JP6243946B2 - Active material-containing particle mixture for non-aqueous electrolyte secondary battery and method for producing the same - Google Patents

Description

  The present invention relates to a particle mixture containing an active material for a non-aqueous electrolyte secondary battery used for an electrode of a non-aqueous electrolyte secondary battery and a method for producing the same.

  Many non-aqueous electrolyte secondary batteries using transition metal composite oxides as electrode active materials have been developed because of their good cycle characteristics and high safety. In such a non-aqueous electrolyte secondary battery, a battery electrode mixture slurry in which an active material and a conductive additive are usually mixed in a binder solution or slurry in which a battery electrode binder is dissolved in a solvent or dispersed in a dispersion medium. Is applied to the current collector, the solvent and the dispersion medium are removed by a method such as drying, and the active material current collectors and the active materials are bound to each other to produce an electrode.

  The battery performance of the nonaqueous electrolyte secondary battery greatly depends on the characteristics of the electrode active material and the conductive additive used, and also depends on the uniformity of the mixed state of the electrode active material and the conductive additive and the filling structure. Under these circumstances, when the electrode active material is made of a transition metal composite oxide, there is a problem that the specific gravity difference from the conductive additive is large and uniform mixing is difficult.

  For example, in Patent Document 1, the mixture of the electrode active material and the conductive assistant is made uniform by using water as a dispersion solvent to which carboxymethyl cellulose is added as a dispersion stabilizer. Moreover, in patent document 2, by adding the polyether which is polyethyleneglycol, polypropyleneglycol, polybutyleneglycol, or those mixtures to the water which is a dispersion | distribution solvent, and adding a binder (binder) further, electrode active material A uniform mixture is obtained while suppressing the separation of the conductive aid.

Japanese Patent Laying-Open No. 2015-201267 Japanese Patent Laying-Open No. 2015-225761

  However, according to the method described in Patent Document 1, separation by a dispersing agent may occur between the electrode active material and the conductive additive, so that even if a uniform mixture is obtained, a densely packed state is obtained. Have difficulty. On the other hand, according to the method described in Patent Document 2, although a uniform and dense mixture of the electrode active material and the conductive auxiliary agent can be obtained, since water is used as the dispersion solvent, the obtained electrode active material is obtained. Moisture tends to remain in the inside more than necessary, and the battery characteristics may be deteriorated.

  Therefore, the subject of this invention is providing the active material containing particle | grain mixture for nonaqueous electrolyte secondary batteries which is a uniform and dense mixture of an electrode active material and a conductive support agent, and its manufacturing method.

  Therefore, the present inventors have made various studies. As a result, a slurry obtained by adding a water-insoluble conductive carbon material and / or a water-soluble carbon material to the transition metal composite oxide particles, cellulose nanofiber (CNF) and And / or a slurry obtained from amorphous spherical carbon (ACS) and the like, and calcined through specific spray drying to obtain electrode active material particles, carbon derived from cellulose nanofibers and amorphous spherical carbon A mixture of particles containing the active material for non-aqueous electrolyte secondary batteries, in which the conductive auxiliary particles composed of at least one of the carbons are mixed with each other independently and uniformly without being supported on the other, is simple. The present invention has been found and the present invention has been completed.

  That is, the present invention relates to electrode active material particles (X) in which at least one of a water-insoluble conductive carbon material and a carbon derived from a water-soluble carbon material is supported on the particle surface of the transition metal composite oxide, and cellulose nanofibers. Provided is an active material-containing particle mixture for a non-aqueous electrolyte secondary battery in which conductive auxiliary agent particles (Y) made of at least one of carbon derived from amorphous carbon and carbon derived from amorphous spherical carbon are mixed as independent particles. To do.

The present invention also includes a step (I) of obtaining a slurry A by adding water-insoluble conductive carbon material and / or water-soluble carbon material and water to the transition metal composite oxide particles,
Step (II) of obtaining slurry B by mixing cellulose nanofibers and / or amorphous spherical carbon and water
Using a spray dryer having at least two injection ports, slurry A obtained in step (I) and slurry B obtained in step (II) are simultaneously spray-dried from different injection ports to form slurry A. Step (III) for obtaining a dry mixture E in which the granulated body C to be formed and the granulated body D formed from the slurry B are mixed, and the dry mixture E obtained in the step (III) is reduced or inert. Baking process in atmosphere (IV)
The manufacturing method of the said active material containing particle | grain mixture for nonaqueous electrolyte secondary batteries is provided.

  According to the present invention, a particle mixture obtained by uniformly and intimately mixing electrode active material particles and conductive additive particles can be obtained by a simple manufacturing method, and by using this, unnecessary moisture can be left. Even if it is a negative electrode or a positive electrode, it can be produced, and excellent battery physical properties can be exhibited even in the obtained secondary battery.

2 is a SEM image showing the particle mixture Z1 obtained in Example 1. FIG. “LMP” in FIG. 1 represents lithium iron manganese phosphate positive electrode active material particles X1 supported by glucose-derived carbon, and “CNF” represents conductive auxiliary agent particles Y1 composed of carbon derived from cellulose nanofibers. Show.

Hereinafter, the present invention will be described in detail.
The active material-containing particle mixture for a non-aqueous electrolyte secondary battery of the present invention comprises electrode active material particles (X) formed by supporting at least one of a water-insoluble conductive carbon material and a carbon derived from a water-soluble carbon material, cellulose nano Conductive auxiliary agent particles (Y) made of at least one of carbon derived from fiber and carbon derived from amorphous spherical carbon are mixed as independent particles. The electrode active material particles (X) and the conductive auxiliary particles (Y) are sufficiently dried, and one particle is uniformly mixed without being supported on the other particle, thereby unnecessary moisture. Is a useful mixture that can be directly used as a battery material without remaining.

The electrode active material particles (X) used in the present invention are particles formed by supporting at least one of a water-insoluble conductive carbon material and a carbon derived from a water-soluble carbon material on the particle surface of the transition metal composite oxide, It is obtained by adding a water-insoluble conductive carbon material and / or a water-soluble carbon material to the transition metal composite oxide and firing.
Such a transition metal composite oxide may be either an oxide used as a positive electrode active material of a secondary battery or an oxide used as a negative electrode active material of a secondary battery, and is not particularly limited. Examples of the positive electrode active material oxide include LiFe _0.3 Mn _0.7 PO ₄ , Li ₂ Fe _0.28 Mn _0.66 Zr _0.03 SiO ₄ , and NaFe _0.3 Mn _0.7 PO _4. Examples of the negative electrode active material oxide include Li ₄ Ti ₅ Examples thereof include O ₁₂ , TiNb ₂ O ₇ , and Ti ₂ Nb ₁₀ O ₂₉ .

LiFe _0.3 Mn _0.7 PO ₄ is prepared by mixing a lithium compound and a phosphoric acid compound, for example, and then preparing a suspension in which a metal salt containing an iron compound and a manganese compound is mixed. By doing so, a thing with high crystallinity can be obtained. 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.
Examples of lithium compounds include hydroxides, carbonates, sulfates, and acetates. Of these, hydroxide is preferable. Examples of the phosphoric acid compound include orthophosphoric acid (H ₃ PO ₄ , phosphoric acid), metaphosphoric acid, pyrophosphoric acid, triphosphoric acid, tetraphosphoric acid, ammonium phosphate, and ammonium hydrogen phosphate. Of these, phosphoric acid is preferably used, and is preferably used as an aqueous solution having a concentration of 70 to 90% by mass. Examples of the iron compound include iron acetate, iron nitrate, and iron sulfate. These may be used alone or in combination of two or more. Among these, iron sulfate is preferable from the viewpoint of improving battery characteristics. Furthermore, examples of the manganese compound include manganese acetate, manganese nitrate, manganese sulfate and the like. These may be used alone or in combination of two or more. Among these, manganese sulfate is preferable from the viewpoint of improving battery characteristics.
As a more specific production method, a suspension obtained by adding iron sulfate as an iron compound and manganese sulfate as a manganese compound to a mixed solution obtained by adding lithium hydroxide as a lithium compound and phosphoric acid as a phosphoric acid compound to water The production method is preferably such that the solid content obtained through hydrothermal reaction is solid-liquid separated and fired. In addition, content of the lithium compound in the said liquid mixture becomes like this. Preferably it is 5-50 mass parts with respect to 100 mass parts of water, More preferably, it is 10-45 mass parts.

Li ₂ Fe _0.28 Mn _0.66 Zr _0.03 SiO ₄ is prepared, for example, by mixing a lithium compound and a silicic acid compound and then preparing a suspension in which a metal salt containing an iron compound, a manganese compound and a zirconium compound is mixed, and by hydrothermal reaction. After obtaining crystals, a crystal having a high degree of crystallinity can be 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.
Examples of lithium compounds include hydroxides, carbonates, sulfates, and acetates. Of these, hydroxide is preferable. Further, the silicic acid compound is not particularly limited as long as it is a reactive silica compound. Amorphous silica, sodium salt (for example, sodium metasilicate (Na ₂ SiO ₃ ), Na ₄ SiO ₄ .H ₂ O) Etc. Examples of the iron compound include iron acetate, iron nitrate, and iron sulfate. These may be used alone or in combination of two or more. Among these, iron sulfate is preferable from the viewpoint of improving battery characteristics. Examples of manganese compounds include manganese acetate, manganese nitrate, manganese sulfate and the like. These may be used alone or in combination of two or more. Among these, manganese sulfate is preferable from the viewpoint of improving battery characteristics. Furthermore, examples of the zirconium compound include zirconium acetate, zirconium nitrate, and zirconium sulfate. These may be used alone or in combination of two or more. Of these, zirconium sulfate is preferable from the viewpoint of improving battery physical properties.
As a more specific production method, a mixed solution in which lithium hydroxide as a lithium compound and sodium metasilicate as a silicate compound are added to water, iron sulfate as an iron compound, manganese sulfate as a manganese compound, and zirconium sulfate as a zirconium compound A production method is preferred in which a suspension is prepared by adding a solid, and the solid content obtained through a hydrothermal reaction is solid-liquid separated and fired. In addition, content of the lithium compound in the said liquid mixture becomes like this. Preferably it is 5-40 mass parts with respect to 100 mass parts of water, More preferably, it is 7-35 mass parts.

NaFe _0.3 Mn _0.7 PO ₄ is prepared, for example, by mixing a sodium compound and a phosphoric acid compound, and then preparing a suspension in which a metal salt containing an iron compound and a manganese compound is mixed. By doing so, a thing with high crystallinity can be obtained. 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.
Examples of sodium compounds include hydroxides, carbonates, sulfates, and acetates. Of these, hydroxide is preferable. Examples of the phosphoric acid compound include orthophosphoric acid (H ₃ PO ₄ , phosphoric acid), metaphosphoric acid, pyrophosphoric acid, triphosphoric acid, tetraphosphoric acid, ammonium phosphate, and ammonium hydrogen phosphate. Of these, phosphoric acid is preferably used, and is preferably used as an aqueous solution having a concentration of 70 to 90% by mass. Examples of the iron compound include iron acetate, iron nitrate, and iron sulfate. These may be used alone or in combination of two or more. Among these, iron sulfate is preferable from the viewpoint of improving battery characteristics. Furthermore, examples of the manganese compound include manganese acetate, manganese nitrate, manganese sulfate and the like. These may be used alone or in combination of two or more. Among these, manganese sulfate is preferable from the viewpoint of improving battery characteristics.
As a more specific production method, a suspension is prepared by adding iron sulfate as an iron compound and manganese sulfate as a manganese compound to a mixed solution obtained by adding sodium hydroxide as a sodium compound and phosphoric acid as a phosphate compound to water. The production method is preferably such that the solid content obtained through hydrothermal reaction is solid-liquid separated and fired. In addition, content of the sodium compound in the said liquid mixture becomes like this. Preferably it is 5-50 mass parts with respect to 100 mass parts of water, More preferably, it is 10-45 mass parts.

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.

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. .

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.

  The transition metal composite oxide is preferably minute from the viewpoint of obtaining a secondary battery having good charge / discharge characteristics, and the average particle size thereof is preferably 20 to 400 nm, more preferably 20 to 200 nm. More preferably, it is 20-100 nm. Such a fine transition metal composite oxide can be obtained by grinding a transition metal composite oxide obtained by a solid phase method or by a hydrothermal method.

The water-insoluble conductive carbon material is a water-insoluble carbon material whose dissolution amount in 100 g of water at 25 ° C. is less than 0.4 g in terms of carbon atom of the water-insoluble conductive carbon material, and is not fired or the like. Both themselves have electrical conductivity and are carbon sources supported on the surface of the transition metal composite oxide particles. Examples of the water-insoluble conductive carbon material include one or more selected from graphite, acetylene black, ketjen black, channel black, furnace black, lamp black, and thermal black. The graphite may be any of artificial graphite (scaly, massive, earthy, graphene) or natural graphite. The BET specific surface area of the water-insoluble conductive carbon material that can be used is preferably 1 to 750 m ² / g, more preferably 3 to 500 m ² / g, from the viewpoint of reducing the amount of adsorbed moisture of the electrode active material. Moreover, from the same viewpoint, the average particle size of the water-insoluble conductive carbon material is preferably 0.02 to 20 μm, more preferably 0.03 to 15 μm.

  The water-soluble carbon material means a carbon material that dissolves in 100 g of water at 25 ° C. in terms of carbon atom of the water-soluble carbon material in an amount of 0.4 g or more, preferably 1.0 g or more. It is a particle surface carbon source of a transition metal composite oxide. 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 enhancing the solubility and dispersibility in a solvent and effectively functioning as a carbon source.

  The carbon atom equivalents of the water-insoluble conductive carbon material and the water-soluble carbon material are obtained as carbon carried on the particle surface of the transition metal composite oxide by the water-insoluble conductive carbon material and the carbonized water-soluble carbon material. Coexist in the electrode active material particles (X). The carbon atom equivalent amount of the water-insoluble conductive carbon material and the water-soluble carbon material corresponds to the total supported amount of carbon derived from the water-insoluble conductive carbon material and the water-soluble carbon material, and in the electrode active material particles (X). In total, it is preferably 1.0 to 20.0% by mass, more preferably 2.0 to 17.5% by mass, and still more preferably 3.0 to 15.0% by mass.

The conductive auxiliary agent particles (Y) used in the present invention comprise at least one of carbon derived from cellulose nanofibers and carbon derived from amorphous spherical carbon.
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, Cellulose molecular chains constituting cellulose nanofibers are formed with a periodic structure of carbon. Such cellulose nanofibers have a fiber diameter of 1 to 500 nm, a fiber length of 1 to 500 μm, and also have good dispersibility in water. Moreover, in the cellulose molecular chain which comprises a cellulose nanofiber, since the periodic structure by carbon is formed, when the cellulose nanofiber is carbonized, the outstanding electroconductivity can be expressed. Therefore, if only cellulose nanofibers are used as a carbon source, the cellulose nanofibers are removed while unnecessary moisture is removed by a spray drying process using a spray dryer followed by a firing process in a reducing atmosphere or an inert atmosphere. Conductive auxiliary material particles (Y) having only excellent conductivity and made of only fiber-derived carbon can be obtained.

Amorphous spherical carbon is a collection of fine carbon crystals obtained by hydrothermal reaction of a mixed solution of water and a water-soluble carbonaceous material such as glucose and then spray drying the resulting slurry water at a high temperature. It is a body, and after passing through such a spray-drying process, it becomes carbon with high crystallinity through a firing process in a reducing atmosphere or an inert atmosphere. Therefore, if only amorphous spherical carbon is used as a carbon source, conductive auxiliary agent particles (Y) having excellent conductivity, consisting only of carbon derived from such amorphous spherical carbon, while removing unnecessary moisture can be obtained. can get. The average particle diameter of such amorphous spherical carbon is 50 nm to 100 μm.
Note that both cellulose nanofibers and amorphous spherical carbon may be used as a carbon source. In this case, after passing through a spray drying process using a spray dryer, a firing process in a reducing atmosphere or an inert atmosphere is performed. Thus, conductive auxiliary agent particles (Y) made of only carbon in which both carbon derived from cellulose nanofibers and carbon derived from amorphous spherical carbon are mixed are obtained while removing unnecessary moisture.

  The content of the conductive auxiliary particles (Y) corresponds to the total of the amount of carbon derived from cellulose nanofibers and the amount of carbon derived from amorphous spherical carbon, and the active material-containing particles for a nonaqueous electrolyte secondary battery of the present invention The total amount in the mixture is preferably 1.0 to 25.0% by mass, more preferably 1.0 to 15.0% by mass, and still more preferably 1.0 to 10.0% by mass. . More specifically, for example, when the electrode active material particle (X) contains a transition metal composite oxide used for the positive electrode, the content of the conductive auxiliary agent particle (Y) is the non-aqueous electrolyte secondary of the present invention. In the battery active material-containing particle mixture, the amount is preferably 1.0 to 25.0% by mass, more preferably 1.0 to 15.0% by mass, and still more preferably 1.0 to 10.0% by mass. %. Moreover, when electrode active material particle (X) contains the transition metal complex oxide used for the electrode for negative electrodes, content of conductive support agent particle (Y) is the active material content particle | grains for nonaqueous electrolyte secondary batteries of this invention In a mixture, Preferably it is 1.0-20.0 mass%, More preferably, it is 1.0-12.0 mass%, More preferably, it is 1.0-8.0 mass%.

In the method for producing an active material-containing particle mixture for a non-aqueous electrolyte secondary battery according to the present invention, a water-insoluble conductive carbon material and / or a water-soluble carbon material, and water are added to particles of a transition metal composite oxide, Step (I) for obtaining slurry A,
Step (II) of obtaining slurry B by mixing cellulose nanofibers and / or amorphous spherical carbon and water
Using a spray dryer having at least two injection ports, slurry A obtained in step (I) and slurry B obtained in step (II) are simultaneously spray-dried from different injection ports to form slurry A. Step (III) for obtaining a dry mixture E in which the granulated body C to be formed and the granulated body D formed from the slurry B are mixed, and the dry mixture E obtained in the step (III) is reduced or inert. Baking process in atmosphere (IV)
Is provided.

  Step (I) is a step of obtaining slurry A by adding water-insoluble conductive carbon material and / or water-soluble carbon material and water to the transition metal composite oxide particles. The transition metal composite oxide is not particularly limited, but the above-mentioned transition metal composite oxide used for the positive electrode can be used.

  The content of the transition metal composite oxide in the slurry A is preferably 10 to 400 parts by mass and more preferably 30 to 200 parts by mass with respect to 100 parts by mass of water. Moreover, the total content of the water-insoluble conductive carbon material and the water-soluble carbon material is preferably 0.5 to 100 parts by mass, more preferably 5 to 50 parts by mass with respect to 100 parts by mass of water.

  In the obtained slurry A, it is preferable to perform a treatment using a disperser (homogenizer) from the viewpoint of uniformly dispersing the transition metal composite oxide and the water-insoluble conductive carbon material and / or the water-soluble 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-axis 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 dispersion efficiency. The degree of dispersion uniformity of the slurry A can be quantitatively evaluated by, for example, light transmittance using a UV / visible light spectroscope or viscosity using an E-type viscometer. By confirming that it is uniform, it is possible to simply evaluate. The processing time with the disperser is preferably 0.5 to 6 minutes, more preferably 1 to 4 minutes.

  Step (II) is a step of obtaining slurry B by mixing cellulose nanofibers and / or amorphous spherical carbon and water. Such mixing is preferably performed with a weak stirring force. Specifically, the weak stirring force is, for example, when stirring is performed using an apparatus including a stirring blade, the rotation speed of the stirring blade is preferably 50 to 500 rpm, more preferably 50 to 200 rpm, The stirring time is preferably 0.5 to 10 minutes, more preferably 0.5 to 5 minutes.

  The total content of cellulose nanofibers and amorphous spherical carbon in the slurry B is preferably 1 to 50 parts by mass, more preferably 1 to 25 parts by mass with respect to 100 parts by mass of water. More specifically, for example, when the conductive additive particles (Y) are composed of only carbon derived from cellulose nanofibers, the total content of cellulose nanofibers and amorphous spherical carbon in the slurry B is 100 parts by mass of water. On the other hand, it is preferably 1 to 40 parts by mass, more preferably 1 to 20 parts by mass. In addition, when the conductive additive particles (Y) are composed of only carbon derived from amorphous spherical carbon, the total content of cellulose nanofibers and amorphous spherical carbon in the slurry B is preferably 100 parts by mass of water. It is 1-50 mass parts, More preferably, it is 1-25 mass parts. Furthermore, when the conductive additive particles (Y) are composed of both carbon derived from cellulose nanofibers and carbon derived from amorphous spherical carbon, the total content of cellulose nanofibers and amorphous spherical carbon in slurry B is water. Preferably it is 1-50 mass parts with respect to 100 mass parts, More preferably, it is 1-25 mass parts.

  In the obtained slurry B, it is preferable to perform the process using a disperser (homogenizer) from a viewpoint of disperse | distributing cellulose nanofiber and / or amorphous spherical carbon uniformly. 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-axis 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 dispersion efficiency. The degree of dispersion uniformity of the slurry B can be quantitatively evaluated by, for example, light transmittance using a UV / visible light spectroscope or viscosity using an E-type viscometer. By confirming that it is uniform, it is possible to simply evaluate. The processing time with the disperser is preferably 0.5 to 6 minutes, more preferably 0.5 to 4 minutes.

  In step (III), a spray dryer having at least two injection ports is used, and slurry A obtained in step (I) and slurry B obtained in step (II) are simultaneously spray-dried from different injection ports. And it is the process of obtaining the dry mixture E in which the granulated body C formed from the slurry A and the granulated body D formed from the slurry B are mixed.

  What is necessary is just to set suitably the mixing ratio of the granulated body C and the granulated body D in the dry mixture E by adjusting the ratio of the injection amount from the spray dryer of the slurry A and the slurry B. Slurry A and Slurry B are simultaneously granulated from different spray ports of the same spray dryer, and become dried granulates. However, since Slurry A and Slurry B are each sprayed from separate spray ports, the resulting granulated material. C and granulated body D are granulated bodies that are formed by drying each slurry without mixing slurry A or slurry B, and are formed by mixing slurry A and slurry B. It is not a granule. Therefore, the obtained dry mixture E is a mixture in which the granulated body C and the granulated body D are mixed independently of each other.

  The temperature of the spray drying is preferably 150 to 320 ° C. from the viewpoint of separately forming the granulated body C and the granulated body D without mixing the slurry A and the slurry B while effectively reducing the water content. Yes, more preferably 170-250 ° C.

The particle size of the granulated body C and granulated body D obtained by spray drying is a D ₅₀ value in the particle size distribution based on the laser diffraction / scattering method, preferably 1 to 20 μm, more preferably 2 to 15 μm. . 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 C and the granulated body D by optimizing the operating condition of a spray dryer suitably.

  Step (IV) is a step of baking the dry mixture E obtained in step (III) in a reducing atmosphere or an inert atmosphere. Thereby, in the granulated body C in the dry mixture E, electrode active material particles (X) in which carbon is supported on the particle surface of the transition metal composite oxide are generated, and at the same time, the granulated body C in the dry mixture E In the granule D, conductive auxiliary agent particles (Y) composed of carbon derived from cellulose nanofibers and / or amorphous spherical carbon are generated. Therefore, these electrode active material particles (X) and conductive auxiliary agent particles (Y) Thus, an active material-containing particle mixture for a non-aqueous electrolyte secondary battery obtained by mixing sufficiently and uniformly as mutually independent particles is obtained. The firing conditions in this step (IV) are a reducing atmosphere or an inert atmosphere, and the firing temperature is preferably 400 ° C. or higher, more preferably 400 to 800 ° C., and the firing time is preferably 10 minutes to 3 hours. More preferably, it is 0.5 to 1.5 hours.

  The ion secondary battery to which the mixed material of the active material for the non-aqueous electrolyte secondary battery of the present invention can be applied is a lithium ion secondary battery or a sodium ion secondary battery, and includes a positive electrode, a negative electrode, an electrolyte, and a separator. If it is said, it will not specifically limit. In such an ion secondary battery, the electrode manufactured from the mixed material of the active material for a non-aqueous electrolyte secondary battery of the present invention may be any of a positive electrode, a negative electrode, or both electrodes.

  Specifically, an electrode using the mixed material of the active material for a non-aqueous electrolyte secondary battery of the present invention is obtained by mixing the obtained mixed material and a binder (for example, polyvinylidene fluoride (PVDF) or styrene butadiene rubber (SBR)). Are mixed in a mass ratio of 88 to 98: 2 to 12, and an electrolytic solution is added thereto and kneaded sufficiently to prepare a slurry (electrode mixture). The obtained slurry is applied to a current collector made of aluminum foil having a thickness of 5 to 40 μm and dried. Then, after punching into a predetermined shape and size, it is pressed to form an electrode. An ion secondary battery is obtained by incorporating and accommodating the obtained electrode (positive electrode or / and negative electrode) and a separately prepared separator.

  The above 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 solution of a lithium ion secondary battery or a sodium ion secondary 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, but in the case of a lithium ion secondary battery, an inorganic salt selected from LiPF ₆ , LiBF ₄ , LiClO ₄ and LiAsF ₆ , a derivative of the inorganic salt, LiSO ₃ CF ₃ , an organic material selected from LiC (SO ₃ CF ₃ ) ₂ and 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 a salt and a derivative of the organic salt. In the case of a sodium ion secondary battery, an inorganic salt selected from NaPF ₆ , Nb1F ₄ , NaClO ₄ and Na1sF ₆ , a derivative of the inorganic salt, NaSO ₃ CF ₃ , NaC (SO ₃ CF ₃ ) ₂ and NaN (SO ₃ CF ₃ ) ₂ , NaN (SO ₂ C ₂ F ₅ ) _2, and an organic salt selected from NaN (SO ₂ CF ₃ ) (SO ₂ C ₄ F ₉ ), and at least one derivative of the organic salt It is preferable.

  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.

"Transition metal composite oxide = production in LiMn _0.7 Fe _0.3 PO _4"
<Manufacturing using conductive auxiliary particles made of CNF>
[Example 1]
1272 g of LiOH.H ₂ O and 4000 mL of water were mixed to obtain slurry water. Next, 1153 g of 85% phosphoric acid aqueous solution was dropped at 35 mL / min while stirring the slurry water obtained at a temperature of 25 ° C. for 3 minutes at a stirring blade rotation speed of 400 rpm. By stirring for 12 hours at a rotational speed of 400 rpm, a slurry a containing Li ₃ PO ₄ was obtained. The slurry a contained 2.97 mol of lithium with respect to 1 mol of phosphorus.
Subsequently, the obtained slurry a was purged with nitrogen to complete the reaction in the slurry a (dissolved oxygen concentration 0.5 mg / L). Next, 1688 g of MnSO ₄ .5H ₂ O and 834 g of FeSO ₄ .7H ₂ O were added to the total amount of the obtained slurry a to obtain a mixed solution a. At this time, the added molar ratio of Mn to Fe (MnSO ₄ · H ₂ O: FeSO ₄ · 7H ₂ O) was 70:30. Subsequently, the obtained mixed liquid a was put into a synthesis container installed in a steam heating autoclave. After the addition, the mixture was heated with stirring at 170 ° C. for 1 hour using saturated steam obtained by heating water (dissolved oxygen concentration less than 0.5 mg / L) with a membrane separator. The pressure in the autoclave was 0.8 MPa. The produced crystal was filtered and washed with 12 parts by mass of water with respect to 1 part by mass of the crystal. 163 g of the washed crystal is repulped with 15.7 g of glucose (anhydrous crystal glucose manufactured by Nippon Food Chemicals Co., Ltd., corresponding to 4% by mass in terms of carbon atom in the active material), and 351 g of slurry A1 (water content 49% by mass) Got.

After mixing 7.9 mL of water with 87.9 g of cellulose nanofiber (Cerish FD-200L, manufactured by Daicel Finechem, water content 20 mass%), the mixture was dispersed for 1 minute with an ultrasonic stirrer (T25, manufactured by IKA), and the whole was uniform. 351 g of slurry B1 was obtained (the content of cellulose nanofibers corresponds to 2 parts by mass in terms of carbon atoms per 100 parts by mass of slurry B1). Both the slurry A1 and the slurry B1 are simultaneously sprayed from different spray ports of the same spray drying apparatus (MDL-050M, manufactured by Fujisaki Electric Co., Ltd.) at a spray flow rate of 500 cm ³ / hour, and spray drying is performed at 180 ° C. a slurry A1-derived granule C1 (diameter = 8 [mu] m at D ₅₀ value in the particle size distribution measurement), (particle size = 3 [mu] m at D ₅₀ value in the particle size distribution measurement) granules D1 from the slurry B1 is mixed A dry mixture E1 was obtained.
The obtained dry mixture E1 was calcined at 700 ° C. for 1 hour in an argon hydrogen atmosphere (hydrogen concentration: 3%), and lithium manganese iron phosphate positive electrode active material particles X1 (LiMn _0.7) supported by glucose-derived carbon. Fe _0.3 PO ₄ , amount of carbon = 4% by mass) and particle mixture Z1 (particles X1 = 96.2% by mass, particles Y1 = 3) with conductive auxiliary agent particles Y1 made of carbon obtained by carbonizing cellulose nanofibers. .8 mass%) was obtained.
An SEM image of the obtained particle mixture Z1 is shown in FIG.

<Manufacturing using conductive auxiliary particles made of ACS>
[Example 2]
After 19.6 g of glucose was mixed with 331 mL of water to obtain a solution, the obtained solution was put into a steam-heated autoclave and subjected to a hydrothermal reaction at 170 ° C. for 3 hours to obtain 351 g of amorphous spherical carbon. A slurry B2 was obtained (the content of amorphous spherical carbon corresponds to 2.5 parts by mass per 100 parts by mass of the slurry B2).

Except for using the slurry B2 instead of the slurry B1, in the same manner as in Example 1, the lithium manganese iron phosphate positive electrode active material particle X2 (LiMn _0.7 Fe _0.3 PO ₄ , carbon supported by carbon derived from glucose, the amount of carbon = 4% by mass) and a conductive mixture particle Y2 made of carbon obtained by firing amorphous spherical carbon and a particle mixture Z2 (particles X2 = 95.2% by mass, particles Y2 = 4.8% by mass). Obtained.

<Manufacturing using Ketjen Black conductive additive>
[Comparative Example 1]
Except that slurry B1 was not added at the time of spray drying, in the same manner as in Example 1, a lithium manganese iron phosphate positive electrode active material (LiMn _0.7 Fe _0.3 PO ₄ / C, supported by glucose-derived carbon, the amount of carbon = 4% by mass).
With respect to 100 parts by mass of the obtained lithium iron manganese phosphate positive electrode active material, 5 parts by mass of ketjen black (KB) as a conductive assistant is used for 3 minutes with a Henschel mixer (FM10C / I, manufactured by Nippon Coke Industries, Ltd.). Particle mixture of lithium manganese iron phosphate positive electrode active material particles X3 (LiMn _0.7 Fe _0.3 PO ₄ , amount of carbon = 4 mass%) formed by mixing and supporting carbon derived from glucose and ketjen black particles Y3 Z3 (particles X3 = 95.2% by mass, particles Y3 = 4.8% by mass) was obtained.

<< Transition metal complex oxide = production in Li ₂ Fe _0.28 Mn _0.66 Zr _0.03 SiO ₄ >>
<Manufacturing using conductive auxiliary particles comprising CNF and ACS>
[Example 3]
856 g of LiOH.H ₂ O, 2794 g of Na ₄ SiO ₄ .nH ₂ O and 750 mL of water were mixed to obtain slurry c. Next, 1586 g of MnSO ₄ .5H ₂ O, 784 g of FeSO ₄ .7H ₂ O, and 106 g of Zr (SO ₄ ) ₂ .4H ₂ O were added to this slurry c to obtain a mixed solution b. The molar ratio of Mn, Fe and Zr (MnSO ₄ .H ₂ O: FeSO ₄ .7H ₂ O: Zr (SO ₄ ) ₂ .4H ₂ O) in the mixed solution b was 66: 28: 3. .
Subsequently, the obtained mixed liquid b was put into a synthesis container installed in a steam heating type autoclave. After the addition, the mixture was heated with stirring at 150 ° C. for 12 hours using saturated steam obtained by heating water (dissolved oxygen concentration less than 0.5 mg / L) with a membrane separator. The pressure in the autoclave was 0.4 MPa. The produced crystal was filtered, and then washed with 12 parts by mass of water with respect to 1 part by mass of the crystal. The washed crystal was lyophilized at −50 ° C. for 12 hours to obtain complex b. The obtained complex b was repulped with 32.2 g of glucose (equivalent to 8% by mass in terms of carbon atom in the active material) to obtain 351 g of slurry A4 (water content: 45 wt%).

195 g of the slurry B1 obtained in Example 1 and 156 g of the slurry B2 obtained in Example 2 were mixed, and 351 g of the slurry B4 (carbon having a cellulose nanofiber content per 100 parts by mass of the slurry B4). The amount in terms of atoms corresponds to 1 part by mass, and the content of amorphous spherical carbon corresponds to 1 part by mass).
Zr-doped lithium manganese iron silicate positive electrode active material doped with carbon derived from glucose, as in Example 1, except that slurry A4 was used instead of slurry A1 and slurry B4 was used instead of slurry B1 Particle X4 (Li ₂ Fe _0.28 Mn _0.66 Zr _0.03 SiO ₄ , amount of carbon = 8 mass%) and carbon formed by carbonizing cellulose nanofibers and carbon formed by firing amorphous spherical carbon are in a mass ratio of 1: A particle mixture Z4 (particles X4 = 95.2% by mass, particles Y4 = 4.8% by mass) with conductive auxiliary agent particles Y4 made of carbon mixed in 1 was obtained.

<Manufacturing using conductive auxiliary particles made of ACS>
[Example 4]
Zr-doped lithium manganese iron silicate positive electrode active material particle X5 doped with carbon derived from glucose was used in the same manner as in Example 3 except that the slurry B2 obtained in Example 2 was used instead of the slurry B4. Particle mixture Z5 (particle X5 = 95) of (Li ₂ Fe _0.28 Mn _0.66 Zr _0.03 SiO ₄ , amount of carbon = 8 mass%) and conductive auxiliary agent particles Y5 made of carbon obtained by firing amorphous spherical carbon 2% by mass, particles Y5 = 4.8% by mass).

<Manufacturing using Ketjen Black conductive additive>
[Comparative Example 2]
A Zr-doped lithium manganese iron silicate positive electrode active material (LiMn _0.7 Fe _0.3 PO ₄ / C) formed by supporting carbon derived from glucose, except that the slurry B4 was not added during spray drying. , Amount of carbon = 8 mass%).
With respect to 100 parts by mass of the Zr-doped lithium manganese iron silicate positive electrode active material supported by the carbon derived from glucose, 5 parts by mass of ketjen black (KB) as a conductive auxiliary agent was added to a Henschel mixer (FM10C). / I) for 3 minutes, Zr-doped lithium manganese iron silicate positive electrode active material particles X6 (LiMn _0.7 Fe _0.3 PO ₄ / C, supported by glucose-derived carbon, amount of carbon = 8 mass% ) And ketjen black particles Y6 were obtained as a particle mixture Z6 (particles X6 = 95.2% by mass, particles Y6 = 4.8% by mass).

"Production in the transition metal complex oxide = NaMn _0.7 Fe _0.3 PO _4"
<Manufacturing using conductive auxiliary particles made of CNF>
[Example 5]
A slurry water was obtained by mixing 1200 g of NaOH and 18000 mL of water. Next, 1154 g of 85% phosphoric acid aqueous solution was dropped at 35 mL / min while stirring the slurry water obtained at a temperature of 25 ° C. for 5 minutes at a rotation speed of the stirring blade of 400 rpm. By stirring for 12 hours at a rotational speed of 400 rpm, a slurry c containing Na ₃ PO ₄ was obtained. The slurry c contained 3.00 mol of sodium per mol of phosphorus.
Next, the obtained slurry c was purged with nitrogen to complete the reaction in the slurry c (dissolved oxygen concentration 0.5 mg / L). Next, 1638 g of MnSO ₄ .5H ₂ O and 834 g of FeSO ₄ .7H ₂ O were added to the total amount of the obtained slurry c to obtain a mixed solution c. At this time, the added molar ratio of Mn to Fe (MnSO ₄ · H ₂ O: FeSO ₄ · 7H ₂ O) was 70:30. Next, the obtained mixed liquid c was charged into a synthesis container installed in a steam heating autoclave purged with nitrogen gas. After the addition, the mixture was heated with stirring at 200 ° C. for 3 hours using saturated steam obtained by heating water (dissolved oxygen concentration less than 0.5 mg / L) with a membrane separator. The pressure in the autoclave was 1.4 MPa. The produced crystal was filtered and washed with 12 parts by mass of water with respect to 1 part by mass of the crystal. 172 g of the washed crystal was repulped with 17.3 g of glucose (corresponding to 4% by mass in terms of carbon atom in the active material) to obtain 351 g of slurry A5 (water content 46% by mass).

Except for using the slurry A5 instead of the slurry A1, in the same manner as in Example 1, sodium manganese iron phosphate positive electrode active material particles X7 (NaMn _0.7 Fe _0.3 PO ₄ , carbon supported by carbon derived from glucose, amount of carbon = 4 mass%) and a particle mixture Z7 (particle X7 = 95.2 mass%, particle Y7 = 4.8 mass%) with conductive auxiliary agent particles Y7 made of carbon obtained by carbonizing cellulose nanofibers. .

<Manufacturing using conductive auxiliary particles comprising CNF and ACS>
[Example 6]
Except for using the slurry B2 obtained in Example 2 instead of the slurry B1, in the same manner as in Example 5, sodium manganese iron phosphate positive electrode active material particles X8 (NaMn _0.7 Fe) supported by glucose-derived carbon _0.3 PO ₄ , the amount of carbon = 4% by mass), and a conductive additive composed of carbon in which carbon formed by carbonizing cellulose nanofibers and carbon formed by firing amorphous spherical carbon are mixed at a mass ratio of 1: 1. A particle mixture Z8 (particles X8 = 95.2% by mass, particles Y8 = 4.8% by mass) with the particles Y8 was obtained.

<Manufacturing using conductive aid particles made of ketjen black>
[Comparative Example 3]
Except that the slurry B1 was not added at the time of spray-drying, the same as in Example 5, a sodium manganese iron phosphate positive electrode active material (NaMn _0.7 Fe _0.3 PO ₄ , carbon content = 4 supported by glucose-derived carbon) Mass%).
5 parts by mass of ketjen black (KB) as a conductive assistant is added to Henshell mixer (FM10C / I) with respect to 100 parts by mass of the sodium manganese iron phosphate positive electrode active material supported by the carbon derived from glucose. Mixing for 3 minutes, sodium manganese iron phosphate positive electrode active material particles X9 (NaMn _0.7 Fe _0.3 PO ₄ , amount of carbon = 4% by mass) supported by glucose-derived carbon and ketjen black particles Y9 A particle mixture Z9 (particles X9 = 95.2% by mass, particles Y9 = 4.8% by mass) was obtained.

<< Transition metal composite oxide = Production in Li ₄ Ti ₅ O ₁₂ >>
<Manufacturing using conductive auxiliary particles made of CNF>
[Example 7]
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. 150 g of the resulting Li ₄ Ti ₅ O ₁₂ was taken, and 186 g of water and 15.0 g of glucose (corresponding to 4% by mass in terms of carbon atom in the active material) were added thereto, and repulped to obtain 351 g of A slurry A6 (water content: 49 mass%) was obtained.

Except for using slurry A6 instead of slurry A1, lithium titanate negative electrode active material particles X10 (Li ₄ Ti ₅ O ₁₂ , carbon content = 4, supported by glucose-derived carbon, in the same manner as in Example 1. Mass mixture) and conductive auxiliary agent particles Y10 made of carbon obtained by carbonizing cellulose nanofibers to obtain a particle mixture Z10 (particle X10 = 95.2 mass%, particle Y10 = 4.8 mass%).

<Manufacturing using conductive auxiliary particles made of ACS>
[Example 8]
Lithium titanate negative electrode active material particles X11 (Li ₄ Ti ₅ O formed by supporting carbon derived from glucose) in the same manner as in Example 7 except that the slurry B2 obtained in Example 2 was used instead of the slurry B1. ₁₂ , the amount of carbon = 4% by mass) and a particle mixture Z11 (particles X11 = 95.2% by mass, particles Y11 = 4.%) of conductive assistant particles Y11 made of carbon obtained by firing amorphous spherical carbon. 8% by mass) was obtained.

<Manufacturing using conductive aid particles made of ketjen black>
[Comparative Example 4]
A lithium titanate negative electrode active material (Li ₄ Ti ₅ O ₁₂ , carbon content = 4% by mass) supported by glucose-derived carbon in the same manner as in Example 7 except that the slurry B1 was not added during spray drying. )
For 100 parts by mass of the lithium titanate negative electrode active material supported by the obtained glucose-derived carbon, 5 parts by mass of ketjen black (KB) as a conductive assistant is added for 3 minutes with a Henschel mixer (FM10C / I). Particle mixture Z112 of lithium titanate negative electrode active material particles X12 (Li ₄ Ti ₅ O ₁₂ , amount of carbon = 4% by mass) formed by supporting carbon derived from glucose and ketjen black particles Y12 by mixing. Particle X12 = 95.2 mass%, Particle Y12 = 4.8 mass%) was obtained.

<< Evaluation of charge / discharge characteristics using secondary battery >>
Using the particle mixtures Z1 to Z12 obtained in Examples 1 to 8 and Comparative Examples 1 to 4, positive electrodes or negative electrodes of lithium ion secondary batteries or sodium ion batteries were produced. Specifically, the mixture and polyvinylidene fluoride were mixed at a mass ratio of 95: 5, and N-methyl-2-pyrrolidone was added thereto and kneaded sufficiently to prepare a positive electrode or negative electrode slurry.
Subsequently, when manufacturing a positive electrode, after apply | coating the said slurry for positive electrodes to the collector which consists of 20-micrometer-thick aluminum foil using a coating machine, it vacuum-dried at 80 degreeC for 12 hours. When manufacturing a negative electrode, the slurry for negative electrodes was applied to a copper foil having a thickness of 10 μm. The metal foil coated with these electrode materials was punched into a disk shape of φ14 mm and pressed at 16 MPa for 2 minutes using a hand press.
Next, a coin-type secondary battery was constructed. When the positive electrode was used, a lithium foil (in the case of a lithium ion secondary battery) or a sodium foil (in the case of a sodium ion secondary battery) punched out to 15 mm in diameter was used for the counter electrode (negative electrode). Moreover, when using said negative electrode, the lithium foil (in the case of a lithium ion secondary battery) or the sodium foil (in the case of a sodium ion secondary battery) pierced to 15 mm in the counter electrode (positive electrode) was used. In the electrolyte solution, LiPF ₆ (in the case of a lithium ion secondary battery) or NaPF ₆ (in the case of a sodium ion secondary battery) is mixed with a mixed solvent in which ethylene carbonate and ethyl methyl carbonate are mixed at a volume ratio of 1: 1. Those dissolved at a concentration of 1 mol / L were used. As the separator, a known one such as a polymer porous film such as polypropylene was used. These battery components were assembled and housed in a conventional manner in an atmosphere with a dew point of −50 ° C. or lower to produce a coin-type secondary battery (CR-2032).

When lithium manganese iron phosphate (LiFe _0.3 Mn _0.7 PO ₄ ) is used as the transition metal composite oxide for the positive electrode in the lithium ion secondary battery, the charging conditions are current 0.1 CA (17 mA / g), voltage 4 The discharge capacity at 3CA was determined with a constant current and constant voltage charge of 0.5 V, a discharge condition of 3 CA (510 mA / g), and a constant current discharge with a final voltage of 2.0 V. Further, when lithium manganese manganese silicate doped with Zr (Li ₂ Fe _0.28 Mn _0.66 Zr _0.03 SiO ₄ ) is used as the transition metal composite oxide for the positive electrode, the charging condition is set to a current of 0.1 CA (33 mA / 33). g), a constant current / constant voltage charge with a voltage of 4.5V, a discharge condition of 1CA (330 mA / g), a constant current discharge with a final voltage of 1.5V, and a discharge capacity at 1CA. Further, when lithium titanate is used as the transition metal composite oxide for the negative electrode, the charging condition is a constant current charging with a current of 0.1 CA (17.5 mA / g) and a voltage of 2.5 V, and the discharging condition is As constant current discharge with a current of 0.1 CA and a final voltage of 1.0 V, the discharge capacity at 0.1 CA was determined.
In the case of a sodium ion secondary battery, the charging condition is a constant current and constant voltage charging with a current of 0.1 CA (15.4 mA / g) and a voltage of 4.5 V, the discharging condition is 3 CA (462 mA / g), and a final voltage of 2.0 V. As a constant current discharge, the discharge capacity at 3CA was determined.
The results are shown in Tables 1-4.

  From the above results, it can be seen that the particle mixture as the positive electrode material or negative electrode material of the example can exhibit superior performance in the obtained battery as compared with the particle mixture as the positive electrode material or negative electrode material of the comparative example.

Claims (9)

  Electrode active material particles (X) in which at least one of a water-insoluble conductive carbon material and a carbon derived from a water-soluble carbon material is supported on the particle surface of the transition metal composite oxide, carbon derived from cellulose nanofibers, and amorphous An active material-containing particle mixture for a non-aqueous electrolyte secondary battery in which conductive auxiliary agent particles (Y) composed of at least one of carbons derived from a spherical carbon are mixed as independent particles.   2. The non-aqueous electrolyte 2 according to claim 1, wherein the total amount of water-insoluble conductive carbon material and water-soluble carbon material in the electrode active material particles (X) is 1.0 to 20.0 mass%. Active material-containing particle mixture for secondary battery.   3. The active material-containing particle mixture for a nonaqueous electrolyte secondary battery according to claim 1, wherein the content of the conductive auxiliary agent particles (Y) is 1.0 to 25.0% by mass.   The active material containing particle mixture for nonaqueous electrolyte secondary batteries according to any one of claims 1 to 3, wherein the average particle diameter of the transition metal composite oxide is 20 to 400 nm. Step (I) of obtaining slurry A by adding water-insoluble conductive carbon material and / or water-soluble carbon material and water to the transition metal composite oxide particles,
Step (II) of obtaining slurry B by mixing cellulose nanofibers and / or amorphous spherical carbon and water
Using a spray dryer having at least two injection ports, slurry A obtained in step (I) and slurry B obtained in step (II) are simultaneously spray-dried from different injection ports to form slurry A. Step (III) for obtaining a dry mixture E in which the granulated body C to be formed and the granulated body D formed from the slurry B are mixed, and the dry mixture E obtained in the step (III) is reduced or inert. Baking process in atmosphere (IV)
The manufacturing method of the active material containing particle | grain mixture for nonaqueous electrolyte secondary batteries of Claim 1 provided with these.   The method for producing an active material-containing particle mixture for a non-aqueous electrolyte secondary battery according to claim 5, wherein the content of the transition metal composite oxide in the slurry A is 10 to 400 parts by mass with respect to 100 parts by mass of water.   The active material for a nonaqueous electrolyte secondary battery according to claim 5 or 6, wherein the total content of cellulose nanofibers and amorphous spherical carbon in the slurry B is 1 to 50 parts by mass with respect to 100 parts by mass of water. A method for producing a contained particle mixture.   The temperature of spray drying in process (III) is 150-320 degreeC, The manufacturing method of the active material containing particle mixture for nonaqueous electrolyte secondary batteries of any one of Claims 5-7. The particle size of the granulated product C and the granulated product D is 1 to 20 µm as a D ₅₀ value in the particle size distribution measurement, containing the active material for a non-aqueous electrolyte secondary battery according to any one of claims 5 to 8. A method for producing a particle mixture.