JP6126192B1 - Oxide-based negative electrode active material for secondary battery and method for producing the same - Google Patents

Abstract

To provide a high-performance lithium ion secondary battery or sodium ion secondary battery, an oxide-based negative electrode active material for a secondary battery capable of effectively suppressing moisture adsorption, and a method for producing the same. . An oxide-based negative electrode active material for a secondary battery in which carbon derived from cellulose nanofibers and carbon derived from a water-soluble carbon material are supported on an oxide for a negative electrode active material. [Selection figure] None

Description

  The present invention relates to an oxide-based negative electrode active material for a secondary battery in which carbon derived from cellulose nanofibers and carbon derived from a water-soluble carbon material are supported on an oxide for a negative electrode active material, and a method for producing the same. .

  Secondary batteries used for portable electronic devices, hybrid cars, electric cars, and the like have been developed, and secondary batteries such as lithium ion secondary batteries and sodium ion secondary batteries are widely known. In such a secondary battery, it is known that the generation of gas accompanying the charging / discharging of the battery may cause a deterioration reaction inside the battery, but if water is present, the risk is further increased.

  In order to avoid the occurrence of such a deterioration reaction, for example, as shown in Patent Document 1, it is effective to reduce the water content of the positive electrode active material used as the positive electrode material of the secondary battery. Similarly, it is effective to reduce the moisture content of the negative electrode material. For example, for a carbon-based negative electrode material, Patent Document 2 discloses moisture adsorbed by subjecting a carbon material to a specific heat treatment. A manufacturing method is disclosed in which, after removal, this is applied directly to a strip-shaped current collector. Further, Patent Document 3 discloses hard carbon (non-graphite) with a large number of closed pores that exhibits specific physical properties in differential thermal analysis. A method for reducing the amount of moisture adsorbed in the negative electrode material is disclosed.

  On the other hand, regarding the oxide-based negative electrode material, Patent Document 4 describes that in a negative electrode including a spinel-structure lithium-titanium composite oxide, the amount of water contained is preferably 0.05% by mass or less per mass of the negative electrode active material. However, no specific study has been made on how to reduce the amount of moisture.

JP2013-152911A JP 2002-190299 A International Publication No. 2007/040007 International Publication No. 2013/137272

  For these reasons, a technique for reducing the amount of adsorbed moisture of the negative electrode active material for secondary batteries using an oxide that can be used as a negative electrode material is strongly desired.

  Accordingly, an object of the present invention is to provide an oxide-based negative electrode active material for a secondary battery that can effectively suppress moisture adsorption in order to obtain a high-performance lithium ion secondary battery or a sodium ion secondary battery, and its It is to provide a manufacturing method.

  Therefore, the present inventors have intensively studied, and the surface of an oxide that can be used as a negative electrode material, that is, a so-called negative electrode active material oxide, has a high affinity with water, and therefore has a drying treatment as compared with a carbon-based negative electrode material. It has been found that it is difficult to remove moisture sufficiently by itself. Further, such oxides for negative electrode active materials often have carbides derived from water-soluble carbon materials such as glucose, which are often used for positive electrode materials, although the surface is often coated with carbon in order to improve electronic conductivity. It has also been found that it is not easy to completely cover the surface of the material only with the surface coating by. Based on such knowledge, the present inventors have further studied variously, and the oxide for the negative electrode active material is derived from a plurality of carbon sources including carbon derived from cellulose nanofibers and carbon derived from a water-soluble carbon material. If it is an oxide-based negative electrode active material for a secondary battery in which carbon is supported, these carbons can effectively coat the surface of the negative electrode active material oxide and effectively suppress moisture adsorption. It has been found that the ion or sodium ion is extremely useful as a negative electrode active material for a secondary battery capable of effectively carrying electric conduction, and the present invention has been completed.

That is, the present invention provides an oxide-based negative electrode active material for a secondary battery in which carbon derived from cellulose nanofibers and carbon derived from a water-soluble carbon material are supported on an oxide for a negative electrode active material. is there.
The present invention also includes the step (I) of obtaining a suspension X by adding cellulose nanofibers, a water-soluble carbon material and water to the oxide X for the negative electrode active material, and spray-drying the obtained suspension X. Then, after obtaining the granulated body Y, a method for producing an oxide-based negative electrode active material for a secondary battery, comprising a step (II) of firing is provided.

  According to the oxide-based negative electrode active material for a secondary battery of the present invention, the carbon oxide derived from cellulose nanofibers and the carbon derived from the water-soluble carbon material are both effectively supplemented as a carbon source to the oxide specific to the negative electrode active material. By supporting the oxide, it is possible to effectively suppress the oxide from being exposed without the presence of carbon in a part of the surface of the oxide for the negative electrode active material. An anode active material for a secondary battery that is effectively reduced can be obtained. Therefore, since such a negative electrode active material can effectively suppress moisture adsorption, in a lithium ion secondary battery or a sodium ion secondary battery using the negative electrode active material, lithium ions or sodium ions effectively carry electric conduction, Excellent battery characteristics such as cycle characteristics can be stably exhibited even in a different use environment.

Hereinafter, the present invention will be described in detail.
The oxide-based negative electrode active material for a secondary battery of the present invention is obtained by supporting carbon derived from cellulose nanofibers and carbon derived from a water-soluble carbon material on an oxide for negative electrode active material. That is, carbon derived from cellulose nanofibers and carbon derived from a water-soluble carbon material coexist as a carbon source, and the carbon derived from one carbon source covers the surface of the oxide for the negative electrode active material. The carbon derived from the other carbon source is effectively supported on the portion where the surface of the oxide for negative electrode active material is exposed without being present. Therefore, the carbon derived from the cellulose nanofibers and the carbon derived from the water-soluble carbon material are combined to effectively suppress the exposure of the surface of the oxide for the negative electrode active material, and over the entire surface of the oxide for the negative electrode active material. Since it is firmly supported, moisture adsorption in the oxide-based negative electrode active material for a secondary battery of the present invention can be effectively prevented.

The oxide for negative electrode active material used in the present invention is not particularly limited as long as it is an oxide generally used as a negative electrode active material of a secondary battery. Specifically, for example, Li ₄ Ti ₅ O ₁₂ , Ti ₂ Examples thereof include oxides selected from Nb ₁₀ O ₂₉ , TiNb ₂ O ₇ , brookite type TiO ₂ , and SiO.

Li ₄ Ti ₅ O ₁₂ can be obtained by firing a titanium compound and a lithium compound. Examples of the titanium compound that can be used include hydrous titanium oxides such as titanium oxide, orthotitanic acid, and metatitanic acid. 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 can be used 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.
After mixing and pulverizing predetermined amounts of these titanium compound and lithium compound, Li ₄ Ti ₅ O ₁₂ is obtained by calcination at a temperature of 700 to 900 ° C. for 8 to 24 hours, and then pulverizing the obtained baked product. Can do.

For Ti ₂ Nb ₁₀ O ₂₉ , 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 a crystal having a high degree of crystallinity is obtained by heat treatment. It can also be obtained by mixing and pulverizing a predetermined material with a ball mill or the like to obtain a solid, followed by firing. As the niobium compound, niobium hydroxide and the like can be used, and as the titanium compound, sulfates such as titanyl sulfate and titanium sulfate, nitrates, chlorides, organic acids and the like can be used. 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 production method in which the liquid is separated into solid and liquid and fired is preferable. In addition, the molar ratio (Nb / Ti) of niobium and titanium in the suspension is preferably 4.0 to 6.0, and more preferably 4.5 to 5.5.

TiNb ₂ O ₇ can be obtained by firing a titanium compound and a niobium compound. Examples of the titanium compound that can be used include hydrous titanium oxides such as titanium oxide, orthotitanic acid, and metatitanic acid. 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. Examples of niobium compounds that can be used 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.
After mixing and pulverizing predetermined amounts of these titanium compound and niobium compound, TiNb ₂ O ₇ can be obtained by calcination at a temperature of 1200 to 1400 ° C. for 4 to 24 hours and then pulverizing the obtained baked product. .

Brookite-type TiO ₂ is a method of hydrothermally treating an aqueous solution containing a hydroxycarboxylic acid titanium complex in a temperature range of 100 ° C. to 300 ° C. while maintaining the pH at 8 to 13, and a titanium compound such as titanyl sulfate is oxalic acid. After peroxylation using hydrogen peroxide or the like, the obtained precipitate can be obtained by baking at a temperature of 550 to 820 ° C. Moreover, a commercial item can also be used suitably.

SiO heats the SiO ₂ and Si to 1250 to 1350 ° C. after mixing with or in a vacuum in a non-oxidizing atmosphere at a predetermined molar ratio, a method of depositing the vaporized SiO, SiO ₂ is hydrogen and the like reducing A method of heating in gas to reduce a predetermined amount, a method of heating SiO ₂ after mixing with a predetermined amount of carbon C, metal, etc. and heating to reduce a predetermined amount, and heating Si with oxygen gas or oxide to oxidize a predetermined amount It can be obtained by a method and a method in which a mixed gas of silicon compound gas such as SiH ₄ and oxygen is subjected to a heating reaction or a plasma decomposition reaction. Moreover, a commercial item can also be used suitably.

  The oxide-based negative electrode active material for a secondary battery of the present invention is obtained by supporting carbon derived from cellulose nanofibers and carbon derived from a water-soluble carbon material on the oxide for negative electrode active material. That is, it is obtained by using cellulose nanofiber and a water-soluble carbon material as a carbon source, and both the carbon obtained by carbonizing the cellulose nanofiber and the carbon obtained by carbonizing the water-soluble carbon material include the above oxide. It is firmly supported. Cellulose nanofiber is a skeletal component that occupies about 50% of all plant cell walls, and is a lightweight high-strength fiber that can be obtained by defibrating plant fibers constituting such cell walls to nano size, It also has good dispersibility in water. In addition, since the cellulose molecular chains constituting the cellulose nanofibers have a periodic structure formed of carbon, they are carbonized and firmly supported on the oxide, which is combined with the water-soluble carbon material. It is possible to obtain a useful negative electrode active material that can effectively improve the discharge characteristics of the secondary battery.

  The cellulose nanofiber that can be used is not particularly limited as long as it is obtained by defibrating the plant fiber constituting the plant cell wall to nano size, for example, serish KY-100S (manufactured by Daicel Finechem), etc. Commercial products can be used. The fiber diameter of the cellulose nanofiber is preferably 4 to 500 nm, more preferably 5 to 400 nm, and still more preferably 10 to 300 nm from the viewpoint of firmly supporting the oxide on the oxide.

  The cellulose nanofibers are then carbonized, and are present in the oxide-based negative electrode active material for secondary batteries of the present invention as carbon supported on the negative electrode active material-derived cellulose nanofibers. The amount of carbon derived from cellulose nanofibers in terms of atoms is preferably 0.10 to 9% by mass, more preferably 0.15 to 8% by mass in the oxide-based negative electrode active material for secondary battery of the present invention. %, More preferably 0.15 to 6% by mass.

  In addition, the atomic equivalent amount of carbon derived from cellulose nanofibers present in the oxide-based negative electrode active material for secondary batteries is calculated from the amount of carbon measured using a carbon / sulfur analyzer and the amount of water-soluble carbon material added. This can be confirmed by subtracting the atomic equivalent amount of carbon derived from the water-soluble carbon material to be obtained.

  The water-soluble carbon material supported as carbon carbonized by the oxide for the negative electrode active material is 0.4 g or more, preferably 1.0 g in terms of carbon atom of the water-soluble carbon material in 100 g of water at 25 ° C. This means a carbon material that dissolves, and functions as a carbon source carried by the oxide for negative electrode active material. 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 these, glucose, fructose, sucrose, and dextrin are preferable, and glucose is more preferable from the viewpoint of improving the solubility and dispersibility in a solvent and effectively functioning as a carbon material.

  The amount of the carbon derived from the water-soluble carbon material is such that the carbon derived from the water-soluble carbon material is effectively supported at the site where the oxide surface for the negative electrode active material is exposed without the carbon derived from cellulose nanofibers. From the above, in the positive electrode active material for a secondary battery of the present invention, it is preferably 0.10 to 9% by mass, more preferably 0.15 to 7% by mass, and further preferably 0.15 to 6% by mass. It is.

  The carbon atom equivalent of the cellulose nanofiber and the water-soluble carbon material is obtained by oxidizing the carbonized cellulose nanofiber and the carbonized water-soluble carbon material as carbon supported on the negative electrode active material oxide for the secondary battery of the present invention. Coexists in the physical negative electrode active material. The carbon atom equivalent amount of the cellulose nanofiber and the water-soluble carbon material corresponds to the total supported amount of the carbon derived from the cellulose nanofiber and the carbon derived from the water-soluble carbon material, and the oxide-based negative electrode for the secondary battery of the present invention. In the active material, the total amount is preferably 0.2 to 18% by mass, more preferably 0.3 to 15% by mass, and further preferably 0.3 to 12% by mass.

  The oxide-based negative electrode active material for a secondary battery of the present invention is efficiently supported on the oxide for negative electrode active material while complementing each other as carbon obtained by carbonizing cellulose nanofibers and a water-soluble carbon material. Yes, by finally firing, these carbon nanofibers and carbon derived from the water-soluble carbon material can be firmly supported on the oxide for negative electrode active material, and the oxide for negative electrode active material without the presence of carbon It is possible to effectively avoid the exposure of the surface.

Specifically, the oxide-based negative electrode active material for a secondary battery of the present invention is a step of obtaining a suspension X by adding cellulose nanofibers, a water-soluble carbon material and water to the oxide X for negative electrode active material ( It can be obtained by a method for producing an oxide-based negative electrode active material for a secondary battery, comprising the step (II) of spraying and drying the obtained suspension X to obtain a granulated body Y, followed by firing (II). it can.

  Step (I) is a step of obtaining a suspension X by adding cellulose nanofibers, a water-soluble carbon material and water to the oxide X for negative electrode active material. As described above, the amount of cellulose nanofiber added in the step (I) may be an amount such that the carbon atom-converted amount of cellulose nanofiber is within the above range as carbon derived from cellulose nanofiber. From the viewpoint of effectively supporting carbon derived from cellulose nanofibers on the surface of the oxide X for negative electrode active material and maintaining sufficient charge / discharge capacity, it is preferably 0 with respect to 100 parts by mass of the oxide X for negative electrode active material. 0.2 to 36 parts by mass, more preferably 0.3 to 32 parts by mass, and still more preferably 0.4 to 24 parts by mass.

  Further, the amount of the water-soluble carbon material added may be an amount such that the carbon-derived equivalent amount of the water-soluble carbon material falls within the above range as the carbon derived from the water-soluble carbon material as described above. From the viewpoint of effectively supporting the carbon derived from the water-soluble carbon material on the surface of the oxide X for active material and maintaining sufficient charge / discharge capacity, it is preferably 0 with respect to 100 parts by mass of the oxide X for negative electrode active material. 0.2 to 36 parts by mass, more preferably 0.3 to 28 parts by mass, and still more preferably 0.4 to 24 parts by mass.

  Furthermore, the amount of water added is such that cellulose nanofibers and water-soluble carbon materials are dispersed well in the suspension X, and these are efficiently supported on the surface of the oxide X for negative electrode active material as carbonized carbon. From the viewpoint, the amount is preferably 30 to 300 parts by mass, more preferably 50 to 250 parts by mass, and further preferably 75 to 200 parts by mass with respect to 100 parts by mass of the oxide X for negative electrode active material.

Step (II) is a step in which the suspension X obtained in step (I) is spray-dried to obtain a granulated body Y and then fired. As the spray drying in the step (II), spray drying by a spray drying method is suitable. For example, a micro mist dryer (MDL-050M manufactured by Fujisaki Electric Co., Ltd.) equipped with a four-fluid nozzle is used as such an apparatus. Can do. As processing conditions of the apparatus used for spray drying, the air pressure is preferably 0.3 to 0.8 MPa, more preferably 0.5 to 0.7 MPa, and the air flow rate is 20 to 60 NL / min. It is preferable that it is 50-60 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 suspension (slurry) flow rate is from the point of obtaining a granulated body Y having a desired average particle size. It is preferable that it is 20-70 g / min, and it is more preferable that it is 50-70 g / min.

  In addition, the average particle diameter of the granulated body Y obtained in the step (II) is preferably 50 to 2000 nm, more preferably from the viewpoint of efficiently supporting both the cellulose nanofibers and the water-soluble carbon material as carbon. 50-1000 nm.

  In the step (II), the obtained granulated body Y is then fired. Firing is preferably performed in a reducing atmosphere or an inert atmosphere. By such firing, carbon derived from the cellulose nanofibers is firmly supported on the surface of the oxide for negative electrode active material, and carbon derived from the water-soluble carbon material also exists as carbon covering the surface of the oxide. Thus, the conductivity of the obtained oxide-based negative electrode active material can be effectively increased.

  The firing temperature is preferably 500 to 1000 ° C, more preferably 600 to 850 ° C, and still more preferably 650 to 750 ° C, from the viewpoint of carbonizing the cellulose nanofiber and the water-soluble carbon material more effectively. The firing time is preferably 10 minutes to 24 hours, more preferably 30 minutes to 12 hours.

The oxide-based negative electrode active material for a secondary battery of the present invention has a synergistic action in which the carbon derived from the cellulose nanofiber and the carbon derived from the water-soluble carbon material are both supported on the oxide for the negative electrode active material. The amount of adsorbed moisture in the oxide-based negative electrode active material for secondary batteries can be effectively reduced. Specifically, the amount of adsorbed moisture of the oxide-based negative electrode active material for secondary battery of the present invention is as follows for the oxide-based negative electrode active material for secondary battery in which the oxide for negative electrode active material is Li ₄ Ti ₅ O _12. , Preferably it is 500 ppm or less, More preferably, it is 450 ppm or less. Further, in the oxide-based negative electrode active material for a secondary battery in which the oxide for the negative electrode active material is Ti ₂ Nb ₁₀ O ₂₉ , the oxide-based negative electrode active material for the secondary battery is preferably 89 ppm or less, and more Preferably, it is 85 ppm or less, and the oxide-based negative electrode active material for a secondary battery in which the oxide for the negative electrode active material is TiNb ₂ O ₇ , preferably 80 ppm or less in the oxide-based negative electrode active material for a secondary battery. Yes, more preferably 75 ppm or less, and in an oxide-based negative electrode active material for a secondary battery in which the anode active material oxide is brookite-type TiO ₂ , it is preferably 520 ppm or less, more preferably 510 ppm or less. Furthermore, in the oxide-based negative electrode active material for a secondary battery in which the oxide for the negative electrode active material is SiO, the oxide-based negative electrode active material for the secondary battery is preferably 128 ppm or less, more preferably 125 ppm or less. is there.
The amount of adsorbed water is such that moisture is adsorbed until equilibrium is reached at a temperature of 20 ° C. and a relative humidity of 50%. Measured as the amount of water volatilized from the start point to the end point, starting from when the temperature rise is resumed from 150 ° C. when held for 20 minutes and ending at the constant temperature state at 250 ° C. The amount of adsorbed water of the oxide-based negative electrode active material for a secondary battery and the amount of water volatilized between the start point and the end point are regarded as the same amount, and the amount of volatilized water is measured. The value is the amount of adsorbed water of the oxide-based negative electrode active material for secondary batteries.

Thus, since the oxide-based negative electrode active material for a secondary battery of the present invention hardly adsorbs moisture, the amount of adsorbed moisture can be effectively reduced without requiring strong drying conditions as a production environment. Both the obtained lithium ion secondary battery and sodium ion secondary battery can stably exhibit excellent battery characteristics even under various usage environments.
When water is adsorbed until equilibrium is reached at a temperature of 20 ° C. and a relative humidity of 50%, the temperature is raised to 150 ° C. and held for 20 minutes, and further raised to a temperature of 250 ° C. and held for 20 minutes. The amount of water volatilized between the start point and the end point, starting from when the temperature rise is resumed from 150 ° C. and the end point when the constant temperature state at 250 ° C. is completed, is measured using a Karl Fischer moisture meter, for example. Can be measured.

In addition, the tap density of the oxide-based negative electrode active material for secondary battery of the present invention is a secondary electrode in which the negative electrode active material oxide is Li ₄ Ti ₅ O ₁₂ from the viewpoint of stably expressing excellent battery characteristics. In the oxide type negative electrode active material for a battery, it is preferably 0.8 to 2.5 g / cm ³ , more preferably 1.2 to 2.5 g / cm ³ . Further, the anode active material for oxide Ti ₂ Nb ₁₀ O ₂₉ is a rechargeable battery for oxide-based negative electrode active material is preferably 0.9~2.7g / cm ^3, more preferably 1.3 was ~2.6g / cm ^3, the negative electrode active material for oxide is TiNb ₂ O ₇ secondary battery oxide-based negative electrode active material is preferably 0.9~2.7g / cm ^3, More preferably, it is 1.3 to 2.6 g / cm ³ , and in an oxide-based negative electrode active material for a secondary battery in which the negative electrode active material oxide is brookite-type TiO ₂ , preferably 0.9 to 3.0 g. / Cm ³ , more preferably 1.1 to 2.8 g / cm ³ . Further, in the oxide-based negative electrode active material for secondary batteries in which the oxide for negative electrode active material is SiO, it is preferably 0.6 to 2.5 g / cm ³ , more preferably 0.8 to 2.5 g / cm 2. cm ³ .

  A method for producing a secondary battery using the obtained oxide-based negative electrode active material for a secondary battery is not particularly limited, and any known method can be used. For example, the negative electrode active material is mixed with additives such as a binder and a solvent to obtain a coating liquid. At this time, if necessary, a conductive additive may be further added and mixed. The binder is not particularly limited, and any known agent can be used. Specific examples include polytetrafluoroethylene, polyvinylidene fluoride, polyvinyl chloride, and ethylene propylene diene polymer. Moreover, it does not specifically limit as this conductive support agent, Any well-known agents other than graphite can be used. Specific examples include acetylene black, ketjen black, and fibrous carbon. Next, such a coating solution is applied onto a current collector such as a copper foil and dried to obtain a negative electrode.

  The secondary battery to which the secondary battery negative electrode containing the secondary battery oxide-based negative electrode active material of the present invention 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.

<< Production Example 1: Oxide for Negative Electrode Active Material = Li ₄ Ti ₅ O ₁₂ >>
[Example 1]
Anatase TiO ₂ (manufactured by Kanto Chemical Co., Inc.) 1.768 kg, Li ₂ CO ₃ (manufactured by Kanto Chemical Co., Ltd.) 0.654 kg, and ethanol (manufactured by Kanto Chemical Co., Ltd., grinding aid) 6 g are mixed. After pulverizing with a ball mill for 4 hours, Li ₄ Ti ₅ O ₁₂ (average particle diameter of 100 nm) was obtained by firing at 800 ° C. for 10 hours in an air atmosphere.

1000 g of the resulting Li ₄ Ti ₅ O ₁₂ was fractionated, and 2000 g of water and 3.75 g of glucose (anhydrous crystalline glucose manufactured by Nippon Shokuhin Kako) were added to 0.15% by mass in terms of carbon atoms in the negative electrode active material. Equivalent), and cellulose nanofiber (Daicel Finechem Selish FD-200L, average fiber diameter 10 to 100 nm) 16.79 g (corresponding to 0.15% by mass in terms of carbon atom in the negative electrode active material) were added, to obtain a suspension ^{a 1.}
Then, the suspension ^{A 1} spray drying; after (spray dryer MDL-050M, Fujisaki made Electric Co.) to obtain a granule A ^1, which in an argon atmosphere of hydrogen (hydrogen concentration: 3%), A negative electrode active material for secondary battery (Li ₄ Ti ₅ O ₁₂ / (CNF + C), carbon content 0.3% by mass, calcined at 750 ° C. for 1 hour, and supporting carbon derived from glucose and carbon derived from cellulose nanofibers )

[Example 2]
62.56 g of glucose (corresponding to 2.5% by mass in terms of carbon atom in the negative electrode active material) and 279.9 g of cellulose nanofiber (in terms of carbon atom equivalent in the negative electrode active material to 2.5% by mass) For the secondary battery in which carbon derived from glucose and carbon derived from cellulose nanofibers are supported in the same manner as in Example 1 except that the suspension B ¹ obtained as the above was used instead of the suspension A ¹ A negative electrode active material (Li ₄ Ti ₅ O ₁₂ / (CNF + C), carbon content 5.0% by mass) was obtained.

[Example 3]
157.3 g of glucose (corresponding to 6.0% by mass in terms of carbon atom in the negative electrode active material) and 671.6g of cellulose nanofiber (in terms of carbon atom equivalent in the negative electrode active material to 6.0% by mass) except for using the suspension C ¹ which was obtained as equivalent) in place of the suspension a ^1, in the same manner as in example 1, for a secondary battery in which the carbon derived from carbon and cellulose nanofibers from glucose was carried A negative electrode active material (Li ₄ Ti ₅ O ₁₂ / (CNF + C), carbon content 12.0% by mass) was obtained.

[Comparative Example 1]
1,000 g of Li ₄ Ti ₅ O ₁₂ obtained by firing in Example 1 was collected, and 2000 g of water and 125.1 g of glucose (corresponding to 5.0% by mass in terms of carbon atom in the negative electrode active material) were added thereto. A negative electrode active material for a secondary battery on which carbon formed by carbonizing glucose was supported in the same manner as in Example 1 except that the suspension D ¹ obtained by addition was used instead of the suspension A ^1. Li ₄ Ti ₅ O ₁₂ / C, carbon content 5.0% by mass).

[Comparative Example 2]
262.2 g of glucose (corresponding to 10.0% by mass in terms of carbon atom in the negative electrode active material) and 1119.3 g of cellulose nanofiber (in terms of carbon atom equivalent in the negative electrode active material to 10.0% by mass) except for using the suspension E ¹ which was obtained as equivalent) in place of the suspension a ^1, in the same manner as in example 1, for a secondary battery in which the carbon derived from carbon and cellulose nanofibers from glucose was carried A negative electrode active material (Li ₄ Ti ₅ O ₁₂ / (CNF + C), carbon content 20.0% by mass) was obtained.

<< Production Example 2: Oxide for Negative Electrode Active Material = Ti ₂ Nb ₁₀ O ₂₉ >>
[Example 4]
In a 500 mL plastic container, put 12.16 g of anatase TiO ₂ (manufactured by Kanto Chemical Co., Ltd.), Nb (OH) ₅ (manufactured by HC Starck) 144.4 g, and 100 g of water, 1300 g of zirconia balls having a diameter of ₃ mm, Mixing and grinding were 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. The obtained cake was freeze-dried at −50 ° C. for 12 hours. The obtained solid was calcined at 1100 ° C. for 12 hours in an air atmosphere to obtain Ti ₂ Nb ₁₀ O ₂₉ .

1000 g of the obtained Ti ₂ Nb ₁₀ O ₂₉ was collected, and 2000 g of water, 3.75 g of glucose (corresponding to 0.15% by mass in terms of carbon atom in the negative electrode active material), and cellulose nanofibers. 79 g (corresponding to 0.15% by mass in terms of carbon atoms content in the anode active material) was added to obtain a suspension ^{F 1.}
Next, the suspension F ¹ was spray-dried to obtain a granulated body F ¹ , which was then calcined at 750 ° C. for 1 hour in an argon-hydrogen atmosphere (hydrogen concentration 3%) to obtain glucose-derived carbon and cellulose. A secondary battery negative electrode active material (Ti ₂ Nb ₁₀ O ₂₉ / (CNF + C), carbon content 0.3 mass%) on which carbon derived from nanofibers was supported was obtained.

[Example 5]
62.56 g of glucose (corresponding to 2.5% by mass in terms of carbon atom in the negative electrode active material) and 279.9 g of cellulose nanofiber (in terms of carbon atom equivalent in the negative electrode active material to 2.5% by mass) except for using the suspension G ¹ which was obtained as equivalent) in place of the suspension F ^1, in the same manner as in example 4, for a secondary battery in which the carbon derived from carbon and cellulose nanofibers from glucose was carried A negative electrode active material (Ti ₂ Nb ₁₀ O ₂₉ / (CNF + C), carbon content 5.0% by mass) was obtained.

[Example 6]
157.3 g of glucose (corresponding to 6.0% by mass in terms of carbon atom in the negative electrode active material) and 671.6g of cellulose nanofiber (in terms of carbon atom equivalent in the negative electrode active material to 6.0% by mass) For the secondary battery in which the carbon derived from glucose and the carbon derived from cellulose nanofibers are supported in the same manner as in Example 4 except that the suspension H ¹ obtained as above was used instead of the suspension F ¹ A negative electrode active material (Ti ₂ Nb ₁₀ O ₂₉ / (CNF + C), carbon content 12.0% by mass) was obtained.

[Comparative Example 3]
1000 g of Ti ₂ Nb ₁₀ O ₂₉ obtained by firing in Example 4 was collected, and 2000 g of water and 125.1 g of glucose (corresponding to 5.0% by mass in terms of carbon atom in the negative electrode active material) were added thereto. A negative electrode active material for secondary battery (Ti ₂ Nb) on which glucose-derived carbon is supported in the same manner as in Example 4 except that the suspension I ¹ obtained by addition was used instead of the suspension F ^1. ₁₀ O ₂₉ / C, carbon content 5.0% by mass).

[Comparative Example 4]
262.2 g of glucose (corresponding to 10.0% by mass in terms of carbon atom in the negative electrode active material) and 1119.3 g of cellulose nanofiber (in terms of carbon atom equivalent in the negative electrode active material to 10.0% by mass) except for using the suspension J ¹ which was obtained as equivalent) in place of the suspension F ^1, in the same manner as in example 4, for a secondary battery in which the carbon derived from carbon and cellulose nanofibers from glucose was carried A negative electrode active material (Ti ₂ Nb ₁₀ O ₂₉ / (CNF + C), carbon content 20.0% by mass) was obtained.

<< Production Example 3: Oxide for Negative Electrode Active Material = TiNb ₂ O ₇ >>
[Example 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 g 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.
After adding 1 part by mass of water to 1 part by mass of the obtained cake to make a slurry, it was spray-dried using MDL-050M in the same manner as in Example 1, and the resulting granulated product was subjected to an atmospheric atmosphere. Under baking at 1300 ° C. for 12 hours, TiNb ₂ O ₇ was obtained.

1,000 g of the obtained TiNb ₂ O ₇ was collected, and 2000 g of water, 3.75 g of glucose (corresponding to 0.15% by mass in terms of carbon atom in the negative electrode active material), and 16.79 g of cellulose nanofibers ( corresponds to 0.15% by mass in terms of carbon atoms content in the anode active material) was added to obtain a suspension K ^1.
Then, after the suspension K ¹ was spray dried to obtain a granule K ^1, which argon atmosphere of hydrogen (hydrogen concentration: 3%), and then calcined 1 hour at 750 ° C., glucose-derived carbon and cellulose A secondary battery negative electrode active material (TiNb ₂ O ₇ / (CNF + C), carbon content 0.3 mass%) on which carbon derived from nanofibers was supported was obtained.

[Example 8]
62.56 g of glucose (corresponding to 2.5% by mass in terms of carbon atom in the negative electrode active material) and 279.9 g of cellulose nanofiber (in terms of carbon atom equivalent in the negative electrode active material to 2.5% by mass) except for using the suspension L ¹ which was obtained as equivalent) in place of the suspension K ^1, in the same manner as in example 7, for a secondary battery in which the carbon derived from carbon and cellulose nanofibers from glucose was carried A negative electrode active material (TiNb ₂ O ₇ / (CNF + C), carbon content 5.0% by mass) was obtained.

[Example 9]
157.3 g of glucose (corresponding to 6.0% by mass in terms of carbon atom in the negative electrode active material) and 671.6g of cellulose nanofiber (in terms of carbon atom equivalent in the negative electrode active material to 6.0% by mass) except for using the suspension M ¹ which was obtained as equivalent) in place of the suspension K ^1, in the same manner as in example 7, for a secondary battery in which the carbon derived from carbon and cellulose nanofibers from glucose was carried A negative electrode active material (TiNb ₂ O ₇ / (CNF + C), carbon content 12.0% by mass) was obtained.

[Comparative Example 5]
1,000 g of TiNb ₂ O ₇ obtained by firing in Example 7 was collected, and 2000 g of water and 125.1 g of glucose (corresponding to 5.0% by mass in terms of carbon atom in the negative electrode active material) were added thereto. The negative electrode active material for secondary battery (TiNb ₂ O ₇ / C) on which carbon derived from glucose was supported was obtained in the same manner as in Example 7 except that the suspension N ¹ obtained in this way was used instead of the suspension K ^1. C, carbon mass 5.0% by mass).

[Comparative Example 6]
262.2 g of glucose (corresponding to 10.0% by mass in terms of carbon atom in the negative electrode active material) and 1119.3 g of cellulose nanofiber (in terms of carbon atom equivalent in the negative electrode active material to 10.0% by mass) For the secondary battery on which carbon derived from glucose and carbon derived from cellulose nanofibers are supported in the same manner as in Example 7, except that the suspension O ¹ obtained as a) was used instead of the suspension K ¹ A negative electrode active material (TiNb ₂ O ₇ / (CNF + C), carbon content 20.0% by mass) was obtained.

<< Production Example 4: Oxide for Negative Electrode Active Material = Brookite TiO ₂ >>
[Example 10]
After adding 2656 g of titanyl sulfate (manufactured by Kishida Chemical Co., Ltd.) to 4000 g of water, the solution was stirred for 24 hours while heating to 50 ° C. to obtain a solution P ¹ . Further, the water 4000 g, was added oxalic acid dihydrate (manufactured by Kanto Chemical (Co.)) 633 g, to obtain a solution ^{P 2} was dissolved under warming to 50 ° C.. Then, the solution P ^1, was added dropwise over a solution P ² 10 minutes, and stirred for 12 hours while heating at 90 ° C.. The obtained precipitate was separated by a filter press and then dried at 80 ° C. for 24 hours to obtain titanium oxyoxalate. The obtained titanium oxyoxalate was baked at 600 ° C. for 2 hours to obtain brookite type TiO ₂ .

1000 g of the obtained brookite-type TiO ₂ was collected, and 2000 g of water, 3.75 g of glucose (corresponding to 0.15% by mass in terms of carbon atom in the negative electrode active material), and 16.79 g of cellulose nanofibers ( Suspension P ¹ was obtained by adding 0.15% by mass in terms of carbon atoms in the negative electrode active material.
Next, the suspension P ¹ was spray-dried to obtain a granulated body P ¹ , which was then calcined at 750 ° C. for 1 hour in an argon-hydrogen atmosphere (hydrogen concentration 3%) to obtain glucose-derived carbon and cellulose. A secondary battery negative electrode active material (Brookite TiO ₂ / (CNF + C), carbon content 0.3 mass%) on which carbon derived from nanofibers was supported was obtained.

[Example 11]
62.56 g of glucose (corresponding to 2.5% by mass in terms of carbon atom in the negative electrode active material) and 279.9 g of cellulose nanofiber (in terms of carbon atom equivalent in the negative electrode active material to 2.5% by mass) except for using the suspension Q ¹ which was obtained as equivalent) in place of the suspension P ^1, in the same manner as in example 10, for a secondary battery in which the carbon derived from carbon and cellulose nanofibers from glucose was carried A negative electrode active material (Brookite TiO ₂ / (CNF + C), carbon content 5.0% by mass) was obtained.

[Example 12]
157.3 g of glucose (corresponding to 6.0% by mass in terms of carbon atom in the negative electrode active material) and 671.6g of cellulose nanofiber (in terms of carbon atom equivalent in the negative electrode active material to 6.0% by mass) For the secondary battery in which carbon derived from glucose and carbon derived from cellulose nanofibers are supported in the same manner as in Example 10, except that the suspension R ¹ obtained as the above was used instead of the suspension P ¹ A negative electrode active material (Brookite type TiO ₂ / (CNF + C), carbon content 12.0% by mass) was obtained.

[Comparative Example 7]
1000 g of brookite-type TiO ₂ obtained by firing in Example 10 was collected, and 2000 g of water and 125.1 g of glucose (corresponding to 5.0 mass% in terms of carbon atom in the negative electrode active material) were added thereto. The negative electrode active material for secondary battery on which carbon derived from glucose was supported (Brookite type TiO ₂ / V) in the same manner as in Example 10 except that the suspension S ¹ obtained in this way was used instead of the suspension P ^1. C, carbon mass 5.0% by mass).

[Comparative Example 8]
262.2 g of glucose (corresponding to 10.0% by mass in terms of carbon atom in the negative electrode active material) and 1119.3 g of cellulose nanofiber (in terms of carbon atom equivalent in the negative electrode active material to 10.0% by mass) For the secondary battery in which carbon derived from glucose and carbon derived from cellulose nanofibers are supported in the same manner as in Example 10 except that the suspension T ¹ obtained as (equivalent) was used instead of the suspension P ¹ A negative electrode active material (Brookite type TiO ₂ / (CNF + C), carbon content 20.0% by mass) was obtained.

<< Production Example 5: Oxide for negative electrode active material = SiO >>
[Example 13]
100 g of commercially available SiO powder (manufactured by Osaka Titanium Technologies Co., Ltd.) was pulverized with a ball mill for 24 hours to obtain SiO powder having an average particle diameter of 200 nm.

1000 g of the obtained SiO was fractionated, and 2000 g of water, 3.75 g of glucose (corresponding to 0.15% by mass in terms of carbon atom in the negative electrode active material), and 16.79 g of cellulose nanofiber (negative electrode active material) by adding equivalent) to 0.15 wt% in terms of carbon atoms content in the medium to give a suspension U ^1.
Next, the suspension U ¹ was spray-dried to obtain a granulated body U ¹ , which was then calcined at 750 ° C. for 1 hour in an argon-hydrogen atmosphere (hydrogen concentration 3%) to obtain glucose-derived carbon and cellulose. A secondary battery negative electrode active material (SiO / (CNF + C), carbon content 0.3 mass%) on which carbon derived from nanofibers was supported was obtained.

[Example 14]
62.56 g of glucose (corresponding to 2.5% by mass in terms of carbon atom in the negative electrode active material) and 279.9 g of cellulose nanofiber (in terms of carbon atom equivalent in the negative electrode active material to 2.5% by mass) except for using the suspension V ¹ obtained by the equivalent) in place of the suspension U ^1, in the same manner as in example 13, for a secondary battery in which the carbon derived from carbon and cellulose nanofibers from glucose was carried A negative electrode active material (SiO / (CNF + C), carbon content 5.0 mass%) was obtained.

[Example 15]
157.3 g of glucose (corresponding to 6.0% by mass in terms of carbon atom in the negative electrode active material) and 671.6g of cellulose nanofiber (in terms of carbon atom equivalent in the negative electrode active material to 6.0% by mass) except for using the suspension W ¹ which was obtained as equivalent) in place of the suspension U ^1, in the same manner as in example 10, for a secondary battery in which the carbon derived from carbon and cellulose nanofibers from glucose was carried A negative electrode active material (SiO / (CNF + C), carbon content 12.0% by mass) was obtained.

[Comparative Example 9]
1000 g of SiO obtained by pulverization in Example 13 was collected, and 2000 g of water and 125.11 g of glucose (corresponding to 5.0 mass% in terms of carbon atom in the negative electrode active material) were added thereto. except for using the suspension X ¹ in place of the suspension U ^1, in the same manner as in example 13, the negative electrode active material for a secondary battery in which the carbon derived from glucose was carried (SiO / C, the amount of carbon 5. 0% by mass) was obtained.

[Comparative Example 10]
262.2 g of glucose (corresponding to 10.0% by mass in terms of carbon atom in the negative electrode active material) and 1119.3 g of cellulose nanofiber (in terms of carbon atom equivalent in the negative electrode active material to 10.0% by mass) except for using the suspension Y ^1, obtained by the equivalent) in place of the suspension U ^1, in the same manner as in example 13, for a secondary battery in which the carbon derived from carbon and cellulose nanofibers from glucose was carried A negative electrode active material (SiO / (CNF + C), carbon content 20.0% by mass) was obtained.

<Measurement of adsorbed water content>
Each obtained negative electrode active material was allowed to stand in an environment at a temperature of 20 ° C. and a relative humidity of 50% for 1 day to adsorb moisture until it reached equilibrium, heated to a temperature of 150 ° C. and held for 20 minutes, and then further heated to When the temperature is raised to 250 ° C. and held for 20 minutes, the start point is when the temperature rise is resumed from 150 ° C., the end point is when the constant temperature state at 250 ° C. is finished, and volatilization occurs between the start point and the end point. The measured moisture content was measured using a Karl Fischer moisture meter (MKC-610, manufactured by Kyoto Denshi Kogyo Co., Ltd.) and determined as the amount of adsorbed moisture in the negative electrode active material.
The results are shown in Table 1.

<< Evaluation of charge / discharge characteristics using secondary battery >>
Each obtained negative electrode active material, acetylene black (conductive agent), and polyvinylidene fluoride (binding agent) were mixed at a mass ratio of 85: 10: 5, and N-methyl-2-pyrrolidone was added thereto. The mixture was sufficiently kneaded 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 10 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, a Li foil punched out to φ15 mm was used as a counter electrode, and a solution obtained by dissolving LiPF ₆ at a concentration of 1 mol / L in a mixed solvent in which ethylene carbonate and ethylmethyl carbonate were mixed at a volume ratio of 3: 7 was used as an electrolyte. A polymer porous film (made of polypropylene) was used as a separator, and was housed and housed in a conventional manner in an atmosphere with a dew point of −50 ° C. or lower to produce a coin-type lithium secondary battery (CR-2032).

For each lithium secondary battery created, the upper limit voltage, the lower limit voltage, and the two charge / discharge rates (rate A and rate B) in the charge / discharge test were set to the values shown in Table 1, respectively, under an ambient temperature of 30 ° C. 50 cycles of repeated charge / discharge tests were performed at each rate, the initial discharge capacity (mAh / g) and the discharge capacity after 50 cycles (mAh / g) were measured, and the capacity retention rate (%) was calculated by the following formula (2). Asked.
Capacity retention (%) = (discharge capacity after 50 cycles) / (discharge capacity after 1 cycle) × 100 (2)
The results are shown in Table 1.
In addition, these values are so preferable that a numerical value is large, and the influence by the amount of moisture to adsorb | suck to a battery characteristic tends to appear in the capacity | capacitance retention rate in a quick charge / discharge rate.

  From the above results, it can be seen that the negative electrode active material of the example can surely reduce the amount of adsorbed moisture as compared with the negative electrode active material of the comparative example, and can also exhibit excellent performance in the obtained battery.

Claims (7)

In the oxide for negative electrode active material , 0.10-9 mass% of carbon derived from cellulose nanofibers in terms of carbon atom , and one or more selected from saccharides, polyols, polyethers, and organic acids An oxide-based negative electrode active material for a secondary battery, which is supported by 0.10 to 9% by mass of carbon derived from a water-soluble carbon material. The oxide-based negative electrode active material for a secondary battery according to claim 1, wherein the total supported amount of carbon derived from cellulose nanofibers and carbon derived from a water-soluble carbon material is 0.3 to 12% by mass. The oxide-based negative electrode active material for a secondary battery according to claim 1 or 2, wherein the water-soluble carbon material is glucose. Negative electrode active material for _{oxide, Li 4 Ti 5 O 12,} Ti 2 Nb 10 O 29, TiNb 2 O 7, brookite TiO _2, and any one of claims 1 to 3 is an oxide selected from SiO 1 An oxide-based negative electrode active material for a secondary battery according to Item. One type selected from 0.2 to 36 parts by mass of cellulose nanofibers, saccharides, polyols, polyethers, and organic acids, with respect to 100 parts by mass of the negative electrode active material oxide X. Step (I) in which a suspension X is obtained by adding 0.2 to 36 parts by mass of water-soluble carbon material and water with respect to 100 parts by mass of the negative electrode active material oxide X, and two or more types The manufacturing method of the oxide type negative electrode active material for secondary batteries provided with the process (II) baked, after spray-drying the obtained suspension X and obtaining the granulated body Y. The manufacturing method of the oxide type negative electrode active material for secondary batteries of Claim 5 whose average particle diameter of the granulated body Y is 50-2000 nm. The oxide according to claim 5 or 6 , wherein the oxide for the negative electrode active material is an oxide selected from Li ₄ Ti ₅ O ₁₂ , Ti ₂ Nb ₁₀ O ₂₉ , TiNb ₂ O ₇ , brookite type TiO ₂ , and SiO. The manufacturing method of the oxide type negative electrode active material for secondary batteries.