JP2020011872A - Carbon nanotube dispersion liquid and its use - Google Patents

Abstract

To provide a carbon nanotube dispersion liquid using a carbon nanotube having a half width of 2° to 6° in X-ray powder diffraction analysis and a dispersion agent containing a triazine derivative having an acidic functional group.SOLUTION: A carbon nanotube dispersion liquid contains a carbon nanotube (A), a solvent (B) and a dispersion agent (C), in which in X-ray powder diffraction analysis, the carbon nanotube (A) has a peak at a diffraction angle 2θ=25° ±2°, a half width of the peak of 2° to 6° and has G/D ratio of 0.5-5.0 when the maximum peak intensity is represented by G in a range of 1560-1600 cmand the maximum peak intensity is represented by D in a range of 1310-1350 cmin Raman spectrum, and the dispersion agent (C) contains a triazine derivative having an acidic functional group represented by the general formula (1).SELECTED DRAWING: None

Description

  The present invention relates to a dispersion of carbon nanotubes. More specifically, a carbon nanotube dispersion liquid, a resin composition containing a carbon nanotube dispersion liquid and a resin, a mixture slurry containing a carbon nanotube dispersion liquid, a resin and an active material, an electrode film coated with the same, an electrode film and lithium And a lithium ion secondary battery comprising:

  In recent years, with the spread of mobile phones, notebook personal computers, and the like, lithium ion secondary batteries have been receiving attention. Lithium ion secondary batteries usually include a negative electrode made of a carbon-based material, a positive electrode containing an active material that allows lithium ions to enter and exit reversibly, and a non-aqueous electrolyte that immerses them. It is manufactured by applying an electrode paste composed of a substance, a conductive material and a binder to a current collector plate.

  In the positive electrode, the conductivity of the active material is increased by the blending of the conductive material. However, if the dispersion of the conductive material in the active material is insufficient, the improvement of the conductivity is also insufficient. Therefore, a slurry for forming an electrode of a lithium ion secondary battery, which contains an electrode active material, a conductive material, a binder, and a polar solvent and has an average particle size of 500 nm or less when the conductive material is dispersed, has been proposed. (For example, see Patent Document 1).

  As the conductive material, carbon black, Ketjen black, fullerene, graphene, fine carbon material and the like are used. In particular, carbon nanotubes, which are a type of fine carbon fiber, are tube-shaped carbon with a diameter of 1 μm or less, and can be used as a conductive material for lithium ion secondary batteries due to their high conductivity based on their unique structure. Are being considered. Among them (see, for example, Patent Documents 2, 3, and 4), multi-walled carbon nanotubes having an outer diameter of 10 nm to several tens of nm are relatively inexpensive and are expected to be put to practical use.

  When a carbon nanotube having a small average outer diameter is used, a conductive network can be efficiently formed with a small amount, and the amount of a conductive material contained in a positive electrode and a negative electrode for a lithium ion secondary battery can be reduced. However, carbon nanotubes having a small average outer diameter have a strong cohesive force and are difficult to disperse, so that a carbon nanotube dispersion having sufficient dispersibility could not be obtained.

  Therefore, various attempts have been made to improve the dispersibility of the carbon nanotube in the dispersion medium. For example, a method has been proposed in which carbon nanotubes are dispersed in acetone while being irradiated with ultrasonic waves (see Patent Document 5). However, there is a problem that even if the dispersion can be performed during the irradiation of the ultrasonic waves, the carbon nanotubes start to aggregate when the irradiation is completed, and the carbon nanotubes aggregate when the concentration of the carbon nanotubes increases.

  Further, a method of stabilizing the dispersion of carbon nanotubes using various dispersants has been proposed. For example, dispersion in water and NMP (N-methyl-2-pyrrolidone) using a polymer dispersant such as a water-soluble polymer polyvinylpyrrolidone has been proposed (see Patent Documents 2, 3, and 6). However, in Patent Literature 2, although an electrode manufactured using carbon nanotubes having an outer diameter of 10 to 150 nm is evaluated, there is a problem that the electrode resistance is high. In addition, Patent Literature 3 proposes a dispersion using carbon nanotubes having a small DBP oil absorption, but has a problem that it is difficult to obtain high conductivity although the dispersibility is improved. In the cited document 6, the dispersion using single-walled carbon nanotubes having a small outer diameter is examined, but it is difficult to disperse the carbon nanotubes in a solvent at a high concentration. In Patent Document 7, a carbon nanotube dispersion liquid containing a carbon nanotube and a triazine derivative having an acidic functional group is examined, but it has been difficult to disperse the carbon nanotube having an outer diameter of 10 nm at a high concentration. Therefore, obtaining a carbon nanotube dispersion liquid in which carbon nanotubes having a small outer diameter are uniformly and highly dispersed in a dispersion medium has been an important issue for expanding applications.

JP 2006-309958 A JP 2011-70908 A JP 2014-19619 A JP 2008-285368 A JP-A-2000-86219 JP 2005-162877 A JP 2005-220245 A

  The problem to be solved by the present invention is to solve the above-mentioned conventional problems, and has a carbon nanotube having a half-value width of 2 ° to 6 ° in powder X-ray diffraction and a triazine derivative having an acidic functional group. It is to provide a carbon nanotube dispersion using a dispersant containing:

  Another object of the present invention is to provide a carbon nanotube dispersion and a carbon nanotube resin composition for obtaining an electrode film having high adhesion and conductivity. More specifically, an object of the present invention is to provide a carbon nanotube dispersion liquid, a carbon nanotube resin composition, and a mixture slurry having high dispersibility. More specifically, an object of the present invention is to provide a lithium ion secondary battery having excellent rate characteristics and high-temperature storage characteristics.

  The inventors of the present invention have intensively studied to solve the above-mentioned problems. The inventors have found that the use of a carbon nanotube dispersion liquid containing a carbon nanotube having a half-value width of 2 ° to 6 ° in X-ray diffraction and a triazine derivative having an acidic functional group makes it possible to obtain a conductive property. And that an electrode film having excellent adhesion can be obtained.

That is, the present invention relates to a carbon nanotube dispersion liquid containing a carbon nanotube (A), a solvent (B), and a dispersant (C), wherein the carbon nanotube (A) has a diffraction angle in powder X-ray diffraction analysis. A peak is present at 2θ = 25 ° ± 2 °, the half width of the peak is 2 ° to 6 °, and the maximum peak intensity in the range of 1560 to 1600 cm ⁻¹ is G in the Raman spectrum, and 1310 to 1350 cm. ^When the maximum peak intensity within the range of ^-1 is D, the G / D ratio is 0.5 to 5.0, and the dispersant (C) is an acid represented by the following general formula (1). The present invention relates to a carbon nanotube dispersion liquid containing a triazine derivative having a functional group.

[In the general formula (1), R ¹ represents a group represented by -X ¹ -Y ¹ . X ¹ represents an arylene group which may have a substituent, and Y ¹ represents a sulfo group, a carboxyl group or a phosphate group.
Q ¹ represents an -OH or -NH-R ^2. Q ² represents an -OH or -NH-R ^3. R ² and R ³ each independently represent an aryl group which may have a substituent, a heterocyclic group which may have a substituent, or a group represented by -X ¹ -Y ¹ . However, R ² and R ³ are not simultaneously -X ¹ -Y ¹ . ]

The present invention also relates to the carbon nanotube dispersion liquid, wherein the carbon nanotube (A) has a BET specific surface area of 200 to 550 m ² / g.

Further, the present invention is that the maximum peak intensity in the range of 1560～1600Cm ^-1 in the Raman spectrum of the carbon nanotube (A) G, a maximum peak intensity in the range of 1310～1350Cm ^-1 upon the D The carbon nanotube dispersion liquid having a G / D ratio of 1.0 to 3.0.

  Further, the present invention provides a method for producing a carbon nanotube (A) in which the total amount of iron, cobalt, nickel, aluminum, magnesium, silica, manganese, and molybdenum is less than 0.5% by mass based on the entire carbon nanotube (A). The present invention relates to the above-mentioned carbon nanotube dispersion liquid.

The present invention also relates to the carbon nanotube dispersion liquid, wherein the volume resistivity of the carbon nanotube (A) is from 1.0 × 10 ^{−2 to} 2.5 × 10 ⁻² Ω · cm.

  Further, according to the present invention, the carbon nanotube (A) has a peak at a diffraction angle 2θ = 25 ° ± 2 ° in the powder X-ray diffraction analysis, and the half width of the peak is 2 ° or more and less than 3 °. The above-mentioned carbon nanotube dispersion liquid characterized by the above-mentioned.

  The present invention also relates to the above-mentioned carbon nanotube dispersion liquid, wherein the average outer diameter of the carbon nanotube (A) is more than 3 nm and less than 16 nm.

  The present invention also relates to the above carbon nanotube dispersion, wherein the solvent (B) is an amide organic solvent or water.

  The present invention also relates to a carbon nanotube resin composition containing the carbon nanotube dispersion liquid and a binder (D).

  The present invention also relates to a mixture slurry containing the carbon nanotube resin composition and an active material (E).

  The present invention also relates to an electrode film (F) coated with the mixture slurry.

  Further, the present invention is a lithium ion secondary battery including a positive electrode, a negative electrode, and an electrolyte containing lithium, wherein at least one of the positive electrode and the negative electrode is the above-mentioned electrode film. Related to secondary batteries.

  By using the carbon nanotube dispersion liquid of the present invention, a resin composition, a mixture slurry, and an electrode film having excellent conductivity and adhesion can be obtained. In addition, a lithium ion secondary battery having excellent rate characteristics and high-temperature storage characteristics can be obtained. Therefore, the carbon nanotube dispersion liquid of the present invention can be used in various application fields requiring high conductivity, adhesion, and durability.

  Hereinafter, the carbon nanotube dispersion liquid, the resin composition, the mixture slurry, the electrode film coated with the same, and the lithium ion secondary battery of the present invention will be described in detail.

(1) Carbon nanotube (A)
The carbon nanotube (A) of the present embodiment has a shape obtained by winding planar graphite into a cylindrical shape. The carbon nanotube (A) may be a mixture of single-walled carbon nanotubes. The single-walled carbon nanotube has a structure in which one layer of graphite is wound. Multi-walled carbon nanotubes have a structure in which two or more layers of graphite are wound. Further, the side wall of the carbon nanotube (A) may not have a graphite structure. For example, a carbon nanotube having a sidewall having an amorphous structure can be used as the carbon nanotube (A).

  The shape of the carbon nanotube (A) of the present embodiment is not limited. Examples of such shapes include various shapes including a needle shape, a cylindrical tube shape, a fish bone shape (fishbone or cup laminated type), a trump shape (platelet), and a coil shape. In this embodiment, the shape of the carbon nanotube (A) is preferably a needle shape or a cylindrical tube shape, among others. The carbon nanotube (A) may have a single shape or a combination of two or more shapes.

  Examples of the form of the carbon nanotube (A) of the present embodiment include graphite whiskers, filamentous carbon, graphite fibers, ultrafine carbon tubes, carbon tubes, carbon fibrils, carbon microtubes, and carbon nanofibers. It is not limited to. The carbon nanotube (A) may have a single form or a form in which two or more kinds are combined.

  The outer diameter of the carbon nanotube (A) of the present embodiment is preferably more than 3 nm and less than 25 nm, more preferably more than 3 nm and less than 20 nm, even more preferably more than 3 nm and less than 16 nm. .

  The standard deviation of the outer diameter of the carbon nanotube (A) of the present embodiment is preferably from 2 to 8 nm, more preferably from 3 to 6 nm.

  The outer diameter and the average outer diameter of the carbon nanotube (A) of the present embodiment are determined as follows. First, the carbon nanotube (A) is observed and imaged by a transmission electron microscope. Next, in the observation photograph, arbitrary 300 carbon nanotubes (A) are selected, and the outer diameter of each is measured. Next, an average outer diameter (nm) of the carbon nanotube (A) is calculated as a number average of the outer diameter.

  The fiber length of the carbon nanotube (A) of the present embodiment is preferably from 0.1 to 150 μm, more preferably from 1 to 10 μm.

  The carbon purity of the carbon nanotube (A) of the present embodiment is represented by the content (% by mass) of carbon atoms in the carbon nanotube (A). The carbon purity is preferably 90% by mass or more, more preferably 95% by mass or more, still more preferably 99% by mass or more, and more preferably 99.5% by mass or more, based on 100% by mass of the carbon nanotube (A).

  The amount of metal contained in the carbon nanotube (A) of the present embodiment is preferably less than 10% by mass, more preferably less than 5% by mass, even more preferably less than 1% by mass, based on 100% by mass of the carbon nanotube (A). , Less than 0.5% by mass. Examples of the metal contained in the carbon nanotube (A) include a metal and a metal oxide used as a catalyst when synthesizing the carbon nanotube (A). Specific examples include metals such as cobalt, nickel, aluminum, magnesium, silica, manganese and molybdenum, metal oxides, and composite oxides thereof.

  Various conventionally known methods can be used as the method for purifying the carbon nanotube (A) of the present embodiment. For example, an acid treatment, a graphitization treatment, and a chlorination treatment may be mentioned.

  The acid used for acid-treating the carbon nanotube (A) of the present embodiment may be any acid that can dissolve the metal and metal oxide contained in the carbon nanotube (A). Preferably, among inorganic acids, hydrochloric acid, sulfuric acid and nitric acid are particularly preferred.

  The acid treatment of the carbon nanotube (A) of the present embodiment is preferably performed in a liquid phase, and more preferably, the carbon nanotube is dispersed and / or mixed in the liquid phase. The acid-treated carbon nanotubes are preferably washed with water and dried.

  The graphitization treatment of the carbon nanotube (A) of the present embodiment can be performed by heating the carbon nanotube (A) at 1500 to 3500 ° C. in an inert atmosphere having an oxygen concentration of 0.1% by volume or less.

  In the chlorination treatment of the carbon nanotube (A) of the present embodiment, a chlorine gas is introduced under an inert atmosphere having an oxygen concentration of 0.1% by volume or less, and the carbon nanotube (A) is heated at 800 ° C. to 2000 ° C. Can be performed.

  The carbon nanotube (A) of the present embodiment usually exists as secondary particles. The shape of the secondary particles may be, for example, a state in which carbon nanotubes (A), which are general primary particles, are intricately intertwined. An aggregate of linear carbon nanotubes (A) may be used. Secondary particles, which are aggregates of linear carbon nanotubes (A), are more likely to be unraveled than entangled ones. In addition, the linear one has better dispersibility than the entangled one, so that it can be suitably used as the carbon nanotube (A).

  The carbon nanotube (A) of the present embodiment may be a surface-treated carbon nanotube. Further, the carbon nanotube (A) may be a carbon nanotube derivative provided with a functional group represented by a carboxyl group. Alternatively, a carbon nanotube (A) containing a substance typified by an organic compound, a metal atom, or fullerene can be used.

  The layer configuration of the carbon nanotube (A) can be analyzed by powder X-ray diffraction analysis according to the following method.

  First, the carbon nanotubes (A) are packed in a predetermined sample holder so that the surface is flat, set in a powder X-ray diffraction analyzer, and measured by changing the irradiation angle of the X-ray source from 15 ° to 35 °. For example, CuKα radiation is used as the X-ray source. The carbon nanotube (A) can be evaluated by reading the diffraction angle 2θ at which a peak appears at that time. In graphite, a peak is usually detected at around 2θ of 26 °, and it is known that this is a peak due to interlayer diffraction. Since the carbon nanotube (A) also has a graphite structure, a peak due to graphite interlayer diffraction is detected near this. However, since the carbon nanotube has a cylindrical structure, its value differs from that of graphite. When a peak appears at a position where the value 2θ is 25 ° ± 2 °, it can be determined that the composition includes a composition having a multilayer structure instead of a single layer. Since the peak appearing at this position is a peak due to interlayer diffraction of the multilayer structure, the number of layers of the carbon nanotube (A) can be determined. Since the single-walled carbon nanotube has only one wall, no peak appears at a position of 25 ° ± 2 ° only with the single-walled carbon nanotube. However, even a single-walled carbon nanotube is not a 100% single-walled carbon nanotube, and when multi-walled carbon nanotubes or the like are mixed, a peak may appear at a position where 2θ is 25 ° ± 2 °. .

  In the carbon nanotube (A) of the present embodiment, a peak appears at a position where 2θ is 25 ° ± 2 °. The layer configuration can also be analyzed from the half width of the peak at 25 ° ± 2 ° detected by powder X-ray diffraction analysis. That is, it is considered that the number of layers of the multi-walled carbon nanotube (A) increases as the half width of the peak decreases. Conversely, the larger the half width of this peak, the smaller the number of carbon nanotube layers.

  The carbon nanotube (A) of the present embodiment has a peak at a diffraction angle 2θ = 25 ° ± 2 ° when the powder X-ray diffraction analysis is performed, and the half width of the peak is 2 ° to 6 °. It is more preferably at least 5 ° and less than 5 °, and further preferably at least 2 ° and less than 3 °.

The G / D ratio of the carbon nanotube (A) of the present embodiment is determined by Raman spectroscopy. In the carbon nanotube (A) of the present embodiment, when the maximum peak intensity in the range of 1560 to 1600 cm ^-1 is G and the maximum peak intensity in the range of 1310 to 1350 cm ^-1 is D in the Raman spectrum, The G / D ratio is 0.5 to 5.0, preferably 1.0 to 3.0, and more preferably 1.5 to 2.5.

There are various laser wavelengths used in Raman spectroscopy. Here, 532 nm and 632 nm are used. The Raman shift seen near 1590 cm ^-1 in the Raman spectrum is called a G band derived from graphite, and the Raman shift seen near 1350 cm ^-1 is called a D band derived from defects in amorphous carbon or graphite. A carbon nanotube having a higher G / D ratio has a higher degree of graphitization.

The volume resistivity of the carbon nanotube (A) of the present embodiment is preferably from 1.0 × 10 ^{−2 to} 2.5 × 10 ⁻² Ω · cm, and from 1.0 × 10 ^{−2 to} 2.0 ×. More preferably, it is 10 ⁻² Ω · cm. The volume resistivity of the carbon nanotube (A) can be measured using a powder resistivity measuring device (manufactured by Mitsubishi Chemical Analytech Co., Ltd .: Loresta GP powder resistivity measuring system MCP-PD-51)). .

BET specific surface area of the carbon nanotubes of the present embodiment (A) is preferably those 100~800m ² / g, more preferably a 150~600m ² / g, particularly preferably from 200~550m ² / g.

The carbon nanotube (A) of the present embodiment has a peak at a diffraction angle 2θ = 25 ° ± 2 ° in the powder X-ray diffraction analysis, and the half width of the peak is 2 ° to 6 °, and the Raman spectrum When the maximum peak intensity in the range of 1560 to 1600 cm ^-1 is G and the maximum peak intensity in the range of 1310 to 1350 cm ^-1 is D, the G / D ratio is 0.5 to 5.0. There is no particular limitation, and carbon nanotubes produced by any method may be used. For example, after obtaining a carbon nanotube by a laser ablation method, an arc discharge method, a thermal CVD method, a plasma CVD method, and a combustion method, the carbon nanotube (A) is heated in an atmosphere having an oxygen concentration of 1% by volume or less. Can be obtained. The temperature at the time of heating is preferably from 700 to 2500C, more preferably from 900 to 2000C, and even more preferably from 1200 to 1800C.

  The carbon nanotube (A) according to the present embodiment is obtained by introducing chlorine gas into an atmosphere having an oxygen concentration of 1% by volume or less and a temperature of 700 to 1000 ° C. to convert the metal contained in the carbon nanotube (A) into a metal chloride. It is preferable to obtain carbon nanotubes (A) by heating to ２０００2000 ° C. to volatilize metal chlorides and obtain a carbon nanotube by introducing chlorine gas into an atmosphere having an oxygen concentration of 1% by volume or less and 700-1000 ° C. It is further preferable that after the metal contained in A) is converted into a metal chloride, the pressure is reduced and the metal chloride is volatilized to obtain a carbon nanotube (A).

(2) Solvent (B)
The solvent (B) of the present embodiment is not particularly limited as long as the carbon nanotubes (A) can be dispersed, but is a mixture of water and / or a water-soluble organic solvent. It is preferred that

  Examples of the water-soluble organic solvent include alcohols (methanol, ethanol, propanol, isopropanol, butanol, isobutanol, secondary butanol, tertiary butanol, benzyl alcohol, etc.) and polyhydric alcohols (ethylene glycol, diethylene glycol, triethylene glycol, polyethylene). Glycol, propylene glycol, dipropylene glycol, polypropylene glycol, butylene glycol, hexanediol, pentanediol, glycerin, hexanetriol, thiodiglycol, etc., polyhydric alcohol ethers (ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene) Glycol monobutyl ether, diethylene glycol monomethyl ether Diethylene glycol monoethyl ether, diethylene glycol monobutyl ether, propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol monobutyl ether, ethylene glycol monomethyl ether acetate, triethylene glycol monomethyl ether, triethylene glycol monoethyl ether, triethylene glycol monobutyl ether, Ethylene glycol monophenyl ether, propylene glycol monophenyl ether, etc.), amines (ethanolamine, diethanolamine, triethanolamine, N-methyldiethanolamine, N-ethyldiethanolamine, morpholine, N-ethylmorpholine, ethylenediamine, diethylenediamine, Liethylenetetramine, tetraethylenepentamine, polyethyleneimine, pentamethyldiethylenetriamine, tetramethylpropylenediamine, etc., amides (N-methyl-2-pyrrolidone (NMP), N-ethyl-2-pyrrolidone (NEP), N, N -Dimethylformamide, N, N-dimethylacetamide, N, N-diethylacetamide, N-methylcaprolactam, etc., heterocyclic systems (cyclohexylpyrrolidone, 2-oxazolidone, 1,3-dimethyl-2-imidazolidinone, γ- Butyrolactone, etc.), sulfoxides (dimethylsulfoxide, etc.), sulfones (hexamethylphosphorotriamide, sulfolane, etc.), lower ketones (acetone, methylethylketone, etc.), tetrahydrofuran, urea, aceto It can be used, such as tolyl. Among these, water or an amide organic solvent is more preferable, and N-methyl-2-pyrrolidone and N-ethyl-2-pyrrolidone are particularly preferable among the amide organic solvents.

  When only the amide organic solvent is used as the solvent (B) in the present embodiment, the amount of water in the solvent (B) is preferably 500 ppm or less, more preferably 300 ppm or less, and more preferably 100 ppm or less. Is particularly preferred.

(3) Dispersant (C)
The dispersant (C) of the present embodiment contains a triazine derivative having an acidic functional group represented by the general formula (1).

In the general formula (1), R ¹ represents a group represented by -X ¹ -Y ¹ . X ¹ represents an arylene group which may have a substituent, and Y ¹ represents a sulfo group, a carboxyl group or a phosphate group.

The “substituents” of the arylene group which may have a substituent of X ¹ may be the same or different, and specific examples thereof include a hydroxyl group, a halogen group such as fluorine, chlorine and bromine, a nitro group, an alkyl group and the like. Groups, aryl groups, cycloalkyl groups, alkoxyl groups, aryloxy groups, alkylthio groups, arylthio groups and the like. Further, these substituents may be plural.

  The “arylene group” of the arylene group which may have a substituent includes a phenylene group, a naphthylene group and the like.

Q ¹ represents an -OH or -NH-R ^2. Q ² represents an -OH or -NH-R ^3. R ² and R ³ each independently represent an aryl group which may have a substituent, a heterocyclic group which may have a substituent, or a group represented by -X ¹ -Y ¹ . However, R ² and R ³ are not simultaneously -X ¹ -Y ¹ .

The “substituent” of the optionally substituted aryl group and the optionally substituted heterocyclic group of R ² and R ³ has the same meaning as the substituent of X ¹ .

Examples of the “aryl group” of the optionally substituted aryl group of R ² and R ³ include a phenyl group and a naphthyl group.

The “heterocyclic group” of the heterocyclic group which may have a substituent of R ² and R ³ is, for example, an aromatic or aliphatic heterocyclic ring containing a nitrogen atom, an oxygen atom, a sulfur atom, and a phosphorus atom. Specific examples include a thienyl group, a benzo [b] thienyl group, a naphtho [2,3-b] thienyl group, a pyrrolyl group, a thianthrenyl group, a furyl group, a pyranyl group, an isobenzofuranyl group, a chromenyl group, Xanthenyl group, phenoxathiinyl group, 2H-pyrrolyl group, imidazolyl group, pyrazolyl group, pyridyl group, pyrazinyl group, pyrimidinyl group, pyridazinyl group, indolizinyl group, isoindolyl group, 3H-indolyl group, indolyl group, 1H-indazolyl group , A purinyl group, a 4H-quinolizinyl group, an isoquinolyl group, a quinolyl group, a phthalazinyl group, a naphthyridinyl group, a quinoxalini Group, quinazolinyl group, cinnolinyl group, pteridinyl group, 4aH-carbazolyl group, carbazolyl group, β-carbolinyl group, phenanthridinyl group, acridinyl group, perimidinyl group, phenanthrolinyl group, phenazinyl group, phensalzinyl group, isothiazolyl Group, phenothiazinyl group, isoxazolyl group, flazanyl group, phenoxazinyl group, isochromanyl group, chromanyl group, pyrrolidinyl group, pyrrolinyl group, imidazolidinyl group, imidazolinyl group, pyrazolidinyl group, pyrazolinyl group, piperidyl group, piperidinyl group, indolinyl group, indolinyl group, indolinyl group , Quinuclidinyl, morpholinyl, thioxanthryl, benzofuryl, benzothiazolyl, benzoxazolyl, benzimidazolyl, benzotriazolyl Group, and the like. In particular, a heterocyclic group containing at least one of a nitrogen atom and an oxygen atom is preferable because of its excellent dispersibility, and a carbazolyl group and a benzoimidazolyl group are more preferable.

  Further, the content of the triazine derivative is preferably 0.5 to 50% by mass, more preferably 0.5 to 30% by mass, and still more preferably 0.5 to 25% by mass based on the carbon nanotube.

The dispersant used in the present invention may contain a basic substance together with the triazine derivative. As the basic substance, an amine or an inorganic base is preferable.
Inorganic bases include alkali metal hydroxides, alkaline earth metal hydroxides, alkali metal carbonates, alkaline earth metal carbonates, alkali metal phosphates, alkaline earth metal phosphates And the like.

  Examples of the alkali metal hydroxide include lithium hydroxide, sodium hydroxide, potassium hydroxide and the like.

  Examples of the alkaline earth metal hydroxide include magnesium hydroxide, calcium hydroxide, strontium hydroxide, barium hydroxide and the like.

  Examples of the alkali metal carbonate include lithium carbonate, sodium carbonate, sodium hydrogen carbonate, potassium carbonate, potassium hydrogen carbonate and the like.

  Examples of the alkaline earth metal carbonate include magnesium carbonate, calcium carbonate, strontium carbonate, barium carbonate and the like.

  Examples of the alkali metal phosphate include lithium phosphate, trisodium phosphate, disodium hydrogen phosphate, tripotassium phosphate, and dipotassium hydrogen phosphate.

  Examples of the alkaline earth metal phosphate include magnesium phosphate, calcium phosphate, strontium phosphate, and barium phosphate.

  The amount of the inorganic base used in the present invention is not particularly limited, but is preferably 0.1 mol or more and 5 mol or less with respect to 1 mol of the triazine derivative represented by the general formula (1). 0.2 mol or more and 1 mol or less are more preferable.

  The inorganic base can be added during the production of the dispersant and / or the dispersion composition.

(4) Carbon Nanotube Dispersion The carbon nanotube dispersion of the present embodiment contains the carbon nanotube (A), the solvent (B), and the dispersant (C).

  In order to obtain the carbon nanotube dispersion liquid of the present embodiment, it is preferable to perform a process of dispersing the carbon nanotubes (A) in the solvent (B). The dispersion apparatus used for performing such processing is not particularly limited.

  As the dispersing device, a dispersing device usually used for pigment dispersion or the like can be used. For example, mixers such as disperser, homomixer, and planetary mixer, homogenizers (Advanced Digital Sonifer (registered trademark) manufactured by BRANSON, Model 450DA), "Clearmix" manufactured by M-Technic, "Fillmix" manufactured by PRIMIX, and silver such as "Abramix" manufactured by Son Co., Ltd.), paint conditioner (Red Devil Co., Ltd.), colloid mill ("PUC Colloid Mill" manufactured by PUC, "Colloid Mill MK" manufactured by IKA), corn mill ("Corn Mill" manufactured by IKA) MKO ”), ball mills, sand mills (“ Dyno mill ”manufactured by Shinmaru Enterprises, etc.), attritors, pearl mills (“ DCP mills ”manufactured by Eirich, etc.), media-type dispersing machines such as co-ball mills, and wet jet mills. (Eg "Genus PY" manufactured by Genus, "Starburst" manufactured by Sugino Machine Co., Ltd., "Nanomizer" manufactured by Nanomizer, etc.), media-less such as "Clear SS-5" manufactured by M-Technic, and "MICROS" manufactured by Nara Machine Co., Ltd. Examples include a disperser and other roll mills, but are not limited thereto.

  The solid content of the carbon nanotube dispersion of the present embodiment is preferably 0.1 to 30% by mass, more preferably 0.5 to 25% by mass, and preferably 1 to 10% by mass based on 100% by mass of the carbon nanotube dispersion. % Is preferable, and 2 to 8% by mass is particularly preferable.

  The amount of the dispersant (C) in the carbon nanotube dispersion liquid of the present embodiment is preferably 3 to 300% by mass based on 100% by mass of the carbon nanotube (A). From the viewpoint of conductivity, it is preferably used in an amount of 5 to 100% by mass, and more preferably 10 to 50% by mass.

  The fiber length of the carbon nanotubes (A) in the carbon nanotube dispersion liquid of the present embodiment is preferably 0.1 to 10 μm, more preferably 0.2 to 5 μm, and particularly preferably 0.3 to 2 μm.

(4) Binder (D)
The binder (D) is a resin that holds the carbon nanotube (A) and the dispersant (C) in the solvent (B).

  Examples of the binder (D) of the present embodiment include ethylene, propylene, vinyl chloride, vinyl acetate, vinyl alcohol, maleic acid, acrylic acid, acrylic acid ester, methacrylic acid, methacrylic acid ester, acrylonitrile, styrene, vinyl butyral, Polymers or copolymers containing vinyl acetal, vinyl pyrrolidone, etc. as constituent units; polyurethane resin, polyester resin, phenol resin, epoxy resin, phenoxy resin, urea resin, melamine resin, alkyd resin, acrylic resin, formaldehyde resin, silicone resin Cellulose resins such as carboxymethylcellulose; rubbers such as styrene-butadiene rubber and fluororubber; and conductive resins such as polyaniline and polyacetylene. Further, modified products or mixtures of these resins, and copolymers may be used. Particularly, it is preferable to use a polymer compound having a fluorine atom in the molecule, for example, polyvinylidene fluoride, polyvinyl fluoride, tetrafluoroethylene or the like from the viewpoint of resistance.

  The weight average molecular weight of these resins as the binder (D) of the present embodiment is preferably from 10,000 to 2,000,000, more preferably from 100,000 to 1,000,000, and more preferably from 200,000 to 1 , 000,000 is particularly preferred. If the molecular weight is small, the resistance and adhesion of the binder may be reduced. When the molecular weight is increased, the resistance and adhesion of the binder are improved, but the viscosity of the binder itself is increased and the workability is reduced, and at the same time, it acts as an aggregating agent, and the dispersed particles may aggregate significantly.

  In view of industrial applicability assumed by the present invention, the binder (D) preferably contains a polymer compound having a fluorine atom, and is preferably a polymer compound having a fluorine atom. More preferably, it is a polymer, and particularly preferably polyvinylidene fluoride.

(5) Carbon nanotube resin composition The carbon nanotube resin composition of the present embodiment contains a carbon nanotube (A), a solvent (B), a dispersant (C), and a binder (D).

  In order to obtain the carbon nanotube resin composition of the present embodiment, it is preferable to mix the carbon nanotube dispersion liquid (C) and the binder (D) to make them uniform. As the mixing method, various conventionally known methods can be used. The carbon nanotube resin composition can be produced by using the dispersing apparatus described for the carbon nanotube dispersion.

(6) Active material (E)
The active material (E) of the present embodiment is a material that forms a basis for a battery reaction. The active material is divided into a positive electrode active material and a negative electrode active material from electromotive force.

The positive electrode active material is not particularly limited, but a metal compound such as a metal oxide or metal sulfide capable of doping or intercalating lithium ions, a conductive polymer, or the like can be used. Examples thereof include oxides of transition metals such as Fe, Co, Ni, and Mn, composite oxides with lithium, and inorganic compounds such as transition metal sulfides. Specifically, transition metal oxide powders such as MnO, V ₂ O ₅ , V ₆ O ₁₃ , and TiO ₂ , lithium nickelate having a layered structure, lithium cobaltate, lithium manganate, and lithium manganate having a spinel structure can be used. Examples thereof include a composite oxide powder of lithium and a transition metal, a lithium iron phosphate-based material that is a phosphate compound having an olivine structure, and a transition metal sulfide powder such as TiS ₂ and FeS. Further, conductive polymers such as polyaniline, polyacetylene, polypyrrole, and polythiophene can also be used. Further, the above-mentioned inorganic compounds and organic compounds may be used as a mixture.

The negative electrode active material is not particularly limited as long as it can dope or intercalate lithium ions. For example, metal Li, its alloys such as tin alloy, silicon alloy, lead alloy, and the like, Li _x Fe ₂ O ₃ , Li _x Fe ₃ O ₄ , and Li _x WO ₂ (x is a number of 0 <x <1) ), Metal oxides such as lithium titanate, lithium vanadate, and lithium silicate; conductive polymer systems such as polyacetylene and poly-p-phenylene; and amorphous carbonaceous materials such as soft carbon and hard carbon. And carbon-based materials such as artificial graphite such as highly graphitized carbon material, or carbonaceous powder such as natural graphite, carbon black, mesophase carbon black, resin fired carbon material, gas-grown carbon fiber, and carbon fiber. These negative electrode active materials can be used alone or in combination of two or more.

  The positive electrode active material is preferably a composite oxide with lithium containing a transition metal such as Al, Fe, Co, Ni, and Mn, and a composite oxide with lithium containing any of Al, Co, Ni, and Mn. Is more preferable, and a composite oxide with lithium containing Ni and / or Mn is particularly preferable. Particularly good effects can be obtained when these active materials are used.

BET specific surface area of the active material is preferably a 0.1 to 10 m ² / g, more preferably a 0.2~5m ² / g, further preferably from 0.3~3m ² / g.

  The average particle size of the active material is preferably in the range of 0.05 to 100 μm, and more preferably in the range of 0.1 to 50 μm. The average particle diameter of the active material referred to in the present specification is an average value of the particle diameter of the active material measured by an electron microscope.

(7) Mixture slurry The mix slurry of the present embodiment contains carbon nanotubes (A), a solvent (B), a dispersant (C), a binder (D), and an active material (E).

  In order to obtain the mixture slurry of the present embodiment, it is preferable to perform a treatment of adding the active material to the carbon nanotube resin composition and then dispersing the active material. The dispersion apparatus used for performing such processing is not particularly limited. The mixture slurry can be obtained by using the dispersing apparatus described for the carbon nanotube dispersion liquid.

  The amount of the active material (E) in the mixture slurry is preferably from 20 to 85% by mass, particularly preferably from 40 to 85% by mass, based on 100% by mass of the mixture slurry.

  The amount of the carbon nanotubes (A) in the mixture slurry is preferably 0.05 to 10% by mass, more preferably 0.1 to 5% by mass, based on 100% by mass of the active material. It is preferably about 3% by mass.

  The amount of the binder (A) in the mixture slurry is preferably 0.5 to 20% by mass, more preferably 1 to 10% by mass, and more preferably 1 to 5% by mass, based on 100% by mass of the active material. % Is particularly preferred.

  The solid content of the mixture slurry is preferably 30 to 90% by mass, and more preferably 40 to 85% by mass, based on 100% by mass of the mixture slurry.

  The water content in the mixture slurry is preferably at most 500 ppm, more preferably at most 300 ppm, particularly preferably at most 100 ppm.

(7) Electrode film The electrode film of the present embodiment is a coating film in which an electrode mixture layer is formed by applying and drying a mixture slurry on a current collector.

  The material and shape of the current collector used for the electrode film of the present embodiment are not particularly limited, and those suitable for various secondary batteries can be appropriately selected. For example, examples of the material of the current collector include metals and alloys such as aluminum, copper, nickel, titanium, and stainless steel. Further, as the shape, generally, a flat foil is used, but a roughened surface, a perforated foil, and a mesh-shaped current collector can also be used.

  The method for applying the mixture slurry on the current collector is not particularly limited, and a known method can be used. Specifically, die coating, dip coating, roll coating, doctor coating, knife coating, spray coating, gravure coating, screen printing, electrostatic coating, etc. Examples of the method include standing drying, a blast dryer, a warm air dryer, an infrared heater, a far infrared heater, and the like, but are not particularly limited thereto.

  After the application, a rolling process using a lithographic press or a calender roll may be performed. The thickness of the electrode mixture layer is generally from 1 μm to 500 μm, preferably from 10 μm to 300 μm.

(8) Lithium ion secondary battery The lithium ion secondary battery of the present embodiment includes a positive electrode, a negative electrode, and an electrolyte.

  As the positive electrode, an electrode film produced by applying and drying a mixture slurry containing a positive electrode active material can be used.

  As the negative electrode, an electrode film produced by applying and drying a mixture slurry containing a negative electrode active material can be used.

As the electrolyte, various conventionally known electrolytes can be used. For example, LiBF ₄ , LiClO ₄ , LiPF ₆ , LiAsF ₆ , LiSbF ₆ , LiCF ₃ SO ₃ , Li (CF ₃ SO ₂ ) ₂ N, LiC ₄ F ₉ SO ₃ , Li (CF ₃ SO ₂ ) ₃ C, LiI , LiBr, LiCl, LiAlCl, LiHF ₂ , LiSCN, or LiBPh ₄ (where Ph is a phenyl group), but is not limited thereto. The electrolyte is preferably dissolved in a non-aqueous solvent and used as an electrolyte.

  The non-aqueous solvent is not particularly limited, for example, carbonates such as ethylene carbonate, propylene carbonate, butylene carbonate, dimethyl carbonate, ethyl methyl carbonate, and diethyl carbonate; γ-butyrolactone, γ-valerolactone, and γ Lactones such as -octanoic lactone; tetrahydrofuran, 2-methyltetrahydrofuran, 1,3-dioxolan, 4-methyl-1,3-dioxolan, 1,2-methoxyethane, 1,2-ethoxyethane, and 1, Grimes such as 2-dibutoxyethane; esters such as methyl formate, methyl acetate and methyl propionate; sulfoxides such as dimethyl sulfoxide and sulfolane; and nitriles such as acetonitrile And the like. These solvents may be used alone or in combination of two or more.

  It is preferable that the lithium secondary battery of the present embodiment includes a separator. Examples of the separator include a polyethylene nonwoven fabric, a polypropylene nonwoven fabric, a polyamide nonwoven fabric and those obtained by subjecting them to a hydrophilic treatment, but are not particularly limited thereto.

  Although the structure of the lithium ion secondary battery of the present embodiment is not particularly limited, it is usually composed of a positive electrode and a negative electrode, and a separator provided as necessary, and is used in a paper type, a cylindrical type, a button type, a laminated type, and the like. It can be made into various shapes according to the purpose.

  Hereinafter, the present invention will be described more specifically with reference to examples. The present invention is not limited to the following examples unless it exceeds the gist. In the examples, “carbon nanotube” may be abbreviated as “CNT”.

<Method of measuring physical properties>
The physical properties of the CNTs used in each of the following Examples and Comparative Examples were measured by the following methods.

<X-ray powder diffraction analysis of CNT>
CNT was placed on the central concave portion of an aluminum sample plate (outer diameter φ46 mm, thickness 3 mm, sample portion φ26.5 mm, thickness 2 mm), and flattened using a slide glass. Thereafter, the medicine packaging paper was placed on the surface on which the sample was placed, and the surface on which the aluminum high sheet packing was placed was flattened by applying a load of 1 ton. Thereafter, the packing paper and the aluminum high sheet packing were removed to obtain a sample of the CNT for powder X-ray diffraction analysis. Thereafter, a sample for CNT powder X-ray diffraction analysis was installed in an X-ray diffractometer (Ultima 2100, manufactured by Rigaku Corporation) and operated from 15 ° to 35 ° to perform analysis. Sampling is performed every 0.02 °, and the scan speed is 2 ° / min. And The voltage was 40 kV, the current was 40 mA, and the X-ray source was CuKα radiation. The plots obtained at the diffraction angles 2θ = 25 ° ± 2 ° obtained at this time were simply moving averaged at 11 points, and the half width of the peak was taken as the half width of CNT. The baseline was a line connecting the plots of 2θ = 16 ° and 2θ = 34 °.

<Raman spectroscopic analysis of CNT>
The CNT was set on a Raman microscope (XproRA, manufactured by Horiba, Ltd.), and the measurement was performed using a laser wavelength of 532 nm. The measurement conditions were as follows: capture time 60 seconds, integration number 2 times, neutral density filter 10%, objective lens magnification 20 times, confocus hole 500, slit width 100 μm, and measurement wavelength 100 to 3000 cm ⁻¹ . The CNT for measurement was fractionated on a slide glass and flattened using a spatula. Of the obtained peak, the maximum peak intensity in the range of 1560～1600Cm ^-1 in the spectrum G, and maximum peak intensity in the range of 1310～1350Cm ^-1 is D, the ratio of G / D of CNT G / D ratio.

<Volume resistivity of CNT>
Using a powder resistivity measurement device (manufactured by Mitsubishi Chemical Analytech Co., Ltd .: Loresta GP powder resistivity measurement system MCP-PD-51)), a sample mass of 1.2 g was used, and a probe unit for powder was used. The needle / ring electrode, electrode spacing 5.0 mm, electrode radius 1.0 mm, sample radius 12.5 mm), the applied voltage limiter was 90 V, and the volume resistivity [Ω · cm] of the conductive powder under various pressures was adjusted. It was measured. The value of the volume resistivity of CNT at a density of 1 g / cm ³ was evaluated.

<Measurement of CNT purity>
The CNT was acid-decomposed using a microwave sample pretreatment device (ETHOS1 manufactured by Milestone General Co., Ltd.) to extract the metal contained in the CNT. Thereafter, analysis was performed using a multi-type ICP emission spectrometer (manufactured by Agilent, 720-ES), and the amount of metal contained in the extract was calculated. The purity of CNT was calculated as follows.
(Equation 1) CNT purity (%) = ((CNT mass-metal mass in CNT) 中 CNT mass) × 100
<Specific surface area of CNT>
After weighing 0.03 g of CNT using an electronic balance (manufactured by Sartorius, MSA225S100DI), the CNT was dried at 110 ° C. for 15 minutes while being degassed. Then, the specific surface area of CNT was measured using a fully automatic specific surface area measuring device (HM-model 1208, manufactured by MOUNTECH).

<Measurement of viscosity of CNT dispersion>
After allowing the CNT dispersion to stand in a thermostat at 25 ° C. for 1 hour or more, sufficiently stirring the CNT dispersion, and using a viscometer (TOKISANGYO CO. LTD, VISCOMTER, MODEL BL), the stirring speed is 6 rpm. The viscosity at 60 rpm was measured.

<Volume resistivity of electrode film>
After applying the mixture slurry on an aluminum foil using an applicator so that the basis weight per electrode is 20 mg / cm ² , the coating is applied at 120 ° C. ± 5 ° C. for 25 minutes in an electric oven. Was dried. Then, the surface resistivity (Ω / □) of the dried coating film was measured using Loresta GP, MCP-T610 manufactured by Mitsubishi Chemical Analytech Co., Ltd. After the measurement, the volume resistivity (Ω · cm) of the electrode film was multiplied by the thickness of the electrode mixture layer formed on the aluminum foil. The thickness of the electrode film was obtained by subtracting the thickness of the aluminum foil from the average value obtained by measuring three points in the electrode film using a film thickness meter (manufactured by NIKON, DIGIMICRO MH-15M). The volume resistivity (Ω · cm) was used.

<Peel strength of electrode film>
After applying the mixture slurry on an aluminum foil using an applicator so that the basis weight per electrode is 20 mg / cm ² , the coating is applied at 120 ° C. ± 5 ° C. for 25 minutes in an electric oven. Was dried. Thereafter, two pieces were cut into a rectangle of 90 mm × 20 mm with the coating direction as the major axis. The peel strength was measured by a 180 ° peel test using a table type tensile tester (Strograph E3, manufactured by Toyo Seiki Seisaku-sho, Ltd.). Specifically, a 100 mm × 30 mm double-sided tape (No. 5000NS, manufactured by Nitoms Co., Ltd.) was stuck on a stainless steel plate, and the prepared battery electrode mixture layer was brought into close contact with the other surface of the double-sided tape. Peeling was performed while pulling upward from below at a constant speed (50 mm / min), and the average value of the stress at this time was taken as the peel strength.

<Rate characteristics of lithium ion secondary battery>
The laminated lithium secondary battery was set in a constant temperature room at 25 ° C., and charge / discharge measurement was performed using a charge / discharge device (SM-8, manufactured by Hokuto Denko Corporation). After performing constant-current constant-voltage charging (cut-off current 0.6 mA) at a charging end voltage of 4.3 V at a charging current of 12 mA (0.2 C), constant-current discharging is performed at a discharging end voltage of 3 V at a discharging current of 12 mA. went. After repeating this operation three times, a constant current constant voltage charge (cutoff current 0.6 mA) was performed at a charge end voltage of 4.3 V with a charge current of 12 mA (0.2 C), and a discharge current of 12 mA (0.2 C). And a constant current discharge was performed at 120 mA (2 C) until the discharge end voltage reached 3.0 V, and the discharge capacity was determined. The rate characteristic can be expressed by the ratio of 0.2 C discharge capacity to 2 C discharge capacity, and the following equation 1.
(Equation 2) Rate characteristics = 2C discharge capacity / 0.2C discharge capacity × 100 (%)

<High temperature storage characteristics of lithium ion secondary batteries>
The laminated lithium ion secondary battery was placed in a constant temperature room at 25 ° C., and charge / discharge measurement was performed using a charge / discharge device (SM-8, manufactured by Hokuto Denko Corporation). After performing constant-current constant-voltage charging (cut-off current 0.6 mA) at a charging end voltage of 4.3 V at a charging current of 12 mA (0.2 C), a discharging end voltage of 3 V at a discharging current of 12 mA (0.2 C). At a constant current. This operation was repeated three times, and the third discharge capacity was set to 0.2 C discharge capacity at 25 ° C. Thereafter, constant-current and constant-voltage charging (cut-off current: 0.6 mA) was performed at a charging end voltage of 4.3 V with a charging current of 12 mA (0.2 C), and stored in a constant temperature room set at 55 ° C. for 7 days. Finally, a constant current discharge was performed at a discharge current of 12 mA (0.2 C) at a discharge end voltage of 3 V to determine a discharge capacity. The high-temperature storage characteristics can be expressed by the ratio of the 0.2 C discharge capacity at 25 ° C. to the 0.2 C discharge capacity after storage at 55 ° C. for 7 days, and is expressed by the following formula 2.
(Equation 3) High-temperature storage characteristics = 0.2 C discharge capacity after storage at 55 ° C. for 7 days / 0.2 C discharge capacity at 25 ° C. × 100 (%)

<Example of CNT synthesis catalyst and CNT production>
The CNTs used in each of the following Examples and Comparative Examples were produced by the following methods.

Catalyst for CNT synthesis (A)
60 parts by mass of cobalt hydroxide, 138 parts by mass of magnesium acetate tetrahydrate and 16.2 parts by mass of manganese acetate are each weighed in a heat-resistant container and dried at 170 ± 5 ° C. for 1 hour using an electric oven. After evaporating the water, the SPEED dial was adjusted to 3 using a crusher (Wonder Crusher WC-3, manufactured by Osaka Chemical Co., Ltd.) and crushed for 1 minute. Then, using a grinder (Wonder Crusher WC-3, manufactured by Osaka Chemical Co., Ltd.), each of the pulverized powders was adjusted to a SPPED dial of 2 and mixed for 30 seconds to mix and prepare a catalyst precursor for CNT synthesis (A). Was prepared. Then, the catalyst precursor for CNT synthesis (A) is transferred to a heat-resistant container, and calcined in a muffle furnace (FO510, manufactured by Yamato Scientific Co., Ltd.) in an air atmosphere at 450 ± 5 ° C. for 30 minutes. The mixture was pulverized in a mortar to obtain a catalyst (A) for CNT synthesis.

Catalyst for CNT synthesis (B)
60 parts by mass of cobalt hydroxide, 138 parts by mass of magnesium acetate tetrahydrate, 16.2 parts by mass of manganese carbonate, and 4.0 parts by mass of Aerosil (AEOSIL (registered trademark) 200, manufactured by Nippon Aerosil Co., Ltd.) After being weighed in a container and dried for 1 hour at a temperature of 170 ± 5 ° C. using an electric oven to evaporate the water, SPEED of the SPEED was crushed using a crusher (Wonder Crusher WC-3, manufactured by Osaka Chemical Co., Ltd.). The dial was adjusted to 3 and crushed for 1 minute. Then, using a crusher (Wonder Crusher WC-3, manufactured by Osaka Chemical Co., Ltd.), each of the crushed powders was adjusted to a SPEED dial of 2 and mixed for 30 seconds to prepare a catalyst precursor for CNT synthesis (B). Was prepared. Then, the catalyst precursor for CNT synthesis (B) is transferred to a heat-resistant container, and calcined in a muffle furnace (FO510, manufactured by Yamato Scientific Co., Ltd.) in an air atmosphere at 450 ± 5 ° C. for 30 minutes. The mixture was pulverized in a mortar to obtain a CNT synthesis catalyst (B).

Catalyst for CNT synthesis (C)
1000 parts by mass of magnesium acetate tetrahydrate is weighed in a heat-resistant container, dried in an electric oven at an atmosphere temperature of 170 ± 5 ° C. for 6 hours, and then pulverized (sample mill KIIW-I, Co., Ltd.). (Dalton Co., Ltd.), and a 1 mm screen was attached and pulverized to obtain a dried and pulverized product of magnesium acetate. 45.8 parts of dried and ground magnesium acetate, 8.1 parts of manganese carbonate, 1.0 part of silicon oxide (SiO ₂ , manufactured by Nippon Aerosil Co., Ltd .: AEROSIL (registered trademark) 200), 200 parts of steel beads (bead diameter 2.0 mmφ) 200 The portion was charged into an SM sample bottle (manufactured by Sansho Co., Ltd.), and crushed and mixed for 30 minutes using a paint conditioner manufactured by Red Devil. Then, using a stainless sieve, the pulverized and mixed powder and steel beads (bead diameter: 2.0 mmφ) were separated to obtain a catalyst carrier for CNT synthesis. Thereafter, 30 parts by mass of cobalt (II) hydroxide was weighed into a heat-resistant container and dried at an atmosphere temperature of 170 ± 5 ° C. for 2 hours to obtain a cobalt composition containing CoHO ₂ . Thereafter, 54.9 parts by mass of the catalyst carrier for CNT synthesis and 29 parts by mass of the cobalt composition were charged into a pulverizer (Wonder Crusher WC-3, manufactured by Osaka Chemical Co., Ltd.), a standard lid was attached, and the SPEED dial was set to 2 parts. And crushed and mixed for 30 seconds to obtain a catalyst precursor for CNT synthesis. The catalyst precursor for CNT synthesis was transferred to a heat-resistant container, and calcined in a muffle furnace (FO510, manufactured by Yamato Scientific Co., Ltd.) for 30 minutes in an air atmosphere at 450 ± 5 ° C., followed by crushing in a mortar. A catalyst for CNT synthesis (C) was obtained.

Catalyst for CNT synthesis (D)
In the same manner as in Example 1 of JP-A-2015-123410, a CNT synthesis catalyst (D) was obtained.

<Synthesis of CNT (A)>
A quartz glass heat-resistant dish on which 2 g of the catalyst for synthesizing CNT (A) was sprayed was placed at the center of a horizontal reaction tube that can be pressurized and heated by an external heater and had an internal volume of 10 L. Evacuation was performed while injecting nitrogen gas, the air in the reaction tube was replaced with nitrogen gas, and the atmosphere in the horizontal reaction tube was set to an oxygen concentration of 1% by volume or less. Next, the mixture was heated by an external heater until the central temperature in the horizontal reaction tube reached 680 ° C. After the temperature reached 680 ° C., propane gas as a carbon source was introduced into the reaction tube at a flow rate of 2 L / min, and a contact reaction was performed for 1 hour. After the completion of the reaction, the gas in the reaction tube was replaced with nitrogen gas, the gas in the reaction tube was replaced with nitrogen gas, and the temperature of the reaction tube was cooled to 100 ° C. or less and taken out to obtain CNT (A). .

<Synthesis of CNT (B)>
CNT (B) was obtained in the same manner as in the synthesis of CNT (A) except that CNT synthesis catalyst (A) was changed to CNT synthesis catalyst (B).

<Synthesis of CNT (C)>
A quartz glass heat-resistant dish on which 1 g of the CNT synthesis catalyst (C) was sprayed was placed at the center of a horizontal reaction tube having a 10 L internal volume, which can be pressurized and heated by an external heater. Evacuation was performed while injecting nitrogen gas, the air in the reaction tube was replaced with nitrogen gas, and the atmosphere in the horizontal reaction tube was heated to 710 ° C. After the temperature reached 710 ° C., ethylene gas as a hydrocarbon was introduced into the reaction tube at a flow rate of 2 L / min, and a contact reaction was performed for 7 minutes. After completion of the reaction, the gas in the reaction tube was replaced with nitrogen gas, and the temperature of the reaction tube was cooled to 100 ° C. or less, and then taken out to obtain CNT (C).

<Synthesis of CNT (D)>
CNT (D) was obtained in the same manner as in the synthesis of CNT (C) except that the contact reaction time was changed from 7 minutes to 15 minutes.

<Synthesis of CNT (E)>
CNT (E) was obtained in the same manner as in the synthesis of CNT (C) except that the atmosphere temperature was changed from 710 ° C to 680 ° C.

<Synthesis of CNT (F)>
1000 g of CNT (E) was weighed into a carbon heat-resistant container. Thereafter, a carbon heat-resistant container containing CNTs was set in the furnace. Then, the inside of the furnace was evacuated to 1 Torr (133 Pa) or less, and the carbon heater was energized to raise the temperature of the inside of the furnace to 1000 ° C. Next, argon gas was introduced into the furnace to adjust the pressure in the furnace to 70 Torr (9.33 kPa), and then 1 L of argon gas per minute was introduced into the furnace. Thereafter, in addition to the argon gas, a chlorine gas is introduced, and the pressure in the furnace is adjusted to 90 Torr (11.99 kPa). After the pressure reaches the pressure, 0.3 L of chlorine gas per minute is supplied to the furnace. Was introduced. After holding for 1 hour in this state, energization was stopped, introduction of argon gas and chlorine gas was stopped, and vacuum cooling was performed. Finally, after performing vacuum cooling at a pressure of 1 Torr (133 Pa) or less for 12 hours, after confirming that the inside of the furnace has been cooled to room temperature, nitrogen gas is introduced into the furnace until the atmospheric pressure is reached. The conductive container was taken out to obtain CNT (F).

<Synthesis of CNT (G)>
10 kg of the CNT (E) was weighed into a 120 L heat-resistant container, and the heat-resistant container containing the CNT was placed in a furnace. Thereafter, nitrogen gas was introduced into the furnace, and the air in the furnace was discharged while maintaining the positive pressure. After the oxygen concentration in the furnace became 0.1% or less, the furnace was heated to 1600 ° C. over 30 hours. While maintaining the furnace temperature at 1600 ° C., chlorine gas was introduced at a rate of 50 L / min for 50 hours. Thereafter, nitrogen gas was introduced at a rate of 50 L / min, and the mixture was cooled while maintaining a positive pressure to obtain CNT (G).

<Synthesis of CNT (H)>
CNT (H) was obtained in the same manner as in Example 9 of JP-A-2015-123410 except that the catalyst for CNT synthesis (D) was used.

<Synthesis of CNT (I)>
1000 g of CNT (manufactured by KUMHO PETROCHEMICAL, 100T) was weighed in a carbon heat-resistant container. Thereafter, a carbon heat-resistant container containing CNTs was set in the furnace. Then, the inside of the furnace was evacuated to 1 Torr (133 Pa) or less, and the carbon heater was energized to raise the temperature of the inside of the furnace to 1000 ° C. Next, argon gas was introduced into the furnace to adjust the pressure in the furnace to 70 Torr (9.33 kPa), and then 1 L of argon gas per minute was introduced into the furnace. Thereafter, in addition to the argon gas, a chlorine gas is introduced, and the pressure in the furnace is adjusted to 90 Torr (11.99 kPa). After the pressure reaches the pressure, 0.3 L of chlorine gas per minute is supplied to the furnace. Was introduced. After holding for 1 hour in this state, energization was stopped, introduction of argon gas and chlorine gas was stopped, and vacuum cooling was performed. Finally, after performing vacuum cooling at a pressure of 1 Torr (133 Pa) or less for 12 hours, after confirming that the inside of the furnace has been cooled to room temperature, nitrogen gas is introduced into the furnace until the atmospheric pressure is reached. The conductive container was taken out to obtain CNT (I).

<Synthesis of CNT (J)>
CNT (J) was obtained in the same manner as for CNT (I) except that the internal temperature of the furnace was changed to 1050 ° C.

<Synthesis of CNT (K)>
10 kg of CNT (manufactured by KUMHO PETROCHEMICAL, 100T) was weighed into a 120 L heat-resistant container, and the heat-resistant container containing CNT was placed in a furnace. Thereafter, nitrogen gas was introduced into the furnace, and the air in the furnace was discharged while maintaining the positive pressure. After the oxygen concentration in the furnace became 0.1% or less, the furnace was heated to 1600 ° C. over 30 hours. While maintaining the furnace temperature at 1600 ° C., chlorine gas was introduced at a rate of 50 L / min for 50 hours. Thereafter, nitrogen gas was introduced at a rate of 50 L / min to cool while maintaining the positive pressure, to obtain CNT (K).

<Synthesis of CNT (L)>
10 kg of CNT (manufactured by KUMHO PETROCHEMICAL, 100T) was weighed into a 120 L heat-resistant container, and the heat-resistant container containing CNT was placed in a furnace. Thereafter, nitrogen gas was introduced into the furnace, and the air in the furnace was discharged while maintaining the positive pressure. After the oxygen concentration in the furnace became 0.1% or less, the furnace was heated to 1800 ° C. over 30 hours. While maintaining the furnace temperature at 1800 ° C., chlorine gas was introduced at a rate of 50 L / min for 50 hours. Thereafter, nitrogen gas was introduced at a rate of 50 L / min, and the mixture was cooled while maintaining a positive pressure to obtain CNT (L).

<Synthesis of CNT (M)>
10 kg of CNT (manufactured by KUMHO PETROCHEMICAL, 100T) was weighed into a 120 L heat-resistant container, and the heat-resistant container containing CNT was placed in a furnace. Thereafter, nitrogen gas was introduced into the furnace, and the air in the furnace was discharged while maintaining the positive pressure. After the oxygen concentration in the furnace became 0.1% or less, the furnace was heated to 2000 ° C. over 30 hours. While maintaining the furnace temperature at 2000 ° C., chlorine gas was introduced at a rate of 50 L / min for 50 hours. Thereafter, nitrogen gas was introduced at a rate of 50 L / min, and the mixture was cooled while maintaining a positive pressure to obtain CNT (M).

<Synthesis of CNT (N)>
1000 g of CNT (manufactured by KUMHO PETROCHEMICAL, 100T) was weighed in a 7 L carbon heat-resistant container, and the heat-resistant container containing CNT was placed in a furnace. Thereafter, nitrogen gas was introduced into the furnace, and the air in the furnace was discharged while maintaining the positive pressure. After the oxygen concentration in the furnace became 0.1% or less, the inside of the furnace was heated to 2900 ° C. over 30 hours, and then kept at 2900 ° C. for 3 hours. Thereafter, heating in the furnace was stopped, and the sample was cooled, and then CNT (N) was obtained.

<Preparation of negative electrode mixture slurry and negative electrode>
The negative electrode mixture slurry and the negative electrode used in each of the following Examples and Comparative Examples were produced by the following methods.

<Preparation of negative electrode mixture slurry>
49 parts by mass of artificial graphite (manufactured by Nippon Graphite Co., CGB-20) as a negative electrode active material, 25 parts by mass of an aqueous solution in which 2% by mass of carboxymethyl cellulose (manufactured by Daicel Chemical Industries, Ltd., # 1190) was dissolved (solid content: 0.5 Parts by mass) in a planetary mixer and kneaded. Then, 22 parts by mass of ion-exchanged water and 1 part by mass of styrene butadiene emulsion (TRD2001, manufactured by JSR Corporation) (0.5 part by mass as a solid content) were mixed. A negative electrode mixture slurry was obtained.
<Preparation of negative electrode>
After applying the above-mentioned negative electrode mixture slurry on a 20 μm thick copper foil serving as a current collector using an applicator, the slurry was dried in an electric oven at 120 ° C. ± 5 ° C. for 25 minutes and dried per unit area of the electrode. Was adjusted to be 12 mg / cm ² . Further, rolling treatment was performed by a roll press (3t hydraulic roll press, manufactured by Sank Metal Co., Ltd.) to produce a negative electrode having a mixture layer density of 1.5 g / cm ³ .

<Dispersant>
The structures of the triazine derivatives A to Q represented by the general formula (1) of the present invention are shown below. The method for producing the triazine derivatives A to Q represented by the general formula (1) used in the present invention is not particularly limited, and a known method can be applied. For example, a method described in JP-A-2004-217842 can be applied. The disclosures in the above publications are incorporated herein by reference.

Table 1 shows the CNTs used in the examples and comparative examples, the outer diameter of the CNTs, the standard deviation of the outer diameter (nm), the half width (°), the G / D ratio, the volume resistivity of the CNTs (Ω · cm), The CNT purity and CNT specific surface area (m ² / g) are shown.

Table 2 shows the dispersants used in Examples, Comparative Examples and Reference Examples.

(Example 1)
In a glass bottle (M-225, manufactured by Kashiyo Glass Co., Ltd.), 4.0 parts of CNT (A), 0.6 part of dispersant (E), 0.03 part of sodium carbonate, 75.4 parts of NMP and zirconia After 80 parts of beads (bead diameter 0.5 mmφ) were charged and subjected to a dispersion treatment for 6 hours using a paint conditioner manufactured by Red Devil Co., zirconia beads were separated to obtain a CNT dispersion liquid (A1).

(Examples 2 to 22), (Comparative Examples 1 to 6)
CNT dispersions (B1) to (Z1) in the same manner as in Example 1 except that CNT, CNT concentration, dispersant, dispersant addition amount, sodium carbonate addition amount, and dispersion treatment time listed in Table 3 were changed. I got

(Examples 23 to 35), (Reference Example 1)
CNT dispersions (J4 to J17) were obtained in the same manner as in Example 1 except that CNT, CNT concentration, dispersant, dispersant addition amount, sodium carbonate addition amount and dispersion treatment time listed in Table 4 were changed. Was.

  Table 5 shows the evaluation results of the CNT dispersions prepared in Examples 1 to 35, Comparative Examples 1 to 6, and Reference Example 1. The value obtained by dividing the viscosity of the CNT dispersion at 6 rpm by the viscosity of the CNT dispersion at 60 rpm was defined as a TI value.

(Example 36)
In a plastic container having a capacity of 150 cm ³ , 10.6 parts by mass of NMP in which 8% by mass of PVDF (manufactured by Solvey, Solef # 5130) was dissolved was weighed. Thereafter, 0.5 parts by mass of the CNT dispersion liquid (A1) was added, and the mixture was stirred at 2000 rpm for 30 seconds using a rotation / revolution mixer (Nawataro Nawataro, ARE-310, manufactured by Shinkey Corporation). Further, 6.5 parts by mass of the CNT dispersion liquid (A1) was added, and the mixture was stirred at 2000 rpm for 30 seconds using a rotation / revolution mixer (Awatori Naritaro, ARE-310, manufactured by Shinkey Corporation) to obtain a CNT resin composition. (A1) was obtained. After that, 55.1 parts by mass of a positive electrode active material (manufactured by BASF Toda Battery Materials GK, HED (registered trademark) NCM-111 1100) was added, and a rotation / revolution mixer (Nawataro Nawataro, manufactured by Shinky Corporation, ARE- Using 310), the mixture was stirred at 2000 rpm for 2.5 minutes. Finally, 2.3 parts by mass of NMP was added, and the mixture was stirred at 2,000 rpm for 2.5 minutes using a rotation / revolution mixer (Awatori Neritaro, ARE-310, manufactured by Shinky Corporation) to obtain a mixture slurry (A1). Was.

(Examples 37 to 62, Examples 64 to 70), (Comparative Examples 7 to 12), (Reference Example 2)
Except that the CNT dispersions listed in Table 6 were changed, the mixture slurry (B1) to (J17) were obtained in the same manner as in Example 37.

(Example 63)
In a plastic container having a capacity of 150 cm ³ , 10.6 parts by mass of NMP in which 8% by mass of PVDF (manufactured by Solvey, Solef # 5130) was dissolved was weighed. Thereafter, 0.5 parts by mass of the CNT dispersion (J8) was added, and the mixture was stirred for 30 seconds at 2000 rpm using a rotation / revolution mixer (Nawataro Nawataro, ARE-310, manufactured by Shinkey). Further, 4.6 parts by mass of the CNT dispersion liquid (J9) was added, and the mixture was stirred at 2000 rpm for 30 seconds using a rotation / revolution mixer (Awate Naritaro, ARE-310, manufactured by Shinkey Co.) to obtain a CNT resin composition. (J9) was obtained. After that, 55.1 parts by mass of a positive electrode active material (manufactured by BASF Toda Battery Materials GK, HED (registered trademark) NCM-111 1100) was added, and a rotation / revolution mixer (Nawataro Nawataro, manufactured by Shinky Corporation, ARE- Using 310), the mixture was stirred at 2000 rpm for 2.5 minutes. Finally, 4.3 parts by mass of NMP was added, and the mixture was stirred at 2,000 rpm for 2.5 minutes using a rotation / revolution mixer (Shinky's Awatori Neritaro, ARE-310) to obtain a mixture slurry (J9). Was.

(Example 71)
The mixture slurry (A1) was applied on an aluminum foil using an applicator so that the weight per unit of electrode was 20 mg / cm ^2, and then, in an electric oven at 120 ° C. ± 5 ° C. for 25 minutes. Then, the coating film was dried to obtain an electrode film (A1).

(Examples 72 to 105), (Comparative Examples 13 to 18), (Reference Example 3)
The electrode films (B1) to (J17) were obtained in the same manner as in Example 71 except that the mixture slurry shown in Table 7 was changed.

  Table 8 shows the evaluation results of the mixture slurries prepared in Examples 71 to 105 and Comparative Examples 13 to 18. The conductivity was evaluated as follows: when the volume resistivity (Ω · cm) of the electrode film is less than 5, ++++ (best), 5 or more but less than 10 is +++ (excellent), 10 or more and less than 20 is ++ (good), and 20 or more is less than 100. + (Acceptable) and 100 or more were regarded as-(impossible). Adhesion (N / cm) was evaluated as 1 or more as +++ (excellent), 0.5 or more and less than 1 as ++ (good), and 0.3 or more and less than 0.5 (impossible).

(Example 106)
The electrode film (A1) was rolled by a roll press (3t hydraulic roll press, manufactured by Sank Metal Co., Ltd.) to produce a positive electrode having a mixture layer density of 3.1 g / cm ³ .

(Examples 107 to 140), (Comparative Examples 19 to 24), (Reference Example 4)
A positive electrode was produced in the same manner as in Example 106 except that the electrode films listed in Table 9 were changed.

(Example 141)
The positive electrode (A1) and the negative electrode were punched into 45 mm × 40 mm and 50 mm × 45 mm, respectively, and the separator (porous polypropylene film) inserted therebetween was inserted into an aluminum laminate bag, and was placed in an electric oven at 60 ° C. for 1 hour. Dried. Thereafter, in a glove box filled with argon gas, LiPF ₆ was added at a concentration of 1 M to an electrolytic solution (a mixed solvent obtained by mixing ethylene carbonate, dimethyl carbonate, and diethyl carbonate at a ratio of 1: 1: 1 (volume ratio)). After injecting 2 mL of the dissolved non-aqueous electrolyte, the aluminum laminate was sealed and a laminated lithium ion secondary battery (A1) was produced.

(Examples 142 to 175), (Comparative Examples 25 to 30), (Reference Example 5)
Laminated lithium ion secondary batteries (B1) to (J17) were produced in the same manner except that the cathodes listed in Table 10 were changed.

  Table 11 shows the evaluation results of the laminated lithium secondary batteries manufactured in Examples 141 to 175, Comparative Examples 25 to 30, and Reference Example 5. The rate characteristics are ++ (excellent) when the rate characteristic is 80% or more, ++ (good) when the rate characteristic is 70% or more and less than 80%, + (acceptable) when the rate characteristic is 60% or more and less than 70%, and less than 60%. Those were marked-(impossible). The high-temperature storage characteristics are as follows: high-temperature storage characteristics of 80% or more are +++ (excellent); 70% or more and less than 80% are ++ (good); Those less than were rated-(impossible).

  Table 12 shows the evaluation results of the CNTs used in Examples 1 to 9, Examples 12 to 22, and Comparative Examples 1 to 6 and the laminated lithium ion secondary batteries manufactured using the CNT dispersion liquid. The overall evaluation is a five-point scale (5 (best) when the sum of the number of + in the evaluation of the rate characteristics and high-temperature storage characteristics of the laminated lithium-ion secondary battery is 6 or more: 5 (best), 5: 4 (excellent) In the rate characteristics or the high-temperature storage characteristics, 1 (impossible) in the rate characteristics or high-temperature storage characteristics was set to 3 (good), 4 to 3 (good), 3 to 2 (acceptable), and 2 or less. ).

In the above example, in the powder X-ray diffraction analysis, a peak is present at a diffraction angle 2θ = 25 ° ± 2 °, the half width of the peak is 2 ° to 6 °, and the Raman spectrum is 1560 to 1600 cm ^−1. When the maximum peak intensity in the range of G is 13 and the maximum peak intensity in the range of 1310 to 1350 cm ^-1 is D, the G / D ratio is 0.5 to 5.0. And a carbon nanotube dispersion liquid containing a triazine derivative. In the example, a lithium ion secondary battery having better rate characteristics than the comparative example was obtained. Therefore, it has been clarified that the present invention can provide a lithium secondary battery having conductivity that cannot be realized by the conventional carbon nanotube dispersion liquid.

Although the present invention has been described with reference to the exemplary embodiments, the present invention is not limited to the above. Various changes that can be understood by those skilled in the art can be made to the configuration and details of the present invention within the scope of the invention.

Claims (12)

A carbon nanotube dispersion liquid containing a carbon nanotube (A), a solvent (B), and a dispersant (C), wherein the carbon nanotube (A) has a diffraction angle 2θ = 25 ° ± 2 in powder X-ray diffraction analysis. And a half-width of the peak is 2 ° to 6 °, and the maximum peak intensity within the range of 1560 to 1600 cm ⁻¹ is Ra in the Raman spectrum, and the maximum peak intensity within the range of 1310 to 1350 cm ⁻¹ Where the maximum peak intensity is D, the G / D ratio is 0.5 to 5.0, and the dispersant (C) has an acidic functional group represented by the following general formula (1). A carbon nanotube dispersion liquid comprising:
[In the general formula (1), R ¹ represents a group represented by —X ¹ —Y ¹ . X ¹ represents an arylene group which may have a substituent, and Y ¹ represents a sulfo group, a carboxyl group or a phosphate group.
Q ¹ represents an -OH or -NH-R ^2. Q ² represents an -OH or -NH-R ^3. R ² and R ³ each independently represent an aryl group which may have a substituent, a heterocyclic group which may have a substituent, or a group represented by -X ¹ -Y ¹ . However, R ² and R ³ are not simultaneously -X ¹ -Y ¹ . ] BET specific surface area of the carbon nanotube (A) is a carbon nanotube dispersion liquid as claimed in claim 1, wherein it is 200~550m ² / g. When the maximum peak intensity in the range of 1560 to 1600 cm ^-1 is G and the maximum peak intensity in the range of 1310 to 1350 cm ^-1 is D in the Raman spectrum of the carbon nanotube (A), the G / D ratio is: The carbon nanotube dispersion according to claim 1, wherein the dispersion is 1.0 to 3.0.   The total amount of iron, cobalt, nickel, aluminum, magnesium, silica, manganese, and molybdenum in the carbon nanotube (A) is less than 0.5% by mass based on the entire carbon nanotube (A). The carbon nanotube dispersion liquid according to claim 1. The carbon nanotube dispersion liquid according to any one of claims 1 to 4, wherein the volume resistivity of the carbon nanotube (A) is 1.0 × 10 ^{-2 to} 2.5 × 10 ^-2 Ω · cm.   The carbon nanotube (A) has a peak at a diffraction angle 2θ = 25 ° ± 2 ° in the powder X-ray diffraction analysis, and the half width of the peak is 2 ° or more and less than 3 °. 6. The carbon nanotube dispersion according to any one of 1 to 5.   The carbon nanotube dispersion liquid according to any one of claims 1 to 6, wherein the average outer diameter of the carbon nanotube (A) is more than 3 nm and less than 16 nm.   The carbon nanotube dispersion according to any one of claims 1 to 7, wherein the solvent (B) is an amide organic solvent or water.   A carbon nanotube resin composition comprising the carbon nanotube dispersion liquid according to claim 1 and a binder (D).   A mixture slurry comprising the carbon nanotube resin composition according to claim 9 and an active material (E).   An electrode film (F) coated with the mixture slurry according to claim 10.   A lithium ion secondary battery comprising a positive electrode, a negative electrode, and an electrolyte containing lithium, wherein at least one of the positive electrode and the negative electrode is the electrode film according to claim 11, wherein the lithium ion secondary battery is a lithium ion secondary battery. battery.