAWING: Figure 1

Description

  The present invention relates to a method for producing a negative electrode active material for a non-aqueous electrolyte secondary battery, and a negative electrode active material for a non-aqueous electrolyte secondary battery, including a step of obtaining a transition metal composite oxide negative electrode material.

  Conventionally, the use of graphite as a negative electrode for lithium ion batteries has been widespread. Such graphite has an operating potential in the vicinity of 0.1 to 0.3 V on the basis of lithium, and plays a large role in realizing higher voltage and higher energy density of the lithium ion battery.

  On the other hand, since the operating potential of such graphite is also near the deposition potential of metallic lithium, when the battery is overcharged, metallic lithium leaking from the immobile film on the graphite surface crystallizes toward the counter electrode and dendrites are generated. End up. Further, in the discharge process, the dendrite root part elutes and the tip part separates from the graphite surface and remains in the battery. The metallic lithium that remains in the electrolyte and floats is also called dead lithium, and it becomes very active micro metallic lithium, which not only lowers the charge / discharge efficiency but also causes internal short circuits and heat generation in the battery. There is also a risk of causing this.

In order to avoid the generation of dendrite and the generation of dead lithium, a material whose operating potential of the negative electrode is 1 V or more with respect to lithium is required. For example, titanium niobium oxide (TiNb ₂ O ₇ , Ti ₂ Nb ₁₀ O ₂₉ ) If present, it is reported that a high capacity of 250 to 280 mAh / g is exhibited in a potential range of 1 V or more based on lithium.

By the way, in the manufacture of a non-aqueous electrolyte secondary battery, when a transition metal composite oxide such as titanium niobium oxide or lithium titanate (Li ₄ Ti ₅ O ₁₂ ) is used as a negative electrode material, the surface is made of conductive carbon or the like. After forming an active material for a negative electrode carrying a conductive material, it is applied to a current collector as a mixture slurry for a battery electrode in which the active material and a conductive additive are mixed, and then the solvent and dispersion medium are removed to remove the active material A negative electrode is formed by bonding together.

  The battery performance of such a non-aqueous electrolyte secondary battery greatly depends on the characteristics of the electrode active material. As a manufacturing method for supporting conductive carbon on an electrode material, for example, Patent Document 1 discloses a manufacturing method in which an organic material is mixed with an electrode material and carbonized to coat the electrode material with conductive carbon. Patent Document 2 discloses a manufacturing method in which an electrode material and conductive carbon are mixed by a wet ball mill, and then the electrode material and conductive carbon are combined by mechanical energy. Furthermore, Patent Document 3 discloses a manufacturing method in which a negative electrode material is coated with conductive carbon by a chemical vapor deposition method.

  In addition, the surface and the inside of secondary particles, which are granulated bodies of electrode material particles (primary particles) obtained by the production methods described in these documents, are both pores (structured) that are not filled with conductive carbon. In order to obtain a transition metal composite oxide negative electrode active material that can sufficiently improve battery performance, it is desirable to reduce such pores.

US Patent Application Publication No. 2004/0140458 JP 2010-218884 A JP 2000-215887 A

  However, these transition metal composite oxide secondary particles have pores communicating from the surface to the inside, and open pores are formed. However, the transition metal composite oxide (primary particles) undergoes transition by firing to produce transition metal composite oxide (primary particles). Sintering between metal composite oxides also occurs and the pore size is reduced, so it is difficult to fill the pores with conductive carbon via the open pores after the formation of secondary particles of the transition metal composite oxide, reducing the pores This tends to be difficult. Therefore, although it requires processing such as adding mechanical energy separately to the active material to crush pores, on the other hand, the crystallinity of the transition metal composite oxide is reduced, and the battery performance that the active material should exhibit is also reduced. Therefore, further improvement is desired.

  Therefore, the subject of the present invention is not only the negative electrode active material for non-aqueous electrolyte secondary batteries having open pores obtained using the transition metal composite oxide, but also having a carbon source supported on the surface of the active material, An object of the present invention is to provide a method for producing a negative electrode active material for a non-aqueous electrolyte secondary battery, and a negative electrode active material for a non-aqueous electrolyte secondary battery, in which pores inside the active material are sufficiently filled with a carbon source.

  Therefore, the present inventors have made various studies, and as a result, a raw material compound for producing a transition metal composite oxide or a transition metal composite oxide, and one or more of a specific amount of an organic acid, a saccharide, and sodium chloride, By calcination of the mixture with water in an oxygen atmosphere, it was found that transition metal composite oxide particles having open pores formed by pores having a large pore diameter can be obtained. The inventors have also found that a negative electrode active material for a non-aqueous electrolyte secondary battery that can exhibit the same or higher performance than the negative electrode active material obtained by the production method is obtained, and the present invention has been completed.

That is, in the present invention, a transition metal composite oxide or a raw material compound for producing a transition metal composite oxide, any one or more of an organic acid, a saccharide, and sodium chloride are mixed with water, and water is 100 masses. Step (I) of obtaining slurry A in which the total amount of organic acid and saccharide added to parts is 2 to 15 parts by mass,
Step (II) for obtaining the transition metal composite oxide particles X having open pores by drying the obtained slurry A and then firing in an oxygen atmosphere.
The obtained transition metal composite oxide particles X having open pores, a carbon material and water are obtained to obtain a slurry B, and then the obtained slurry B is stirred and dried to obtain a granulated body Y ( III), and step (IV) of firing the obtained granulated body Y in a reducing atmosphere or an inert atmosphere.
The manufacturing method of the negative electrode active material for nonaqueous electrolyte secondary batteries is provided.

In the present invention, carbon derived from a carbon material is supported on the transition metal composite oxide particles X having open pores,
The present invention provides a negative electrode active material for a non-aqueous electrolyte secondary battery in which the mode value of the pore diameter of the transition metal composite oxide particles X obtained by mercury porosimetric pore diameter distribution measurement is 80 to 1000 nm.

  According to the present invention, in the negative electrode active material for a non-aqueous electrolyte secondary battery using a transition metal composite oxide, not only the carbon material exhibiting conductivity is favorably supported on the surface of the active material but also the active material. Since the pores in the substance are also effectively and efficiently filled with the carbon material exhibiting conductivity, good performance can be ensured in the obtained battery.

₂ is a SEM image of secondary particles of TiNb ₂ O ₇ obtained in Example 1. FIG. FIG. 3 is a diagram showing a pore size distribution obtained by a mercury intrusion method of secondary particles of TiNb ₂ O ₇ obtained in Example 1. 4 is a SEM image of secondary particles of TiNb ₂ O ₇ obtained in Comparative Example 1. FIG. 3 is a diagram showing a pore size distribution obtained by a mercury intrusion method of secondary particles of TiNb ₂ O ₇ obtained in Comparative Example 1.

Hereinafter, the present invention will be described in detail.
The method for producing a negative electrode active material for a non-aqueous electrolyte secondary battery according to the present invention includes a transition metal composite oxide or a raw material compound for producing a transition metal composite oxide, and any one of an organic acid, a saccharide, and sodium chloride. The above (I) which mixes the above and water, and obtains slurry A whose total addition amount of organic acid and saccharides with respect to 100 mass parts of water is 2-15 mass parts,
Step (II) for obtaining the transition metal composite oxide particles X having open pores by drying the obtained slurry A and then firing in an oxygen atmosphere.
The obtained transition metal composite oxide particles X having open pores, a carbon material and water are obtained to obtain a slurry B, and then the obtained slurry B is stirred and dried to obtain a granulated body Y ( III), and step (IV) of firing the obtained granulated body Y in a reducing atmosphere or an inert atmosphere.
Is provided.

In the step (I), a transition metal composite oxide or a raw material compound for producing a transition metal composite oxide, any one or more of an organic acid, a saccharide and sodium chloride, and water are mixed, and water is 100 masses. This is a step of obtaining slurry A in which the total amount of organic acid and saccharide added to 2 parts is 2 to 15 parts by mass.
The transition metal composite oxide used in the present invention is not particularly limited as long as it is a transition metal composite oxide used as a negative electrode active material of a secondary battery. Specifically, for example, Li ₄ Ti ₅ O ₁₂ , TiNb ₂ Examples thereof include O ₇ and Ti ₂ Nb ₁₀ O ₂₉ .

Li ₄ Ti ₅ O ₁₂ can be produced, for example, by firing a titanium compound and a lithium compound. Also, a suspension is prepared using a predetermined raw material compound such as a titanium compound and a lithium compound, and a hydrothermal reaction is performed. It can also be produced by heat treatment after obtaining crystals.
Examples of the titanium compound as the raw material compound include titanium oxide, hydrous titanium oxide such as orthotitanic acid and metatitanic acid, and these may be used alone or in combination of two or more. Among these, anatase TiO ₂ is preferable from the viewpoint of improving battery physical properties. Examples of the lithium compound that is a raw material compound include lithium oxide and lithium hydroxide, and specific examples include lithium carbonate, lithium hydroxide, and lithium nitrate. These may be used alone or in combination of two or more. Among these, lithium carbonate is preferable from the viewpoint of improving battery physical properties.

More specifically, in the case of using a production method by a solid phase method, a predetermined amount of the titanium compound and the lithium compound are mixed and pulverized, then calcined at a temperature of 700 to 900 ° C. for 8 to 24 hours, and then obtained calcined Li ₄ Ti ₅ O ₁₂ can be obtained by grinding the product.
Moreover, when using the manufacturing method by a hydrothermal method, after mixing the said titanium compound and lithium compound as a raw material compound and obtaining a slurry, reaction temperature of 180-220 degreeC, the pressure of 0.5-1.0 MPa, Li ₄ Ti ₅ O ₁₂ can be obtained by hydrothermal reaction for 20 hours and drying the slurry after the reaction.
In the step (I), instead of using Li ₄ Ti ₅ O ₁₂ produced in advance by the solid phase method or the hydrothermal method, the titanium is used as a raw material compound for producing Li ₄ Ti ₅ O _12. A slurry and A may be obtained by mixing a compound and a lithium compound. In this case, Li ₄ Ti ₅ O ₁₂ can also be formed in the slurry A by subjecting the slurry A to a hydrothermal reaction in advance before the process (II) described later.

For TiNb ₂ O ₇ , for example, a suspension is prepared using a predetermined material such as a niobium compound and a titanium compound, a crystal is obtained by a hydrothermal reaction, and then a crystal having high crystallinity is produced by heat treatment. Can do. It can also be produced by mixing and pulverizing a predetermined material with a ball mill or the like and then firing it.
Niobium hydroxide or the like can be used as the raw material niobium compound, and as the titanium compound as the raw material compound, sulfates such as titanyl sulfate and titanium sulfate, nitrates, chlorides, organic acids, etc. can be used. Can do. Such titanium compounds, including cases where they are inevitably mixed, are partly made of different metals M other than titanium and niobium (M is Sn, Zr, Fe, Bi, Cr, Mo, Na, Mg, Al and Si). And at least one selected from the group consisting of different metals (M) in the titanium compound from the viewpoint of securing better battery physical properties, preferably 30% by mass or less. More preferably, it is 15 mass% or less.

As a more specific production method, niobium hydroxide is used as a niobium compound, anatase TiO ₂ is used as a titanium source, a suspension is prepared with hydrogen peroxide and water, and a solid content obtained through a hydrothermal reaction is prepared. A method of solid-liquid separation and baking is preferable. In addition, the molar ratio (Nb / Ti) of niobium and titanium in the suspension is preferably 1.6 to 2.4, and more preferably 1.8 to 2.2.
In step (I), instead of using TiNb ₂ O ₇ produced in advance as a transition metal composite oxide, the above-mentioned niobium compound and titanium compound are mixed as a raw material compound for producing TiNb ₂ O ₇ , and a slurry is obtained. A may be obtained. In this case, TiNb ₂ O ₇ can also be formed in the slurry A by subjecting the slurry A to a hydrothermal reaction in advance before the process (II) described later.

Ti ₂ Nb ₁₀ O ₂₉ can be produced, for example, by mixing and pulverizing a titanium compound and a niobium compound and then firing. Moreover, it can manufacture also by heat-processing, after preparing suspension using predetermined materials, such as a niobium compound and a titanium compound, and obtaining a crystal | crystallization by hydrothermal reaction.
Examples of the niobium compound that is a raw material compound include niobium oxide and niobium hydroxide. These may be used alone or in combination of two or more. Of these, niobium pentoxide (Nb ₂ O ₅ ) is preferable from the viewpoint of improving battery physical properties. Examples of the titanium compound as the raw material compound include titanium oxide, hydrous titanium oxide such as orthotitanic acid and metatitanic acid, and these may be used alone or in combination of two or more. Among these, anatase TiO ₂ is preferable from the viewpoint of improving battery physical properties. Such titanium compounds, including cases where they are inevitably mixed, are partly made of different metals M other than titanium and niobium (M is Sn, Zr, Fe, Bi, Cr, Mo, Na, Mg, Al and Si). And at least one selected from the group consisting of different metals (M) in the titanium compound from the viewpoint of securing better battery physical properties, preferably 30% by mass or less. More preferably, it is 15 mass% or less.

More specifically, in the case of using a production method by a solid phase method, after mixing and pulverizing predetermined amounts of the niobium compound and the titanium compound, firing is performed at a temperature of 1200 to 1400 ° C. for 4 to 24 hours, and then obtained firing. By grinding the product, Ti ₂ Nb ₁₀ O ₂₉ can be obtained.
In the step (I), instead of using Ti ₂ Nb ₁₀ O ₂₉ produced in advance as the transition metal composite oxide, the niobium compound and the titanium compound are used as raw material compounds for producing Ti ₂ Nb ₁₀ O _29. The slurry A may be obtained by mixing. In this case, Ti ₂ Nb ₁₀ O ₂₉ can also be formed in the slurry A by subjecting the slurry A to a hydrothermal reaction in advance before the process (II) described later.

  When the transition metal composite oxide is used in the step (I), the content of the transition metal composite oxide (primary particles) in the slurry A is preferably 20 to 80 mass with respect to 100 parts by mass of water in the slurry A. Part, more preferably 40 to 60 parts by weight. At this time, the particle diameter of the transition metal composite oxide (primary particles) is preferably 20 to 900 nm, more preferably 20 to 600 nm, from the viewpoint of developing good battery performance. The particle size of the transition metal composite oxide (primary particles) means the maximum value of the passing length of such particles in SEM observation, and the average particle size is the amount of 20 particles extracted arbitrarily. Mean value of In addition, when the raw material compound for producing | generating a transition metal composite oxide is used instead of the transition metal composite oxide, the total content of these raw material compounds is the content of the transition metal composite oxide (primary particles). It is the same.

  Any of these organic acids, saccharides and sodium chloride used in step (I) is used, and a raw material compound for producing a transition metal composite oxide (primary particles) or a transition metal composite oxide In addition, 2 to 15 parts by mass in total are added to 100 parts by mass of water in the slurry water A which is an aqueous solution. Next, the organic particles added to the transition metal composite oxide particles X (secondary particles) formed by aggregation of the primary particles of the transition metal composite oxide by drying in the step (II) described later. The acid, saccharide and sodium chloride are precipitated as solid substances and scattered so as to fill the voids between the primary particles remaining in the secondary particles, so-called pores. Thereafter, the organic acid and the saccharide are burned and disappeared by firing in an oxygen atmosphere in the step (II), and the sodium chloride is volatilized and disappeared. As a result, the transition metal composite oxide particles X (secondary Particles) have pores having an appropriate pore size as traces of the presence of the solid substance consisting of the specific amount of organic acid, saccharide or sodium chloride inside, and the pores are transition metal composite oxide particles X (two It is considered that open pores can be formed by communicating from the surface to the inside of the secondary particles).

Examples of such saccharides include monosaccharides such as glucose, fructose, galactose and mannose; disaccharides such as maltose, sucrose and cellobiose; and polysaccharides such as starch and dextrin. Above all, from the viewpoint of effectively depositing a solid substance in the drying step of step (II) so that pores having an appropriate pore diameter communicate from the surface of the particle X to the inside when the organic acid is burned and disappeared. 1 type, or 2 or more types selected from glucose, fructose, sucrose, and dextrin are preferred, and glucose is more preferred.
Examples of the organic acid include organic acids such as citric acid, tartaric acid, and ascorbic acid. Above all, from the viewpoint of effectively depositing a solid substance in the drying step of step (II) so that pores having an appropriate pore diameter communicate from the surface of the particle X to the inside when the organic acid is burned and disappeared. Citric acid is preferred.
Such sodium chloride is not particularly limited, and commonly available sodium chloride can be used.

  In step (I), only these saccharides may be used, only organic acids may be used, only sodium chloride may be used, or two or more selected from saccharides, organic acids and sodium chloride may be used in combination. It may be used. Among these, when these saccharides, organic acids, and sodium chloride are burnt or volatilized and disappear, the pores having an appropriate pore diameter communicate from the surface of the particle X to the inside, and are effective in the drying step of the step (II). From the viewpoint of precipitating a solid substance, it is preferable to use one or more selected from organic acids and saccharides.

  The total amount of the organic acid, saccharide and sodium chloride added to the slurry A is 2 to 15 parts by mass, preferably 3 to 10 parts by mass with respect to 100 parts by mass of water in the slurry A.

  In the step (I), any one or more of the transition metal composite oxide and the organic acid, saccharide and sodium chloride are preferably added to water, and the order of addition is not particularly limited. Moreover, also when using the raw material compound for producing | generating a transition metal complex oxide, it is preferable to add any one or more of the raw material compound and an organic acid, a saccharide, and sodium chloride to water. The order is not particularly limited. When the raw material compound for producing such a transition metal composite oxide is used, the obtained slurry A is transferred to the step (II) as it is, or the obtained slurry A is subjected to a hydrothermal reaction and then the step described later. It is only necessary to move to (II).

  In addition, in obtaining the slurry A in the step (I), from the viewpoint of miniaturizing the transition metal composite oxide particles having the open pores in the step (II) described later, a step described later is performed when the predetermined raw materials are mixed. It is preferable to perform the same stirring as in the slurry B in (III).

  Step (II) is a step in which the slurry A obtained in step (I) is dried and then fired in an oxygen atmosphere to obtain transition metal composite oxide particles X having open pores. By drying the slurry A, a granulated body X1 in which a transition metal composite oxide is mixed with a solid substance derived from one or more of organic acids, sugars and sodium chloride, or a transition metal composite oxide is produced. To obtain a granulated body X2 in which a raw material compound and a solid substance derived from at least one of organic acids, sugars and sodium chloride are mixed, and this is baked in an oxygen atmosphere to obtain an organic acid. The solid substance derived from any of saccharides and sodium chloride disappears, and particles X (secondary particles) consisting only of transition metal composite oxides having open pores in which pores communicate from the particle surface to the inside can be obtained.

As a drying method of the slurry A in the step (II), any of usual drying methods such as constant temperature drying, spray drying, freeze drying, vacuum drying and the like can be used, but the transition metal composite oxide particles X ( From the viewpoint of effectively controlling the size of the secondary particles), spray drying is more preferable.
For producing a granulated body X1 obtained by spray drying, in which a transition metal composite oxide is mixed with a solid substance derived from at least one of organic acids, sugars and sodium chloride, or a transition metal composite oxide The particle size of the granulated body X2 formed by mixing the raw material compound and a solid substance derived from any one or more of organic acids, sugars and sodium chloride is a D ₅₀ value in the particle size distribution based on the laser diffraction / scattering method, Preferably it is 1-20 micrometers, More preferably, it is 2-15 micrometers. Here, the D ₅₀ value in the particle size distribution measurement is a value obtained by a volume-based particle size distribution based on the laser diffraction / scattering method, and the D ₅₀ value means a particle size (median diameter) at a cumulative 50%. . Therefore, what is necessary is just to adjust the particle size of this granulated body X1 or X2 by optimizing the operating condition of a spray-drying apparatus suitably. For example, as a treatment condition in a micro mist dryer (MDL-050M manufactured by Fujisaki Electric Co., Ltd.) equipped with a four-fluid nozzle, the air pressure is preferably 0.3 to 0.8 MPa, and 0.5 to 0 0.7 MPa is more preferable, the air flow rate is preferably 20 to 60 NL / min, and more preferably 50 to 60 NL / min. Further, it is preferable hot air amount is 0.6~1.2m ³ / min, more preferably from 0.8~1.1m ³ / min, inlet temperature, and even at 100 to 250 ° C. Preferably, it is 150-200 degreeC. Further, the exhaust temperature is preferably 70 to 150 ° C, more preferably 80 to 120 ° C, and the flow rate of the slurry A is preferably 20 to 70 g / min, and 50 to 70 g / min. Is more preferable.

  Next, the obtained granulated body X1 or X2 is fired in an oxygen atmosphere. Due to this firing, the saccharide and / or organic acid-derived solid substance contained in the granulated body X1 or X2 burns and burns out, or the sodium chloride contained in the granulated body X1 or X2 volatilizes and adjoins transition. Sintering between the metal composite oxides (primary particles) proceeds well, and the crystallinity of the transition metal composite oxide particles X formed in the granulated body X1 or X2 is enhanced. Thus, it is possible to obtain strong transition metal composite oxide particles X (secondary particles).

The firing temperature in the step (II) increases the crystallinity of the resulting transition metal composite oxide particles X and effectively reduces the pores present in the transition metal composite oxide particles X due to excessive sintering. From the viewpoint of suppression, the temperature is preferably 600 to 1200 ° C, more preferably 600 to 1100 ° C, and still more preferably 700 to 1000 ° C. More specifically, when sodium chloride is contained in the granulated body X1 or X2, it is preferably 850 to 1200 ° C., more preferably from the viewpoint of volatilizing sodium chloride and completely eliminating it. It is 900-1200 degreeC, More preferably, it is 950-1200 degreeC. Further, the firing time is preferable from the viewpoint of effectively suppressing the pores of the transition metal composite oxide particles X from being reduced in size by excessive sintering while enhancing the crystallinity of the obtained transition metal composite oxide particles X. Is 0.3 to 7 hours, and more preferably 0.5 to 6 hours. More specifically, when sodium chloride is contained in the granulated body X1 or X2, it is preferably 1 to 7 hours from the viewpoint of volatilizing sodium chloride and completely disappearing, more preferably 2 to 7 hours.
In addition, the atmosphere at the time of baking is the valence of titanium in the transition metal composite oxide particles X in order to complete the burning out of the solid substance derived from saccharides and / or organic acids, or to complete the volatilization of sodium chloride. Therefore, it is necessary to use an oxygen atmosphere, and it is most preferable to use an air atmosphere from the viewpoint of simplicity and economy. The apparatus used for firing is not particularly limited as long as the firing atmosphere and temperature can be adjusted, and any of batch, continuous, and heating (indirect or direct) apparatuses can be used. .

Since the transition metal composite oxide particles X (secondary particles) obtained in the step (II) have open pores formed by communicating pores having an appropriate pore diameter from the surface to the inside, the step (III) described later ), The carbon material can be effectively filled into the secondary particles through the open pores. The size of the pore size (pore diameter) formed in the secondary particles depends on the pore size and its pore size, based on the measurement results of the applied pressure and mercury intrusion amount using a mercury intrusion pore size distribution measuring device (mercury porosimeter). Based on the pore volume (pore diameter distribution), the mode value can be obtained and evaluated. Specifically, the mode value of the pore diameter of the secondary particles obtained in the step (II) is preferably 80 to 1000 nm, more preferably from the viewpoint of effectively filling the secondary particles with the carbon material. Is 100-500 nm.
In addition, the total pore volume (mL / g) in the transition metal composite oxide particles X (secondary particles) obtained in the step (II) is adequately secured in a region where the carbon material is filled inside the secondary particles, From the viewpoint of obtaining a negative electrode active material capable of effectively improving battery physical properties, the amount is preferably 0.1 to 0.6 mL / g, more preferably 0.2 to 0.6 mL / g. The value of the total pore volume can also be measured by the mercury intrusion pore size distribution measuring device.

  In step (III), the transition metal composite oxide particles X having open pores obtained in step (II), a carbon material, and water are mixed to obtain slurry B, and then the obtained slurry B is stirred. This is a step of drying to obtain a granulated body Y. The carbon material that can be used may be a water-soluble carbon material or a water-insoluble carbon material.

  The water-soluble carbon material means a carbon material that can be dissolved in 100 g of water at 25 ° C. in an amount of 0.4 g or more, preferably 1.0 g or more in terms of carbon atom of the water-soluble carbon material. It functions as a carbon source that fills the pores of X. Examples of the water-soluble carbon material include one or more selected from saccharides, polyols, polyethers, and organic acids. More specifically, for example, monosaccharides such as glucose, fructose, galactose and mannose; disaccharides such as maltose, sucrose and cellobiose; polysaccharides such as starch and dextrin; ethylene glycol, propylene glycol, diethylene glycol, polyethylene glycol and butane Examples include polyols and polyethers such as diol, propanediol, polyvinyl alcohol, and glycerin; and organic acids such as citric acid, tartaric acid, and ascorbic acid. Among them, from the viewpoint of enhancing solubility and dispersibility in a solvent and effectively exhibiting a function as a carbon source having conductivity, one or more selected from glucose, fructose, sucrose, and dextrin Is preferred, and glucose is more preferred.

The water-insoluble carbon material is a water-insoluble carbon powder, and is a carbon source that itself has conductivity without being fired. Examples of the water-insoluble carbon material include one or more selected from graphite, acetylene black, ketjen black, channel black, furnace black, lamp black, thermal black, carbon nanofiber, carbon nanotube, and fibrous carbon. Can be mentioned. Among these, acetylene black or ketjen black is preferable from the viewpoint of having a high structure structure. From the viewpoint of effectively filling the pores of the transition metal composite oxide particle X, the average particle size of the water-insoluble carbon material that can be used is preferably 1 to 30 nm, and more preferably 1 to 15 nm.
From the viewpoint of effectively filling the pores of the transition metal composite oxide particles X, such a water-insoluble carbon material is preferably used by being previously dispersed in water.

  From the viewpoint of effectively filling the carbon material with pores of the transition metal composite oxide particles X, the carbon material is added to a suspension composed of the transition metal composite oxide particles X and water to obtain a slurry B. preferable. The content of the transition metal composite oxide particles X in the suspension is preferably 30 to 100 parts by mass, more preferably 50 to 100 parts by mass with respect to 100 parts by mass of water. In addition, the carbon material added to the suspension is conductive because carbon derived from the carbon material fills the pores of the transition metal composite oxide particles X and further covers the surface of the transition metal composite oxide particles X. From the viewpoint of making the amount sufficient to enhance the properties, the amount in terms of carbon atoms is preferably 0.5 to 15 parts by mass, more preferably 1 to 10 parts per 100 parts by mass of the transition metal composite oxide particles X. Part by mass.

  Filling the pores through the open pores in the transition metal composite oxide particles X with the carbon material can be performed by stirring the resulting slurry B. In the slurry B, it is preferable to stir using a disperser (homogenizer) from the viewpoint of uniformly and satisfactorily dispersing the transition metal composite oxide particles X and the carbon material. Examples of such a disperser include a disaggregator, a beater, a low pressure homogenizer, a high pressure homogenizer, a grinder, a cutter mill, a ball mill, a jet mill, a short shaft extruder, a twin screw extruder, an ultrasonic stirrer, and a home juicer mixer. Can be mentioned. Among these, an ultrasonic stirrer is preferable from the viewpoint of increasing the dispersion efficiency. The degree of dispersion uniformity of the slurry B can be quantitatively evaluated by, for example, the light transmittance using a UV / visible light spectrometer or the viscosity using an E-type viscometer, and the turbidity is uniform. It can also be easily evaluated by visually confirming that it is present. The stirring time of the slurry B is preferably 1 minute or more, more preferably 5 to 60 minutes.

  The stirring of the slurry B is preferably performed in a reduced pressure environment from the viewpoint of more efficiently filling the pores with the carbon material through the open pores in the transition metal composite oxide particles X. In order to stir in such a reduced pressure environment, a slurry B stirring tank may be installed in the reduced pressure vessel, and the pressure at this time is preferably 0.09 MPa or less, more preferably 0.001 to 0.00. It is 09MPa, More preferably, it is 0.001-0.05MPa. The stirring time using the disperser under a reduced pressure environment is preferably 0.1 minutes or more, more preferably 0.1 to 5 minutes, and further preferably 0.1 to 3 minutes.

  Next, in step (III), the slurry B after stirring is dried to obtain a granulated body Y in which secondary particles in which pores are filled with a carbon material are mixed. As the drying method of the slurry B, a normal drying method such as constant temperature drying, spray drying, freeze drying, vacuum drying and the like can be used as in the drying method in the step (II). From the viewpoint of effectively controlling the above, spray drying is more preferable.

The granulated body Y obtained after drying is preferably composed of secondary particles alone. Therefore, the preferred particle diameter of the granulated body Y is a D ₅₀ value, preferably 1 to 20 μm, like the granulated body X. More preferably, it is 2-15 micrometers. In order to achieve such a value, for example, when spray drying is performed, the particle size of the granulated body Y may be adjusted by appropriately optimizing the operating conditions of the spray drying apparatus. For example, as a treatment condition in a micro mist dryer (MDL-050M manufactured by Fujisaki Electric Co., Ltd.) equipped with a four-fluid nozzle, the air pressure is preferably 0.5 to 0.9 MPa, and 0.7 to 0 More preferably, the pressure is 0.9 MPa, the air flow rate is preferably 40 to 80 NL / min, and more preferably 60 to 80 NL / min. Further, it is preferable hot air amount is 0.6~1.2m ³ / min, more preferably from 0.8~1.1m ³ / min, inlet temperature, and even at 100 to 250 ° C. Preferably, it is 150-200 degreeC. Furthermore, the exhaust temperature is preferably 70 to 150 ° C, more preferably 80 to 120 ° C, and the flow rate of the slurry B is preferably 5 to 40 g / min, and 10 to 20 g / min. Is more preferable.

  Step (IV) is a step of firing the granulated body Y obtained in step (III) in a reducing atmosphere or an inert atmosphere. Thereby, from the transition metal composite oxide particles X and the carbon material contained in the granulated body Y, carbon is effectively filled and supported in the pores of the transition metal composite oxide particles X through the open pores. A negative electrode active material for a water electrolyte secondary battery is obtained, and a negative electrode active material for a nonaqueous electrolyte secondary battery excellent in battery performance can be realized. The firing conditions for the step (IV) may be in a reducing atmosphere or an inert atmosphere, the firing temperature is preferably 400 ° C. or higher, more preferably 400 to 800 ° C., and the firing time is preferably 10 minutes. -3 hours, more preferably 0.5-1.5 hours.

  The obtained negative electrode active material for a non-aqueous electrolyte secondary battery is useful in that it exhibits very excellent discharge capacity and cycle specification as a negative electrode of a secondary battery such as a lithium ion battery or a sodium ion battery. A secondary battery to which such a negative electrode can be applied is not particularly limited as long as it has a positive electrode, a negative electrode, an electrolytic solution, and a separator as essential components.

  Here, the positive electrode is not particularly limited in its material configuration as long as it can release a predetermined metal ion such as lithium ion or sodium ion at the time of charging and can be occluded at the time of discharging. Things can be used. For example, it is preferable to suitably use various olivine compounds obtained by hydrothermal reaction of the raw materials.

  The electrolytic solution is obtained by dissolving a supporting salt in an organic solvent. The organic solvent is not particularly limited as long as it is an organic solvent that is usually used for an electrolyte of a secondary battery such as a lithium ion battery or a sodium ion battery. For example, carbonates, halogenated hydrocarbons, ethers, ketones , Nitriles, lactones, oxolane compounds and the like can be used.

The type of the supporting salt is not particularly limited. For example, in the case of a lithium ion secondary battery, an inorganic salt selected from LiPF ₆ , LiBF ₄ , LiClO ₄ , LiAsF ₆ , a derivative of the inorganic salt, LiSO ₃ CF ₃ , LiC (SO ₃ CF ₃ ) ₂ , LiN (SO ₃ CF ₃ ) ₂ , LiN (SO ₂ C ₂ F ₅ ) ₂ and LiN (SO ₂ CF ₃ ) (SO ₂ C ₄ F ₉ ) It is preferably at least one of an organic salt and a derivative of the organic salt. In the case of a sodium ion secondary battery, for example, an inorganic salt selected from NaPF ₆ , NaBF ₄ , NaClO ₄ and NaAsF ₆ , a derivative of the inorganic salt, NaSO ₃ CF ₃ , NaC (SO ₃ CF ₃ ) ₂ and NaN ( At least one organic salt selected from SO ₃ CF ₃ ) ₂ , NaN (SO ₂ C ₂ F ₅ ) ₂ and NaN (SO ₂ CF ₃ ) (SO ₂ C ₄ F ₉ ), and a derivative of the organic salt Preferably there is.

  The separator plays a role of electrically insulating the positive electrode and the negative electrode and holding the electrolytic solution. For example, a porous synthetic resin film, particularly a polyolefin polymer (polyethylene, polypropylene) porous film may be used.

EXAMPLES Hereinafter, although this invention is demonstrated concretely based on an Example, this invention is not limited to these Examples.
Each measurement was performed according to the following method, and the obtained results including the manufacturing conditions are shown in Table 1.

<< Measurement of pore size distribution of secondary particles composed of transition metal complex oxide >>
The pore size distribution of the secondary particles composed of the transition metal composite oxides obtained in Example 1 and Comparative Example 1 was measured by a mercury intrusion method using a measuring device (AutoPore IV9505 manufactured by Micromeritics).

<< Measurement of BET specific surface area of secondary particles composed of transition metal composite oxide >>
Using a measuring apparatus (FlowSorbIII 2305 manufactured by Shimadzu Corporation), the BET specific surface area of the secondary particles composed of the transition metal composite oxides obtained in Examples and Comparative Examples was measured by a nitrogen adsorption method.

<< Production Example 1: Production of TiNb ₂ O ₇ >>
In a 5 L plastic container, put 133.2 kg of zirconia balls with a diameter of 1 mm together with 243.2 g of anatase TiO ₂ (manufactured by Kanto Chemical Co., Ltd.), 797.4 g of Nb2O5 (manufactured by Kanto Chemical Co., Ltd.), and 1000 mL of water, and mixed and pulverized. The treatment was performed for 24 hours. Thereafter, the zirconia balls were washed and removed with a wet sieve, and then solid-liquid separated with a filter press.

[Example 1]
To 1000 mL of water, 538 g of dehydrated cake solid content obtained by solid-liquid separation in Production Example 1 was added (slurry concentration equivalent to 35% by mass), and 21.5 g of glucose (anhydrous crystal glucose manufactured by Nippon Shokuhin Kako) (TiNb 4 parts by mass with respect to 100 parts by mass of ₂ O ₇ ) and stirred for 10 minutes with an ultrasonic stirrer (IKA, T25) to obtain slurry A that is uniformly colored as a whole, and then the obtained slurry A was spray dried (spray dryer; MDL-050M manufactured by Fujisaki Electric Co., Ltd.) to obtain granulated body X1 (primary particles). Thereafter, the granulated body X1 was fired at 1100 ° C. for 4 hours in an air atmosphere to obtain secondary particles A1 made of only TiNb ₂ O ₇ . The obtained secondary particles A1 had a BET specific surface area of 8.2 m ² / g, and the secondary particles A1 had an average particle size of 10 μm. Furthermore, the mode value of the pore diameter in the secondary particle A1 measured by the mercury porosimeter of the secondary particle A1 was 200 nm, and the total pore volume was 0.40 mL / g.
The SEM image of the obtained secondary particle A1 is shown in FIG. 1, and the pore size distribution by the mercury intrusion method is shown in FIG. Of the two peaks shown in the pore size distribution in FIG. 2, the left peak is the pores of the secondary particles A1 (secondary particles) (the voids between the primary particles remaining in the secondary particles), and the right side The peak of was a void between secondary particles.

100 g of the obtained secondary particles A1 were collected, mixed with 6.2 g of glucose (corresponding to 5.3 parts by mass in terms of carbon atoms with respect to 100 parts by mass of secondary particles A1) and 200 mL of water, Using a sonic stirrer (T25), the mixture was stirred for 10 minutes under atmospheric pressure to obtain slurry B1 that was uniformly colored as a whole.
Next, the slurry B1 was spray-dried (MDL-050M) to obtain a granulated body Y1, which was then calcined at 700 ° C. for 1 hour in an argon-hydrogen atmosphere (hydrogen concentration 3%). A supported negative electrode active material for a nonaqueous electrolyte secondary battery (TiNb ₂ O ₇ / C, carbon content 5.0 mass%) was obtained.

[Example 2]
For obtaining the secondary particles A1, the amount of glucose added was 32.3 g (6 parts by mass with respect to 100 parts by mass of TiNb ₂ O ₇ ). A negative electrode active material (TiNb ₂ O ₇ / C, carbon content 5.0% by mass) was obtained.

[Example 3]
In order to obtain the secondary particles A1, 21.5 g of citric acid (manufactured by Wako Pure Chemical Industries, Ltd., purity 99.5%) was added instead of glucose (4 parts by mass with respect to 100 parts by mass of TiNb ₂ O ₇ ). Except that, in the same manner as in Example 1, a negative electrode active material for a nonaqueous electrolyte secondary battery (TiNb ₂ O ₇ / C, carbon amount 5.0 mass%) was obtained.

[Example 4]
In obtaining the secondary particles A1, a nonaqueous electrolyte was obtained in the same manner as in Example 1, except that 32.3 g of citric acid was added instead of glucose (6 parts by mass with respect to 100 parts by mass of TiNb ₂ O ₇ ). A negative electrode active material for secondary battery (TiNb ₂ O ₇ / C, carbon content 5.0% by mass) was obtained.

[Example 5]
In obtaining the slurry B1, a negative electrode active material for a non-aqueous electrolyte secondary battery (TiNb ₂ O ₇ / C, carbon content of 5.N), except that the slurry was stirred for 2 minutes under a reduced pressure of 0.04 MPa. 0% by mass) was obtained.

[Example 6]
In obtaining the slurry B1, a negative electrode active material for a non-aqueous electrolyte secondary battery (TiNb ₂ O ₇ / C, carbon content) in the same manner as in Example 1 except that stirring was performed for 0.5 minutes under a reduced pressure treatment of 0.01 MPa. 5.0% by mass) was obtained.

[Comparative Example 1]
In obtaining secondary particles, secondary particles G1 were obtained in the same manner as in Example 1 except that glucose was not added. In the measurement of the obtained secondary particles G1 with a mercury porosimeter, the pores in the secondary particles G1 (the voids between the primary particles remaining in the secondary particles) could not be confirmed.
The SEM image of the obtained secondary particle G1 is shown in FIG. 3, and the pore size distribution by the mercury intrusion method is shown in FIG. Note that the peak shown in the pore size distribution in FIG. 4 was only the peak corresponding to the space between adjacent secondary particles.
Next, a negative electrode active material for a non-aqueous electrolyte secondary battery (TiNb ₂ O ₇ / C, carbon content 5) in the same manner as in Example 1 except that the obtained secondary particles G1 were used instead of the secondary particles A1. 0.0 mass%) was obtained.

[Comparative Example 2]
For obtaining the secondary particles A1, the amount of glucose added was 5.4 g (1 part by mass with respect to 100 parts by mass of TiNb ₂ O ₇ ). A negative electrode active material (TiNb ₂ O ₇ / C, carbon content 5.0% by mass) was obtained.

[Comparative Example 3]
In obtaining the secondary particles A1, a nonaqueous electrolyte secondary was obtained in the same manner as in Example 1 except that 5.4 g of citric acid was added instead of glucose (1 part by mass with respect to 100 parts by mass of TiNb ₂ O ₇ ). A negative electrode active material for battery (TiNb ₂ O ₇ / C, carbon content 5.0% by mass) was obtained.

<< Production Example 2: Production of Li ₄ Ti ₅ O ₁₂ >>
A 1L zirconia ball (13 kg) is placed in a 5 L plastic container together with 1768 g of anatase TiO ₂ (manufactured by Kanto Chemical Co., Ltd.), 654 g of Li ₂ CO ₃ (manufactured by Kanto Chemical Co., Ltd.) and 1000 mL of water. For 24 hours. Thereafter, the zirconia balls were washed and removed with a wet sieve, and then solid-liquid separated with a filter press.

[Example 7]
To 1000 mL of water, 538 g of the dehydrated cake solid content obtained by solid-liquid separation in Production Example 2 was added (slurry concentration corresponding to 35% by mass), and 21.5 g of glucose (100 parts by mass of Li ₄ Ti ₅ O ₁₂ ) was added thereto. 4 parts by mass) was added, and the mixture was stirred with an ultrasonic stirrer (T25) for 10 minutes to obtain a slurry A2 that was uniformly colored as a whole, and then the resulting slurry A2 was spray dried (MDL-050M) And granulated body X2 was obtained. Thereafter, the granulated body X2 was fired at 800 ° C. for 10 hours in an air atmosphere to obtain secondary particles A2 made of only Li ₄ Ti ₅ O ₁₂ .
The obtained secondary particles A2 had a BET specific surface area of 13.1 m ² / g, and the secondary particles A2 had an average particle size of 10 μm. Furthermore, the mode value of the pore diameter of the pore opening measured by the mercury porosimeter of the secondary particle A2 was 500 nm.

100 g of the obtained secondary particles A2 were collected, mixed with 6.2 g of glucose (corresponding to 5.3 parts by mass in terms of carbon atoms with respect to 100 parts by mass of secondary particles A2) and 200 mL of water, The mixture was stirred with a sonic stirrer (T25) for 10 minutes to obtain slurry B2 that was uniformly colored as a whole.
Next, the slurry B2 was spray-dried (MDL-050M) to obtain a granulated body Y2, which was then calcined at 700 ° C. for 1 hour in an argon-hydrogen atmosphere (hydrogen concentration 3%). A supported negative electrode active material for a nonaqueous electrolyte secondary battery (Li ₄ Ti ₅ O ₁₂ / C, carbon content 5.0 mass%) was obtained.

[Comparative Example 4]
In obtaining secondary particles A2, a negative electrode active material for a non-aqueous electrolyte secondary battery (Li ₄ Ti ₅ O ₁₂ / C, carbon mass 5.0 mass) in the same manner as in Example 7 except that glucose was not added. %).

<Evaluation of charge / discharge characteristics>
The negative electrode active materials for non-aqueous electrolyte secondary batteries obtained in Examples and Comparative Examples, ketjen black (conductive agent), and polyvinylidene fluoride (binding agent) were mixed at a mass ratio of 90: 3: 7. Then, N-methyl-2-pyrrolidone was added thereto and kneaded sufficiently to prepare a negative electrode slurry.
The obtained negative electrode slurry was applied to a current collector made of a copper foil having a thickness of 20 μm using a coating machine, and vacuum dried at 80 ° C. for 12 hours. Thereafter, it was punched into a disk shape of φ14 mm and pressed at 16 MPa for 2 minutes using a hand press to obtain a negative electrode.
Next, Li foil punched out to φ15 mm was used as the positive electrode, and an electrolyte was prepared by dissolving LiPF ₆ at a concentration of 1 mol / L in a mixed solvent in which ethylene carbonate and ethyl methyl carbonate were mixed at a volume ratio of 1: 1. Using a polymer porous film (made of polypropylene) as a separator, the separator was incorporated and housed in an ordinary manner in an atmosphere having a dew point of −50 ° C. or lower to produce a coin-type lithium secondary battery (CR-2032).
For each lithium secondary battery that was created, under a temperature of 30 ° C., the charging condition was a constant current of 1 CA (387 mA / g) and a voltage of 3 V, the discharging condition was a constant current of 1 CA (387 mA / g) and a final voltage of 1 V. As constant voltage discharge, discharge capacities at 1 CA and 20 CA were measured (measuring device: HJ-1001SD8 manufactured by Hokuto Denko Co., Ltd.).
The results are shown in Table 2.

Claims (6)

Transition metal composite oxide or raw material compound for producing transition metal composite oxide, any one or more of organic acid, saccharide and sodium chloride and water are mixed, and organic acid and saccharide for 100 parts by mass of water Step (I) for obtaining slurry A having a total addition amount of 2 to 15 parts by mass,
Step (II) for obtaining the transition metal composite oxide particles X having open pores by drying the obtained slurry A and then firing in an oxygen atmosphere.
The obtained transition metal composite oxide particles X having open pores, a carbon material and water are obtained to obtain a slurry B, and then the obtained slurry B is stirred and dried to obtain a granulated body Y ( III), and step (IV) of firing the obtained granulated body Y in a reducing atmosphere or an inert atmosphere.
A method for producing a negative electrode active material for a non-aqueous electrolyte secondary battery.   2. The anode active material for a nonaqueous electrolyte secondary battery according to claim 1, wherein the mode of pore diameter of the transition metal composite oxide particles X having open pores obtained in step (II) is 80 to 1000 nm. Production method.   The method for producing a negative electrode active material for a non-aqueous electrolyte secondary battery according to claim 1 or 2, wherein the stirring in the step (III) is a treatment performed for 0.1 minute or more.   The method for producing a negative electrode active material for a nonaqueous electrolyte secondary battery according to claim 1, wherein the stirring in the step (III) is a treatment performed under a reduced pressure environment of 0.09 MPa or less. Carbon derived from a carbon material is supported on the transition metal composite oxide particles X having open pores,
A negative electrode active material for a non-aqueous electrolyte secondary battery, in which the mode value of the pore diameter of the transition metal composite oxide particles X obtained by mercury porosimetric pore diameter distribution measurement is 80 to 1000 nm.   6. The negative electrode active material for a non-aqueous electrolyte secondary battery according to claim 5, wherein the total pore volume of the transition metal composite oxide particles X determined by mercury intrusion pore size distribution measurement is 0.1 to 0.6 mL / g. .