Conductive material dispersion, method for producing slurry for non-aqueous secondary battery positive electrode, method for producing positive electrode for non-aqueous secondary battery, and method for producing non-aqueous secondary battery

Abstract

The present invention provides a technology which enables a secondary battery to exhibit excellent output characteristics and other characteristics. According to the present invention, a conductive material dispersion liquid that contains a conductive material, a dispersant and a solvent is used during the production of a secondary battery. The conductive material is composed of carbon nanotubes that have a specific surface area of from 800 m2 / g to 1,300 m2 / g; the volume average particle diameter (D90) of the carbon nanotubes in the conductive material dispersion liquid is 50 μm or less; and the dispersant is composed of a hydrogenated acrylonitrile-butadiene copolymer that has a weight average molecular weight of 200,000 or less.

Description

[Technical Field]

[0001] The present invention relates to a conductive material dispersion, a method for producing a slurry for a positive electrode of a non-aqueous secondary battery, a method for producing a positive electrode for a non-aqueous secondary battery, and a method for producing a non-aqueous secondary battery. [Background technology]

[0002] Non-aqueous secondary batteries such as lithium ion secondary batteries (hereinafter simply referred to as "secondary batteries") are small, lightweight, have high energy density, and can be repeatedly charged and discharged, and are therefore used in a wide range of applications. Therefore, in recent years, improvements to battery components such as electrodes have been studied with the aim of further improving the performance of secondary batteries.

[0003] A positive electrode for a secondary battery typically includes a current collector and a positive electrode composite layer formed on the current collector. The positive electrode composite layer is formed, for example, using a slurry for a secondary battery positive electrode, which is obtained by dispersing a positive electrode active material, a conductive material, and a binder in a dispersion medium. In recent years, attempts have been made to improve the slurry for the positive electrode of secondary batteries in order to achieve further improvements in the performance of secondary batteries.

[0004] For example, Patent Document 1 proposes a slurry for secondary battery electrodes containing an electrode active material and a carbon nanotube dispersion. The carbon nanotube dispersion described in Patent Document 1 contains carbon nanotubes, a binder, and a dispersion medium, the binder contains a polymer (A) containing a predetermined structural unit, the ratio of the binder to the total solid content of the carbon nanotube dispersion is a predetermined value or less, and the rate of change in viscosity of the carbon nanotube dispersion before and after leaving it for one week is within a predetermined range. [Prior art documents] [Patent documents]

[0005] [Patent Document 1] International Publication No. 2019 / 181869 Summary of the Invention [Problem to be solved by the invention]

[0006] However, secondary batteries produced using conventional slurries for secondary battery positive electrodes such as those described in Patent Document 1 have room for further improvement in terms of electrical characteristics such as output characteristics and cycle characteristics.

[0007] Therefore, an object of the present invention is to provide a method for producing a slurry for a non-aqueous secondary battery positive electrode that can enable a secondary battery to exhibit excellent output characteristics and cycle characteristics, and a conductive material dispersion that can be suitably used for producing the slurry for a secondary battery positive electrode. Another object of the present invention is to provide a method for producing a positive electrode for a non-aqueous secondary battery that allows the secondary battery to exhibit excellent output characteristics and cycle characteristics. Another object of the present invention is to provide a method for producing a non-aqueous secondary battery that has excellent output characteristics and cycle characteristics. [Means for solving the problem]

[0008] The present inventors have focused on the fact that the use of carbon nanotubes (hereinafter also referred to as "CNTs") with a large specific surface area, such as single-walled carbon nanotubes, as a conductive material for secondary batteries can improve the output characteristics of the batteries. However, according to the inventors' investigations, when CNTs with a large specific surface area are used to prepare a slurry for a secondary battery positive electrode, the spinnability of the resulting slurry for a secondary battery positive electrode is reduced. Furthermore, because it is difficult to uniformly apply such a slurry for a positive electrode to a current collector, the positive electrode composite layer formed by applying the positive electrode slurry has increased surface roughness, which causes a decrease in the cycle characteristics of the secondary battery. Therefore, the present inventors conducted further research and discovered that the above problems can be solved by using a low-molecular-weight hydrogenated acrylonitrile-butadiene copolymer (H-NBR) in combination with CNTs with a large specific surface area. Based on these findings, the present invention was completed.

[0009] That is, the present invention has an object to advantageously solve the above-mentioned problems, and the conductive material dispersion of the present invention is a conductive material dispersion containing a conductive material, a dispersant, and a solvent, wherein the conductive material has a specific surface area of ​​800 m 2 / g or more 1300m 2 The carbon nanotubes in the conductive material dispersion liquid have a volume average particle diameter (D90) of 50 μm or less, the dispersant is a hydrogenated acrylonitrile-butadiene copolymer, and the weight average molecular weight of the hydrogenated acrylonitrile-butadiene copolymer is 200,000 or less. 2 / g or more 1300m 2 / g or less and a volume average particle size (D90) in the conductive material dispersion of 50 μm or less, a hydrogenated acrylonitrile-butadiene copolymer having a weight average molecular weight of 200,000 or less as a dispersant, and a solvent, the conductive material dispersion can provide excellent slurry stability and coating uniformity to a slurry for a secondary battery positive electrode.

[0010] In this specification, the "volume average particle diameter (D90) of CNTs in a conductive material dispersion" refers to the particle diameter of CNTs in a conductive material dispersion when the cumulative volume calculated from the smallest diameter side is 90% in the particle size distribution (volume basis) measured by laser diffraction. In the present invention, the "specific surface area," the "volume average particle diameter (D90) of CNTs in a conductive material dispersion," and the "weight average molecular weight" can each be determined by the methods described in the examples of this specification.

[0011] Here, in the conductive material dispersion of the present invention, the iodine value of the hydrogenated acrylonitrile-butadiene copolymer is preferably 25 mg / 100 mg or less. When the iodine value of the hydrogenated acrylonitrile-butadiene copolymer is 25 mg / 100 mg or less, the dispersibility of the conductive material in the conductive material dispersion can be improved. Furthermore, by using the conductive material dispersion, the slurry stability of the slurry for a secondary battery positive electrode can be improved, and the cycle characteristics of a secondary battery produced using the slurry for a secondary battery positive electrode can be improved. In the present invention, the "iodine value" can be determined by the method described in the examples of this specification.

[0012] In addition, in the conductive material dispersion of the present invention, the content of the dispersant in the conductive material dispersion is preferably 50 parts by mass or more and 400 parts by mass or less per 100 parts by mass of the conductive material. When the content of the dispersant in the conductive material dispersion is within the above range, both the slurry stability and coating uniformity of the slurry for a secondary battery positive electrode can be further improved.

[0013] Furthermore, the present invention aims to advantageously solve the above-mentioned problems, and the method for producing a slurry for a non-aqueous secondary battery positive electrode of the present invention is characterized in that the slurry for a non-aqueous secondary battery positive electrode is obtained by mixing a positive electrode active material, a binder, and any of the above-mentioned conductive material dispersions. In this way, by mixing the positive electrode active material, the binder, and the conductive material dispersion of the present invention, a slurry for a secondary battery positive electrode excellent in slurry stability and coating uniformity can be efficiently produced.

[0014] In the method for producing a slurry for a non-aqueous secondary battery positive electrode of the present invention, the content of the conductive material in the slurry for a non-aqueous secondary battery positive electrode is preferably less than 0.1 parts by mass per 100 parts by mass of the positive electrode active material. If the content of the conductive material in the slurry for a secondary battery positive electrode is less than 0.1 parts by mass per 100 parts by mass of the positive electrode active material, the slurry stability and coating uniformity of the obtained slurry for a secondary battery positive electrode can be further improved.

[0015] In the method for producing a slurry for a non-aqueous secondary battery positive electrode of the present invention, the content of the binder in the slurry for a non-aqueous secondary battery positive electrode is preferably 0.1 parts by mass or more and 6 parts by mass or less per 100 parts by mass of the positive electrode active material. If the content of the binder in the slurry for a secondary battery positive electrode is within the above range, in a positive electrode produced using the slurry for a secondary battery positive electrode, the adhesion between the positive electrode mixture layer and the current collector can be improved, and the resistance of the secondary battery can be kept low.

[0016] The present invention aims to advantageously solve the above-mentioned problems, and is characterized in that the method for manufacturing a positive electrode for a nonaqueous secondary battery of the present invention includes forming a positive electrode mixture layer using the slurry for a positive electrode for a nonaqueous secondary battery obtained by the above-mentioned method. By forming a positive electrode mixture layer using the slurry for a positive electrode for a nonaqueous secondary battery obtained by the above-mentioned method, a positive electrode for a secondary battery that can exhibit excellent output characteristics and cycle characteristics can be manufactured.

[0017] The present invention aims to advantageously solve the above-mentioned problems, and the method for producing a nonaqueous secondary battery of the present invention is characterized by using a positive electrode for a nonaqueous secondary battery obtained by the above-mentioned method for producing a positive electrode for a nonaqueous secondary battery. In this way, by using the positive electrode for a nonaqueous secondary battery obtained by the above-mentioned method, a secondary battery excellent in output characteristics and cycle characteristics can be produced. [Effects of the Invention]

[0018] According to the present invention, it is possible to provide a method for producing a slurry for a positive electrode of a secondary battery, which can enable the secondary battery to exhibit excellent output characteristics and cycle characteristics, and a conductive material dispersion liquid that can be suitably used for producing the slurry for a positive electrode of the secondary battery. Furthermore, according to the present invention, it is possible to provide a method for producing a positive electrode for a secondary battery that allows the secondary battery to exhibit excellent output characteristics and cycle characteristics. Furthermore, the present invention can provide a method for manufacturing a secondary battery that is excellent in output characteristics and cycle characteristics. DETAILED DESCRIPTION OF THE INVENTION

[0019] Hereinafter, embodiments of the present invention will be described in detail. Here, the conductive material dispersion of the present invention can be used when preparing a slurry for a secondary battery positive electrode. Also, the method for producing a slurry for a secondary battery positive electrode of the present invention is produced using the conductive material dispersion of the present invention. Furthermore, the method for producing a positive electrode for a secondary battery of the present invention uses a slurry for a secondary battery positive electrode obtained by the method for producing a positive electrode for a secondary battery of the present invention. And, the method for producing a secondary battery of the present invention uses a positive electrode obtained by the method for producing a positive electrode for a secondary battery of the present invention.

[0020] (Conductive material dispersion) The conductive material dispersion of the present invention is required to contain a conductive material, a dispersant, and a solvent. The conductive material dispersion of the present invention may further contain an additive in addition to the above components. In this specification, the "conductive material dispersion" usually does not contain a positive electrode active material. Since the conductive material dispersion of the present invention contains a conductive material, a dispersant, and a solvent, which will be specifically described below, the use of the conductive material dispersion of the present invention makes it possible to prepare a slurry for a secondary battery positive electrode that is excellent in slurry stability and coating uniformity.The use of the slurry for a secondary battery positive electrode makes it possible to produce a positive electrode that can exhibit excellent output characteristics and cycle characteristics in a secondary battery.

[0021] <Conductive material> The conductive material is used to ensure electrical contact between the positive electrode active materials in the positive electrode mixture layer. The conductive material used in the conductive material dispersion of the present invention can be single-walled CNTs and / or multi-walled CNTs, but single-walled to five-walled CNTs are preferred, and single-walled CNTs are more preferred. Furthermore, the CNTs may be surface-treated with a strong acid such as nitric acid or sulfuric acid.

[0022] [Specific surface area of ​​CNT] The specific surface area of ​​CNT is 800m 2 / g or more, and 850m 2 / g or more, and 1300m2 / g or less, and 1250m 2 When the specific surface area of ​​the CNTs is within the above range, a good conductive path can be formed in the positive electrode mixture layer while ensuring the dispersibility of the conductive material, and therefore the coating uniformity of the slurry for a secondary battery positive electrode and the output characteristics of the secondary battery can be further improved.

[0023] [Volume average particle size (D90) of CNTs in conductive material dispersion] The volume average particle diameter (D90) of the CNTs in the conductive material dispersion must be 50 μm or less, preferably 45 μm or less, more preferably 40 μm or less, and even more preferably 30 μm or less. If the volume average particle diameter (D90) of the CNTs in the conductive material dispersion is 50 μm or less, the dispersibility of the conductive material (CNTs) in the conductive material dispersion can be further improved. Therefore, by using this conductive material dispersion, the slurry stability of the slurry for secondary battery positive electrodes can be further improved, and the cycle characteristics of secondary batteries produced using this slurry for secondary battery positive electrodes can be further improved. The volume average particle size (D90) of the CNTs in the conductive material dispersion can be adjusted appropriately by changing the mixing conditions when preparing the conductive material dispersion.

[0024] Here, the method for producing the CNTs used as the conductive material in the present invention is not particularly limited, and they can be produced using known CNT production methods such as arc discharge, laser ablation, and chemical vapor deposition (CVD).

[0025] <Dispersant> The dispersant is used to disperse the conductive material contained in the conductive material dispersion. In the present invention, a hydrogenated acrylonitrile-butadiene copolymer is used as the dispersant used in the conductive material dispersion. The hydrogenated acrylonitrile-butadiene copolymer is a hydrogenated product obtained by hydrogenating some or all of the carbon-carbon unsaturated bonds in the main chain and side chains derived from the conjugated diene monomer of the acrylonitrile-butadiene copolymer. The conductive material dispersion of the present invention uses a hydrogenated acrylonitrile-butadiene copolymer as a dispersant. Therefore, by using the conductive material dispersion, the surface roughness of the positive electrode mixture layer can be reduced, and the cycle characteristics of the secondary battery can be improved.

[0026] [Properties of hydrogenated acrylonitrile-butadiene copolymer] [Weight average molecular weight] The hydrogenated acrylonitrile-butadiene copolymer used in the present invention must have a weight average molecular weight of not more than 200,000, preferably not more than 100,000, more preferably not more than 80,000, and even more preferably not more than 60,000. By using a low-molecular-weight hydrogenated acrylonitrile-butadiene copolymer having a weight average molecular weight of not more than 200,000, the slurry for the positive electrode of a secondary battery can exhibit both excellent slurry stability and coating uniformity. The weight average molecular weight of the hydrogenated acrylonitrile-butadiene copolymer can be adjusted appropriately by, for example, changing the composition of the hydrogenated acrylonitrile-butadiene copolymer or the hydrogenation conditions.

[0027] [Iodine value] Furthermore, the hydrogenated acrylonitrile-butadiene copolymer used in the present invention preferably has an iodine value of 25 mg / 100 mg or less, more preferably 23 mg / 100 mg or less, and even more preferably 20 mg / 100 mg or less. When the iodine value of the hydrogenated acrylonitrile-butadiene copolymer is 25 mg / 100 mg or less, the dispersibility of the conductive material in the conductive material dispersion can be improved. Furthermore, by using the conductive material dispersion, the slurry stability of the slurry for secondary battery positive electrodes can be improved, and the cycle characteristics of secondary batteries produced using the slurry for secondary battery positive electrodes can be improved. Here, the iodine value of the hydrogenated acrylonitrile-butadiene copolymer may be, for example, 3 mg / mg or more. The iodine value of the hydrogenated acrylonitrile-butadiene copolymer can be adjusted by changing the hydrogenation reaction conditions when preparing the hydrogenated acrylonitrile-butadiene copolymer.

[0028] [Structural unit] The hydrogenated acrylonitrile-butadiene copolymer used in the present invention contains a nitrile group-containing monomer unit and a linear alkylene structural unit having 4 or more carbon atoms, and optionally further contains other monomer units such as the nitrile group-containing monomer unit and the linear alkylene structural unit having 4 or more carbon atoms.

[0029] -Nitrile group-containing monomer unit- In the present invention, the nitrile group-containing monomer unit is a repeating unit derived from a nitrile group-containing monomer. Here, examples of nitrile group-containing monomers capable of forming nitrile group-containing monomer units include α,β-ethylenically unsaturated nitrile monomers. Specifically, the α,β-ethylenically unsaturated nitrile monomer is not particularly limited as long as it is an α,β-ethylenically unsaturated compound having a nitrile group, and examples thereof include acrylonitrile; α-halogenoacrylonitriles such as α-chloroacrylonitrile and α-bromoacrylonitrile; and α-alkylacrylonitriles such as methacrylonitrile and α-ethylacrylonitrile. Among these, acrylonitrile is preferred. These may be used alone or in combination of two or more.

[0030] The content of the nitrile group-containing monomer units in the hydrogenated acrylonitrile-butadiene copolymer is preferably 20% by mass or more, more preferably 23% by mass or more, and even more preferably 25% by mass or more, and is preferably 50% by mass or less, and more preferably 45% by mass or less, when the total repeating units of the hydrogenated acrylonitrile-butadiene copolymer (the sum of monomer units and structural units) is taken as 100% by mass. When the content of the nitrile group-containing monomer units in the hydrogenated acrylonitrile-butadiene copolymer is equal to or greater than the above-mentioned lower limit, the cycle characteristics of a positive electrode for a secondary battery produced using the conductive material dispersion of the present invention can be improved. Furthermore, when the content of the nitrile group-containing monomer units in the hydrogenated acrylonitrile-butadiene copolymer is equal to or less than the above-mentioned upper limit, the flexibility of the electrode can be further improved.

[0031] -Straight-chain alkylene structural unit with 4 or more carbon atoms- In the present invention, the linear alkylene structural unit having 4 or more carbon atoms is a unit represented by the general formula: -C n H 2n It is a repeating unit composed of an alkylene structure represented by - (where n is an integer of 4 or more).

[0032] Here, the method for introducing an alkylene structural unit having 4 or more carbon atoms is not particularly limited, but may be, for example, the following methods (1) and (2): (1) A method in which a polymer is prepared from a monomer composition containing a conjugated diene monomer, and the polymer is hydrogenated to convert the conjugated diene monomer units into alkylene structural units. (2) A method for preparing a polymer from a monomer composition containing a 1-olefin monomer having 4 or more carbon atoms Among these, method (1) is preferred because it is easy to produce the polymer.

[0033] Here, examples of the conjugated diene monomer include conjugated diene compounds having 4 or more carbon atoms, such as 1,3-butadiene, isoprene, 2,3-dimethyl-1,3-butadiene, and 1,3-pentadiene. Among these, 1,3-butadiene is preferred. That is, the linear alkylene structural unit having 4 or more carbon atoms is preferably a structural unit (conjugated diene hydride unit) obtained by hydrogenating a conjugated diene monomer unit, and more preferably a structural unit (1,3-butadiene hydride unit) obtained by hydrogenating a 1,3-butadiene monomer unit. The selective hydrogenation of the conjugated diene monomer units can be carried out by a known method such as an oil phase hydrogenation method or an aqueous phase hydrogenation method. Examples of the 1-olefin monomer having 4 or more carbon atoms include 1-butene and 1-hexene. These can be used alone or in combination of two or more.

[0034] The content of linear alkylene structural units having 4 or more carbon atoms in the hydrogenated acrylonitrile-butadiene copolymer is preferably 20% by mass or more, more preferably 23% by mass or more, even more preferably 25% by mass or more, and preferably 70% by mass or less, more preferably 50% by mass or less, even more preferably 45% by mass or less, and particularly preferably 40% by mass or less, when the total repeating units (total of monomer units and structural units) in the hydrogenated acrylonitrile-butadiene copolymer is taken as 100% by mass. When the content of linear alkylene structural units having 4 or more carbon atoms in the hydrogenated acrylonitrile-butadiene copolymer is equal to or greater than the above-mentioned lower limit, a positive electrode having further improved output characteristics can be produced by using a slurry for a secondary battery positive electrode containing a conductive material dispersion. Furthermore, when the content ratio of the linear alkylene structural unit having 4 or more carbon atoms in the hydrogenated acrylonitrile-butadiene copolymer is equal to or less than the above upper limit, the solubility of the hydrogenated acrylonitrile-butadiene copolymer in solvents such as N-methyl-2-methylpyrrolidone (NMP) is ensured, and therefore the conductive material can be well dispersed in the conductive material dispersion liquid.

[0035] Examples of other monomer units include aromatic vinyl monomer units and hydrophilic group-containing monomer units.

[0036] -Aromatic vinyl monomer unit- In the present invention, the aromatic vinyl monomer unit is a repeating unit derived from an aromatic vinyl monomer. Examples of aromatic vinyl monomers that can form the aromatic vinyl monomer unit include styrene, α-methylstyrene, vinyltoluene, and divinylbenzene. Among these, styrene is preferred. These may be used alone or in combination of two or more.

[0037] The content of aromatic vinyl monomer units in the hydrogenated acrylonitrile-butadiene copolymer is preferably 20% by mass or more, more preferably 30% by mass or more, and preferably 60% by mass or less, and more preferably 50% by mass or less, when the total repeating units (the sum of monomer units and structural units) in the hydrogenated acrylonitrile-butadiene copolymer is taken as 100% by mass. If the content of aromatic vinyl monomer units in the hydrogenated acrylonitrile-butadiene copolymer is within the above range, the dispersibility of the conductive material in the conductive material dispersion is further improved. Therefore, the use of this conductive material dispersion can further improve the slurry stability of the slurry for secondary battery positive electrodes, and the use of this slurry for secondary battery positive electrodes can further improve the cycle characteristics of the secondary battery.

[0038] -Hydrophilic group-containing monomer unit- In the present invention, the hydrophilic group-containing monomer unit refers to a repeating unit derived from a hydrophilic group-containing monomer unit. Here, examples of the hydrophilic group-containing monomer that can form the hydrophilic group-containing monomer unit include polymerizable monomers having a hydrophilic group. Specifically, examples of the hydrophilic group-containing monomer include monomers having an acidic group-containing monomer unit, a hydroxyl group-containing monomer unit, and salts thereof. Examples of the acidic group-containing monomer unit include a carboxylic acid group, a sulfonic acid group, a phosphate group, and the like.

[0039] Examples of the monomer having a carboxylic acid group include monocarboxylic acids and derivatives thereof, dicarboxylic acids and acid anhydrides thereof, and derivatives thereof. Examples of the monocarboxylic acid include acrylic acid, methacrylic acid, and crotonic acid. Examples of the monocarboxylic acid derivatives include 2-ethylacrylic acid, isocrotonic acid, α-acetoxyacrylic acid, β-trans-aryloxyacrylic acid, α-chloro-β-E-methoxyacrylic acid, and β-diaminoacrylic acid. Examples of dicarboxylic acids include maleic acid, fumaric acid, and itaconic acid. Examples of the acid anhydrides of dicarboxylic acids include maleic anhydride, acrylic anhydride, methyl maleic anhydride, and dimethyl maleic anhydride. Examples of dicarboxylic acid derivatives include maleic acid esters such as methylmaleic acid, dimethylmaleic acid, phenylmaleic acid, chloromaleic acid, dichloromaleic acid, fluoromaleic acid, methylallyl maleate, diphenyl maleate, noryl maleate, decyl maleate, dodecyl maleate, octadecyl maleate, and fluoroalkyl maleates. Furthermore, as the monomer having a carboxylic acid group, an acid anhydride which generates a carboxyl group upon hydrolysis can also be used. Other examples include monoesters and diesters of α,β-ethylenically unsaturated polycarboxylic acids such as maleic acid monoester, diethyl maleate, monobutyl maleate, dibutyl maleate, monoethyl fumarate, diethyl fumarate, monobutyl fumarate, dibutyl fumarate, monocyclohexyl fumarate, dicyclohexyl fumarate, monoethyl itaconate, diethyl itaconate, monobutyl itaconate, and dibutyl itaconate.

[0040] Examples of the monomer having a sulfonic acid group include vinyl sulfonic acid, methyl vinyl sulfonic acid, (meth)acrylic acid sulfonic acid, styrene sulfonic acid, (meth)acrylic acid-2-ethyl sulfonate, 2-acrylamido-2-methylpropanesulfonic acid, and 3-allyloxy-2-hydroxypropanesulfonic acid. In the present invention, "(meth)acrylic" means acrylic and / or methacrylic.

[0041] Examples of the monomer having a phosphate group include 2-(meth)acryloyloxyethyl phosphate, methyl-2-(meth)acryloyloxyethyl phosphate, and ethyl-(meth)acryloyloxyethyl phosphate. In the present invention, "(meth)acryloyl" means acryloyl and / or methacryloyl.

[0042] Examples of the monomer having a hydroxyl group include ethylenically unsaturated alcohols such as (meth)allyl alcohol, 3-butene-1-ol, and 5-hexene-1-ol; alkanol esters of ethylenically unsaturated carboxylic acids such as 2-hydroxyethyl acrylate, 2-hydroxypropyl acrylate, 2-hydroxyethyl methacrylate, 2-hydroxypropyl methacrylate, di-2-hydroxyethyl maleate, di-4-hydroxybutyl maleate, and di-2-hydroxypropyl itaconate; and esters of ethylenically unsaturated carboxylic acids such as 2-hydroxyethyl acrylate, 2-hydroxypropyl acrylate, 2-hydroxyethyl methacrylate, di-4-hydroxybutyl maleate, and di-2-hydroxypropyl itaconate; 1 -COO-(C q H 2q O) p -H (wherein p is an integer of 2 to 9, q is an integer of 2 to 4, R 1represents hydrogen or a methyl group.) and esters of (meth)acrylic acid; mono(meth)acrylic acid esters of dihydroxy esters of dicarboxylic acids such as 2-hydroxyethyl-2'-(meth)acryloyloxyphthalate and 2-hydroxyethyl-2'-(meth)acryloyloxysuccinate; vinyl ethers such as 2-hydroxyethyl vinyl ether and 2-hydroxypropyl vinyl ether; alkylene glycols such as (meth)allyl-2-hydroxyethyl ether, (meth)allyl-2-hydroxypropyl ether, (meth)allyl-3-hydroxypropyl ether, (meth)allyl-2-hydroxybutyl ether, (meth)allyl-3-hydroxybutyl ether, (meth)allyl-4-hydroxybutyl ether, and (meth)allyl-6-hydroxyhexyl ether. Examples of suitable alkylene glycol (meth)allyl ethers include mono(meth)allyl ethers of glycerol; polyoxyalkylene glycol (meth)monoallyl ethers such as diethylene glycol mono(meth)allyl ether and dipropylene glycol mono(meth)allyl ether; mono(meth)allyl ethers of halogen- and hydroxy-substituted (poly)alkylene glycols such as glycerol mono(meth)allyl ether, (meth)allyl-2-chloro-3-hydroxypropyl ether, and (meth)allyl-2-hydroxy-3-chloropropyl ether; mono(meth)allyl ethers of polyhydric phenols such as eugenol and isoeugenol and halogen-substituted derivatives thereof; and (meth)allyl thioethers of alkylene glycols such as (meth)allyl-2-hydroxyethyl thioether and (meth)allyl-2-hydroxypropyl thioether. Among these, monomers having a carboxylic acid group are preferred, and methacrylic acid is more preferred. These may be used alone or in combination of two or more.

[0043] The content of the hydrophilic group-containing monomer units in the hydrogenated acrylonitrile-butadiene copolymer is preferably 0.1% by mass or more, more preferably 1% by mass or more, and preferably 10% by mass or less, and more preferably 8% by mass or less, when the total repeating units (the sum of the monomer units and the structural units) in the hydrogenated acrylonitrile-butadiene copolymer is taken as 100% by mass. When the content of the hydrophilic group-containing monomer units in the hydrogenated acrylonitrile-butadiene copolymer is equal to or greater than the above-mentioned lower limit, the flexibility of the secondary battery positive electrode produced using the slurry for the secondary battery positive electrode containing the conductive material dispersion of the present invention can be improved. Furthermore, when the content of the hydrophilic group-containing monomer units in the hydrogenated acrylonitrile-butadiene copolymer is equal to or less than the above-mentioned upper limit, the battery resistance of the secondary battery produced using the slurry for the secondary battery positive electrode containing the conductive material dispersion of the present invention can be reduced.

[0044] [Method of producing hydrogenated acrylonitrile-butadiene copolymer] The method for producing the above-mentioned hydrogenated acrylonitrile-butadiene copolymer is not particularly limited, and for example, the copolymer can be produced by polymerizing a monomer composition containing the above-mentioned monomers optionally in the presence of a molecular weight modifier and a terminator, and then subjecting the obtained copolymer to a hydrogenation reaction.

[0045] The polymerization method for the acrylonitrile-butadiene copolymer is not particularly limited, and any of solution polymerization, suspension polymerization, bulk polymerization, emulsion polymerization, etc. Also, any of ionic polymerization, radical polymerization, living radical polymerization, etc. can be used as the polymerization reaction.

[0046] Furthermore, commonly used emulsifiers, dispersants, polymerization initiators, polymerization aids, molecular weight modifiers, and terminators can be used in the polymerization, and the amounts used can be the same as those used in the polymerization. The solution containing the hydrogenated acrylonitrile-butadiene copolymer and the polymerization solvent obtained by polymerizing the monomer composition can be used as is to prepare a conductive material dispersion. Furthermore, the hydrogenation reaction method is not particularly limited, and can be performed according to a known method.

[0047] [Dispersant content] The content of the dispersant (i.e., hydrogenated acrylonitrile-butadiene copolymer) in the conductive material dispersion is preferably 50 parts by mass or more, more preferably 100 parts by mass or more, and preferably 400 parts by mass or less, and more preferably 300 parts by mass or less, per 100 parts by mass of the conductive material. When the content of the dispersant in the conductive material dispersion is equal to or greater than the above-mentioned lower limit, both the slurry stability and coating uniformity of the slurry for a secondary battery positive electrode obtained using the conductive material dispersion can be further improved. Furthermore, when the content of the dispersant in the conductive material dispersion is equal to or less than the above-mentioned upper limit, an increase in the resistance of a secondary battery produced using the slurry for a secondary battery positive electrode containing the conductive material dispersion can be suppressed, thereby improving the output characteristics of the secondary battery.

[0048] 〔solvent〕 The solvent contained in the conductive material dispersion liquid is not particularly limited, and for example, an organic solvent can be used. Examples of organic solvents include cyclic aliphatic hydrocarbons such as cyclopentane and cyclohexane; aromatic hydrocarbons such as toluene, xylene, and ethylbenzene; ketones such as acetone, ethyl methyl ketone, diisopropyl ketone, cyclohexanone, methylcyclohexane, and ethylcyclohexane; chlorinated aliphatic hydrocarbons such as methylene chloride, chloroform, and carbon tetrachloride; esters such as ethyl acetate, butyl acetate, γ-butyrolactone, and ε-caprolactone; acylonitriles such as acetonitrile and propionitrile; ethers such as tetrahydrofuran and ethylene glycol diethyl ether; alcohols such as methanol, ethanol, isopropanol, ethylene glycol, and ethylene glycol monomethyl ether; and amides such as N-methyl-2-methylpyrrolidone (NMP) and N,N-dimethylformamide. Among these, NMP is preferred. These can be used alone or in combination to form a mixed solvent.

[0049] <Additives> The additives that may be optionally contained in the conductive material dispersion of the present invention are not particularly limited and include, for example, a surface tension modifier, a viscosity modifier, a reinforcing material, etc. These additives may be used alone or in combination of two or more.

[0050] <Preparation of Conductive Material Dispersion> The conductive material dispersion of the present invention can be prepared by mixing the above-mentioned conductive material, dispersant, solvent, and optional additives by a known method. Specifically, the conductive material dispersion can be prepared by mixing the above-mentioned components using a mixer such as a disper, ball mill, sand mill, bead mill, pigment disperser, crusher, ultrasonic disperser, homogenizer, planetary mixer, or Filmix. The solid content concentration of the conductive material dispersion can be, for example, 0.5% by mass or more and 25% by mass or less. Then, the obtained conductive material dispersion can be suitably used, for example, in the method for manufacturing a slurry for a secondary battery positive electrode of the present invention described below.

[0051] (Method for Manufacturing Slurry for Secondary Battery Positive Electrode) In the method for manufacturing a slurry for a secondary battery positive electrode of the present invention, a positive electrode active material, a binder, and the conductive material dispersion of the present invention described above are mixed to obtain a slurry for a secondary battery positive electrode. In addition, in the method for manufacturing a slurry for a secondary battery positive electrode of the present invention, other components may be further mixed in addition to the above-described components. And according to the manufacturing method of the present invention, by using the conductive material dispersion of the present invention, a slurry for a secondary battery positive electrode excellent in slurry stability and coating uniformity can be obtained. Hereinafter, the positive electrode active material, the binder, and other components will be described in order.

[0052] <Positive Electrode Active Material> The positive electrode active material is a substance that transfers electrons at the positive electrode of a secondary battery. And, for example, when the secondary battery is a lithium-ion secondary battery, usually, a substance capable of occluding and releasing lithium is used as the positive electrode active material. In the following, as an example, the positive electrode active material in the case where the secondary battery is a lithium-ion secondary battery will be described, but the present invention is not limited to the following example.

[0053] The positive electrode active material for a lithium-ion secondary battery is not particularly limited, and includes lithium-containing cobalt oxide (LiCoO2), lithium manganate (LiMn2O4), lithium-containing nickel oxide (LiNiO2), lithium-containing composite oxide of Co-Ni-Mn (Li(CoMnNi)O2), lithium-containing composite oxide of Ni-Mn-Al, lithium-containing composite oxide of Ni-Co-Al, olivine-type lithium iron phosphate (LiFePO4), olivine-type lithium manganese phosphate (LiMnPO4), Li2MnO3-LiNiO2-based solid solution, Li 1+x Mn 2-x O4 (where \(0 < X < 2\)) represents a lithium-excess spinel compound, Li[Ni 0.17 Li 0.2 Co 0.07Mn 0.56 ]O2, LiNi 0.5 Mn 1.5 Examples of known positive electrode active materials include O4. Among the above, from the viewpoint of improving the battery capacity of the lithium ion secondary battery, lithium-containing cobalt oxide (LiCoO2), lithium-containing nickel oxide (LiNiO2), lithium-containing composite oxide of Co-Ni-Mn, Li[Ni 0.17 Li 0.2 Co 0.07 Mn 0.56 ]O2 or LiNi 0.5 Mn 1.5 O4 is preferably used, and lithium-containing cobalt oxide (LiCoO2), Li[Ni 0.17 Li 0.2 Co 0.07 Mn 0.56 ]O2, LiNi 0.5 Mn 1.5 O4 or LiNi 0.5 Co 0.2 Mn 0.3 It is more preferable to use O2. These can be used alone or in combination of two or more.

[0054] <Binder> The binder prevents components contained in the positive electrode mixture layer from being released from the positive electrode mixture layer in a positive electrode produced using the slurry for a secondary battery obtained according to the production method of the present invention. The binder used in the production method of a slurry for a secondary battery positive electrode of the present invention is not particularly limited, but it is preferable to use a fluorine-based polymer from the viewpoint of further improving the stability of the slurry for a secondary battery positive electrode.

[0055] [Fluoropolymer] The fluoropolymer is not particularly limited, and examples thereof include polytetrafluoroethylene, polychlorotrifluoroethylene, polyvinylidene fluoride, polyvinyl fluoride, perfluoroalkoxy fluororesin, tetrafluoroethylene-hexafluoropropylene copolymer, ethylene-tetrafluoroethylene copolymer, ethylene-chlorotrifluoroethylene copolymer, vinylidene fluoride-hexafluoropropylene copolymer (vinylidene fluoride-hexafluoropropylene copolymer), etc. Among these, polyvinylidene fluoride (PVdF) is preferred as the fluoropolymer.

[0056] [Other ingredients] Examples of other components include optional components such as reinforcing materials, leveling agents, viscosity modifiers, and electrolyte additives. These are not particularly limited as long as they do not affect the battery reaction. These components may be used alone or in combination of two or more in any ratio.

[0057] In the method for producing a slurry for a secondary battery positive electrode of the present invention, the method for mixing the above-mentioned components is not particularly limited, and for example, mixing can be performed using a mixer similar to that used in preparing the above-mentioned conductive material dispersion liquid.

[0058] <Conductive material content in slurry for secondary battery positive electrode> The content of the conductive material in the slurry for a secondary battery positive electrode obtained by the production method of the present invention is not particularly limited, but is preferably 0.1 parts by mass or less, and more preferably 0.08 parts by mass or less, per 100 parts by mass of the positive electrode active material. If the content of the conductive material in the slurry for a secondary battery positive electrode is 0.1 parts by mass or less, both the slurry stability and coating uniformity of the secondary battery slurry can be sufficiently excellent.

[0059] <Binder Content in Slurry for Secondary Battery Positive Electrode> Furthermore, the content of the binder in the slurry for secondary battery positive electrodes obtained by the production method of the present invention is not particularly limited, but the content of the binder is preferably 0.1 parts by mass or more, preferably 6 parts by mass or less, and more preferably 1 part by mass or less, converted into solid content per 100 parts by mass of the positive electrode active material. If the content of the binder in the slurry for secondary battery positive electrodes is within the above range, in a positive electrode produced using the slurry for secondary battery positive electrodes, the adhesion between the positive electrode mixture layer and the current collector can be increased, and the resistance of the secondary battery can be kept sufficiently low.

[0060] The slurry for a secondary battery positive electrode obtained by the production method of the present invention can be suitably used, for example, in the production method for a secondary battery positive electrode of the present invention described below.

[0061] (Method of manufacturing a positive electrode for a secondary battery) The method for producing a secondary battery electrode of the present invention includes forming a positive electrode composite layer using a slurry for a secondary battery positive electrode obtained by the method for producing a slurry for a secondary battery positive electrode of the present invention. Here, the positive electrode composite layer can be formed, for example, by including a step of applying the slurry for a secondary battery positive electrode obtained by the above-mentioned production method of the present invention to at least one surface of a current collector (application step), and a step of drying the slurry for a secondary battery positive electrode formed on at least one surface of the current collector to form a positive electrode composite layer on at least one surface of the current collector (drying step).

[0062] [Coating process] The method for applying the slurry for a secondary battery positive electrode onto a current collector is not particularly limited, and known methods can be used. Specifically, examples of the application method include a doctor blade method, a dipping method, a reverse roll method, a direct roll method, a gravure method, an extrusion method, and a brush coating method. The thickness of the slurry film on the current collector after application and before drying can be appropriately set depending on the thickness of the positive electrode mixture layer obtained by drying.

[0063] Here, the current collector to which the secondary battery positive electrode slurry is applied is made of a material that is electrically conductive and electrochemically durable. Specifically, the current collector may be made of, for example, iron, copper, aluminum, nickel, stainless steel, titanium, tantalum, gold, platinum, etc. Note that the above materials may be used alone or in combination of two or more in any ratio.

[0064] [Drying process] The method for drying the slurry for a secondary battery positive electrode on the current collector is not particularly limited, and a known method can be used, for example, a drying method using warm air, hot air, or low-humidity air, a vacuum drying method, or a drying method using irradiation with infrared rays or electron beams, etc. By drying the slurry for a secondary battery positive electrode on the current collector in this manner, a positive electrode composite layer can be formed on the current collector, and a positive electrode for a secondary battery including the current collector and the positive electrode composite layer can be obtained.

[0065] After the drying step, the positive electrode mixture layer may be subjected to pressure treatment using a mold press, a roll press, etc. Pressure treatment can improve the adhesion between the positive electrode mixture layer and the current collector.

[0066] The positive electrode obtained by the method for producing a positive electrode for a secondary battery of the present invention includes a current collector and a positive electrode mixture layer formed on the current collector, the positive electrode mixture layer being formed using the slurry for a positive electrode for a secondary battery obtained by the above-mentioned production method of the present invention. That is, the positive electrode mixture layer contains at least a positive electrode active material, carbon nanotubes as a conductive material, and a hydrogenated acrylonitrile-butadiene copolymer as a dispersant. Note that the components contained in the positive electrode mixture layer are the same as those contained in the slurry for a positive electrode for a secondary battery obtained by the production method of the present invention, and the preferred ratios of the components are the same as the preferred ratios of the components in the slurry for a positive electrode for a secondary battery.

[0067] In the positive electrode for a secondary battery obtained by the manufacturing method of the present invention, the positive electrode mixture layer is formed using the slurry for a secondary battery positive electrode containing the conductive material dispersion of the present invention, and therefore the conductive material forms a good conductive network inside the positive electrode mixture layer. Therefore, by using this positive electrode for a secondary battery, the cycle characteristics of the secondary battery can be improved, and the internal resistance can be reduced, thereby improving the output characteristics of the secondary battery.

[0068] (Secondary battery manufacturing method) The method for producing a secondary battery of the present invention uses a positive electrode for a secondary battery obtained by the method for producing a secondary battery of the present invention. The method for producing a secondary battery of the present invention can produce a secondary battery with excellent output characteristics and cycle characteristics. Hereinafter, a description will be given of a case where the secondary battery is a lithium-ion secondary battery as an example, but the present invention is not limited to the following example.

[0069] <Negative electrode> As the negative electrode of the secondary battery, a known negative electrode can be used, specifically, for example, a negative electrode made of a thin plate of metallic lithium or a negative electrode formed by forming a negative electrode mixture layer on a current collector. The current collector can be made of a metal material such as iron, copper, aluminum, nickel, stainless steel, titanium, tantalum, gold, or platinum. The negative electrode composite layer can be a layer containing a negative electrode active material and a negative electrode binder. The negative electrode binder is not particularly limited, and any known material can be used.

[0070] <Electrolyte> As the electrolyte, an organic electrolyte solution in which a supporting electrolyte is dissolved in an organic solvent is usually used. For example, a lithium salt is used as the supporting electrolyte of a lithium ion secondary battery. Examples of lithium salts include LiPF6, LiAsF6, LiBF4, LiSbF6, LiAlCl4, LiClO4, CF3SO3Li, CF4F9SO3Li, CF3COOLi, (CF3CO)2NLi, (CF3SO2)2NLi, and (C2F5SO2)NLi. Among these, LiPF6, LiClO4, and CF3SO3Li are preferred, with LiPF6 being particularly preferred, because they are easily soluble in solvents and exhibit a high degree of dissociation. One type of electrolyte may be used alone, or two or more types may be used in combination at any ratio. Generally, the use of a supporting electrolyte with a higher degree of dissociation tends to result in higher lithium ion conductivity, so the lithium ion conductivity can be adjusted by the type of supporting electrolyte.

[0071] The organic solvent used in the electrolyte is not particularly limited as long as it can dissolve the supporting electrolyte. For example, carbonates such as dimethyl carbonate (DMC), ethylene carbonate (EC), diethyl carbonate (DEC), propylene carbonate (PC), butylene carbonate (BC), and methyl ethyl carbonate (EMC) are preferred. Other suitable solvents include γ-butyrolactone, methyl formate, and other esters. Ethers such as 1,2-dimethoxyethane and tetrahydrofuran are also suitable. Sulfur-containing compounds such as sulfolane and dimethyl sulfoxide are also suitable. Mixtures of these solvents may also be used. Among these, carbonates are preferred because of their high dielectric constant and wide stable potential range. A mixture of ethylene carbonate and ethyl methyl carbonate is particularly preferred.

[0072] <separator> The separator is not particularly limited, but examples thereof include known separators such as organic separators, which are porous members made of organic materials, such as microporous membranes or nonwoven fabrics containing polyolefin resins such as polyethylene and polypropylene, or aromatic polyamide resins.

[0073] In the method for producing a secondary battery of the present invention, a positive electrode is produced according to the method for producing a positive electrode for a secondary battery of the present invention described above. The resulting positive electrode and negative electrode are then stacked together with a separator interposed therebetween, and the stack is then wound or folded as necessary according to the battery shape and placed in a battery container, after which an electrolyte solution is poured into the battery container and sealed. To prevent internal pressure rise, overcharge / discharge, and the like within the secondary battery, a fuse, an overcurrent protection element such as a PTC element, an expanded metal, a lead plate, or the like may be provided as necessary. The shape of the secondary battery may be, for example, a coin type, a button type, a sheet type, a cylindrical type, a rectangular type, a flat type, or the like. [Example]

[0074] The present invention will be described below based on examples, but the present invention is not limited to these examples. In the following description, "%" and "parts" representing amounts are based on mass unless otherwise specified. The proportion of each monomer unit in the polymer usually corresponds to the ratio (feed ratio) of monomers capable of forming each monomer unit in the monomer composition used for polymerizing the polymer. In the examples and comparative examples, various physical properties were measured or evaluated using the following methods.

[0075] <Iodine value> The iodine value of the polymer was determined in accordance with JIS K6235;2006.

[0076] <Weight average molecular weight> The weight-average molecular weight of the polymer was measured by gel permeation chromatography (GPC). Specifically, a calibration curve was prepared using polystyrene as a standard substance, and the weight-average molecular weight was calculated as a value converted from the standard substance. The distribution of the weight-average molecular weight was evaluated by rounding off to the nearest 1 digit when the value was less than 10,000, and by rounding off to the nearest 1 digit when the value was 10,000 or more. The measurement conditions and measurement equipment were as follows: Column: TSKgel α-M x 2 (φ7.8 mm I.D. x 30 cm x 2, Tosoh Corporation) Eluent: dimethylformamide (50 mM lithium bromide, 10 mM phosphoric acid) Flow rate: 0.5mL / min. Sample concentration: Approximately 0.5 g / L (solid concentration) Injection volume: 200μL Column temperature: 40℃ Detector: Differential refractive index detector RI (Tosoh HLC-8320 GPC RI detector) Detector conditions: RI: Pol(+), Res(1.0s) Molecular weight marker: Tosoh standard polystyrene kit PStQuick K

[0077] <Volume average particle diameter (D90) of CNTs in conductive material dispersion> The prepared conductive material dispersion was diluted to an appropriate concentration to prepare a measurement sample. Using a laser diffraction particle size distribution analyzer (Shimadzu Corporation, "SALD-7100") as the measuring device, the particle size distribution (volume basis) of the CNTs was measured with a solvent refractive index of 1.47 (solvent: N-methyl-2-pyrrolidone), and the volume average particle diameter (D90) of the CNTs in the conductive material dispersion was calculated. The concentration of the measurement sample was set to a concentration at which the absorbance measured by the measuring device was 0.2 or less.

[0078] <Slurry stability> The slurry stability of the positive electrode slurry was evaluated based on the viscosity change rate of the positive electrode slurry. Specifically, the viscosity (η1) of the positive electrode slurry immediately after preparation was measured using a Brookfield viscometer (manufactured by Toki Sangyo Co., Ltd., "RB-80L") at a temperature of 25°C, a rotation speed of 60 rpm, and a rotation time of 60 seconds. The positive electrode slurry was then stored in a 25°C environment for 5 days, and the viscosity (η2) of the positive electrode slurry after storage was measured in the same manner as in the measurement of the viscosity (η1) described above. The viscosity change Δη was calculated using the obtained viscosities (η1) and (η2) according to the following formula: Viscosity change Δη (%) = (|η1-η2| / η1) × 100 The slurry stability of the positive electrode slurry was evaluated according to the following criteria: The smaller the viscosity change Δη, the better the slurry stability of the positive electrode slurry, and the better the dispersion state of the conductive material contained in the positive electrode slurry can be maintained. A: The viscosity change Δη is less than 20%. B: The viscosity change Δη is 20% or more and less than 50%. C: Viscosity change Δη is 50% or more.

[0079] <Coating uniformity> The pressed positive electrode was cut into a size of 10 cm x 10 cm. The surface of the cut positive electrode was then visually inspected, and coating uniformity was evaluated based on the number of irregularities (aggregates) on the positive electrode surface. The fewer irregularities (aggregates) observed visually on the positive electrode surface, the more uniformly the positive electrode slurry could be applied, indicating excellent coating uniformity. A: No irregularities (aggregates) can be visually confirmed on the surface of the positive electrode. B: Visually confirmed irregularities (aggregates) on the positive electrode surface in less than five places. C: There are five or more visible irregularities (aggregates) on the positive electrode surface.

[0080] <Output characteristics> The fabricated laminated lithium-ion secondary battery was charged at a constant current of 140 mA in a 25°C environment until the voltage reached 4.2 V, and then charged at a constant voltage of 14 mA at a voltage of 4.2 V. Subsequently, the battery was discharged at a constant current of 140 mA until the battery voltage reached 3 V, which was taken as the initial capacity. The laminated lithium-ion secondary battery whose initial capacity had been measured was charged at a constant current of 0.2 C in a 25°C environment until the battery voltage reached 4.2 V, and then constant voltage charged at 4.2 V until the charging current reached 0.02 C. Subsequently, the battery was discharged at a constant current of 2 C until the battery voltage reached 3.0 V, and this was taken as the 2C capacity. The output characteristic was calculated as [(2C capacity) / (initial capacity)] x 100 (%), and the output characteristic of the lithium-ion secondary battery was evaluated according to the following criteria. The higher the output characteristic value, the better the initial output characteristic of the lithium-ion secondary battery, i.e., the lower the internal resistance. A: Output characteristics are 90% or more. B: Output characteristics are 80% or more and less than 90%. C: Output characteristics are less than 80.

[0081] <Cycle characteristics> The fabricated lithium-ion secondary batteries were charged at a constant current of 1 C in a 45°C environment until the battery voltage reached 4.2 V, and then discharged at a constant current of 1 C until the battery voltage reached 3 V. This cycle was repeated 100 times. The charge / discharge capacity retention rate [= (B) / (A) × 100(%)] was calculated from the 100th discharge capacity (discharge capacity "B") relative to the first discharge capacity (discharge capacity "A"), and the cycle characteristics of the lithium-ion secondary batteries were evaluated according to the following criteria. The higher the charge / discharge capacity retention rate, the better the cycle characteristics of the lithium-ion secondary battery. A: Charge / discharge capacity retention rate is 90% or more B: Charge / discharge capacity retention rate is 80% or more but less than 90% C: Charge / discharge capacity retention rate is less than 80%

[0082] Example 1 <Preparation of Dispersant> A reactor was charged with 180 parts of ion-exchanged water, 25 parts of an aqueous solution of sodium dodecylbenzenesulfonate (10% concentration) as an emulsifier, 40 parts of styrene as an aromatic vinyl monomer, 26 parts of acrylonitrile as a nitrile group-containing monomer, 4 parts of methacrylic acid as a monomer having a carboxylic acid group, and 2 parts of t-dodecyl mercaptan as a molecular weight modifier, in this order. The gas inside the reactor was then purged with nitrogen three times, after which 30 parts of 1,3-butadiene as a conjugated diene monomer was charged. The reactor was maintained at 10°C, and 0.1 parts of cumene hydroperoxide as a polymerization initiator was charged to initiate the polymerization reaction, which was then allowed to proceed with stirring. When the conversion rate of the monomer to polymer reached 85%, 2,2,6,6-tetramethylpiperidine 1-oxyl (TEMPO) was added as a terminator, and then the residual monomer was removed using a rotary evaporator at a water temperature of 60°C to obtain an aqueous dispersion of acrylonitrile-butadiene copolymer (A) as a precursor of the dispersant. The obtained aqueous dispersion of acrylonitrile-butadiene copolymer (A) (total solid content: 48 g) was placed in a 1 L autoclave equipped with a stirrer, and nitrogen gas was passed through for 10 minutes to remove dissolved oxygen in the aqueous dispersion. Then, 50 mg of palladium acetate as a hydrogenation catalyst was dissolved in 180 mL of water containing 4 times the molar amount of nitric acid relative to palladium (Pd), and the solution was added. After the system was purged with hydrogen gas twice, the contents of the autoclave were heated to 50°C while pressurized with hydrogen gas to 3 MPa, and hydrogenation reaction was carried out for 6 hours to obtain hydrogenated acrylonitrile-butadiene copolymer (A) as a dispersant. The iodine value of the obtained hydrogenated acrylonitrile-butadiene copolymer (A) was 15 mg / 100 mg.

[0083] <Preparation of dispersant-containing NMP solution> The aqueous dispersion of the hydrogenated acrylonitrile-butadiene copolymer (A) obtained as described above was mixed with NMP as a solvent to obtain a mixed solution. Next, all of the water contained in the obtained mixed solution was evaporated under reduced pressure to obtain an NMP solution containing the hydrogenated acrylonitrile-butadiene copolymer (A). The obtained NMP solution containing the hydrogenated acrylonitrile-butadiene copolymer (A) was used as a dispersant-containing NMP solution.

[0084] <Preparation of Conductive Material Dispersion> CNT (A) as a conductive material (specific surface area: 1200 m 2 0.06 parts of toluene (1000 rpm, 10 min.), 0.12 parts (solids equivalent) of the dispersant-containing NMP solution obtained as described above, and 99.1 parts of NMP as a solvent were stirred using a disper (3000 rpm, 10 min.), and then mixed for 2 hours at a peripheral speed of 8 m / s using a bead mill using zirconia beads with a diameter of 1 mm to prepare a conductive material dispersion (A) with a solids concentration of 0.9 mass % (0.3 mass % in terms of CNT). The volume average particle diameter (D90) of the CNT (A) in the conductive material dispersion (A) was 20 μm.

[0085] <Preparation of positive electrode slurry> A positive electrode slurry was prepared by mixing 100 parts of lithium cobalt oxide (LiCoO, average particle size: 10 μm) as the positive electrode active material, 0.18 parts (solids equivalent: 0.06 parts CNT equivalent) of the conductive material dispersion (A) prepared as described above, 1.0 part of polyvinylidene fluoride (PVdF, Kureha Corporation, #7208) as the binder, and NMP as the solvent in a planetary mixer at 60 rpm for 30 minutes. The amount of NMP added was adjusted so that the viscosity of the resulting positive electrode slurry (measured using a single-cylindrical rotational viscometer in accordance with JIS Z8803:1991 at 25°C and 60 rpm) was in the range of 4000–5000 mPa·s. The resulting positive electrode slurry was evaluated for slurry stability and coating uniformity. The results are shown in Table 1.

[0086] <Preparation of positive electrode> An aluminum foil having a thickness of 20 μm was prepared as a current collector. The slurry for the positive electrode obtained as described above was coated on one side of the aluminum foil with a comma coater so that the coating weight after drying was 10 mg / cm. 2 The coating was dried at 90°C for 20 minutes and at 120°C for 20 minutes, and then vacuum heated at 60°C for 10 hours to obtain a positive electrode blank. This positive electrode blank was rolled using a roll press to a density of 3.2 g / cm. 3 A sheet-shaped positive electrode was prepared by combining a positive electrode composite layer (on one side) and aluminum foil. The thickness of the sheet-shaped positive electrode was 30 μm. This sheet-shaped positive electrode was cut into a width of 4.6 cm and a length of 50 cm to prepare a positive electrode for a lithium-ion secondary battery.

[0087] <Preparation of negative electrode> A negative electrode slurry was prepared by stirring 100 parts of spherical artificial graphite (volume average particle diameter: 12 μm) as the negative electrode active material, 1.5 parts of styrene-butadiene polymer as the negative electrode binder, 1 part of carboxymethyl cellulose as the thickener, and an appropriate amount of water as the dispersion medium using a planetary mixer. Next, a copper foil having a thickness of 15 μm was prepared as a current collector. The negative electrode slurry obtained as described above was applied to one side of the copper foil in an amount of 7 mg / cm after drying. 2 The coating was applied so that the density became 1.6 g / cm 3 , and then dried at 60°C for 20 minutes and at 120°C for 20 minutes to obtain a negative electrode blank. This negative electrode blank was rolled using a roll press to obtain a negative electrode blank with a density of 1.6 g / cm 3 . 3 A sheet-shaped negative electrode was fabricated consisting of the negative electrode mixture layer (one side) and copper foil, and the sheet-shaped negative electrode was cut into a width of 4.8 cm and a length of 52 cm to prepare a negative electrode for a lithium ion secondary battery.

[0088] <Manufacturing lithium-ion secondary batteries> The positive and negative electrodes obtained as described above were wound around a 20 mm diameter core with a separator (a 15 μm thick microporous polypropylene film) in between to obtain a wound body. The wound body was then compressed in one direction at a speed of 10 mm / sec until it reached a thickness of 4.5 mm. The compressed wound body had an elliptical shape in plan view, with a ratio of its major axis to its minor axis (major axis / minor axis) of 7.7. In addition, an electrolyte solution [composition: LiPF solution with a concentration of 1.0 M (solvent is a mixed solution in which 5 mass% of fluoroethylene carbonate is added to a mixed solvent of ethylene carbonate / ethyl methyl carbonate = 3 / 7 (mass ratio) and 2 volume% of vinylene carbonate is added as an additive] was prepared. The compressed wound body was then placed in an aluminum laminate case together with 3.2 g of nonaqueous electrolyte. A nickel lead wire was connected to a predetermined location on the negative electrode, and an aluminum lead wire was connected to a predetermined location on the positive electrode. The opening of the laminate case was then thermally sealed to obtain a lithium-ion secondary battery. This lithium-ion secondary battery was a pouch-shaped battery measuring approximately 35 mm wide, 50 mm high, and 5 mm thick, with a nominal capacity of 750 mAh. The output and cycle characteristics of the resulting lithium-ion secondary battery were evaluated. The results are shown in Table 1.

[0089] Example 2 As a conductive material, CNT(A) was replaced with CNT(B) (specific surface area: 910 m 2 A conductive material dispersion liquid (B) was prepared in the same manner as in Example 1, except that a conductive material dispersion liquid (A) containing 100% ammonium hydroxide and 100% ammonium hydroxide (100% ammonium hydroxide) was used. A positive electrode slurry, a positive electrode, a negative electrode, and a lithium ion secondary battery were then produced in the same manner as in Example 1, except that the conductive material dispersion liquid (B) was used instead of the conductive material dispersion liquid (A). Various evaluations were then carried out in the same manner as in Example 1. The results are shown in Table 1.

[0090] Example 3 In preparing the positive electrode slurry, the amount of the conductive material dispersion (A) was changed to 0.27 parts in terms of solid content (0.09 parts in terms of CNT), but the same procedure as in Example 1 was repeated to prepare a positive electrode slurry, a positive electrode, a negative electrode, and a lithium ion secondary battery. Various evaluations were then performed in the same manner as in Example 1. The results are shown in Table 1.

[0091] Example 4 In preparing the dispersant, the amount of palladium acetate as a hydrogenation reaction catalyst was changed to 25 mg, and the iodine value of the hydrogenated acrylonitrile-butadiene copolymer as a dispersant was adjusted to 22 mg / 100 mg. Except for this, a positive electrode slurry, a positive electrode, a negative electrode, and a lithium ion secondary battery were produced in the same manner as in Example 1. Then, various evaluations were performed in the same manner as in Example 1. The results are shown in Table 1.

[0092] Example 5 In preparing the positive electrode slurry, the ratio (mass ratio) of the dispersant (hydrogenated acrylonitrile-butadiene copolymer) to the conductive material (CNT (A)) in the conductive material dispersion liquid (A) was adjusted to 1:1, and the positive electrode slurry, positive electrode, negative electrode, and lithium ion secondary battery were produced in the same manner as in Example 1. Then, various evaluations were performed in the same manner as in Example 1. The results are shown in Table 1.

[0093] Example 6 A conductive material dispersion (C) was prepared in the same manner as in Example 1, except that the peripheral speed when mixing the various components in preparing the conductive material dispersion was changed to 6 m / s. The volume average particle diameter (D90) of the CNTs in the obtained conductive material dispersion (C) was 45 μm. A positive electrode slurry, a positive electrode, a negative electrode, and a lithium ion secondary battery were then produced in the same manner as in Example 1, except that the conductive material dispersion (C) was used instead of the conductive material dispersion (A). Various evaluations were then performed in the same manner as in Example 1. The results are shown in Table 1.

[0094] Example 7 In preparing the dispersant, the amount of acrylonitrile as a nitrile group-containing monomer, the amount of methacrylic acid as a carboxylic acid group-containing monomer was changed to 34 parts, the amount of 1,3-butadiene was changed to 4 parts, and the amount of 1,3-butadiene was changed to 62 parts, and styrene was not used. A positive electrode slurry, a positive electrode, a negative electrode, and a lithium ion secondary battery were produced in the same manner as in Example 1. Various evaluations were then performed in the same manner as in Example 1. The results are shown in Table 1.

[0095] Example 8 In preparing the positive electrode slurry, the positive electrode active material was a ternary active material (LiNi 0.5 Co 0.2 Mn 0.3 A positive electrode slurry, a positive electrode, a negative electrode, and a lithium ion secondary battery were produced in the same manner as in Example 1, except that the slurry was changed to 02 (average particle diameter: 10 μm). Various evaluations were then carried out in the same manner as in Example 1. The results are shown in Table 1.

[0096] (Comparative Example 1) A positive electrode slurry, a positive electrode, a negative electrode, and a lithium ion secondary battery were produced in the same manner as in Example 1, except that a hydrogenated acrylonitrile-butadiene copolymer was not used as a dispersant in preparing the positive electrode slurry. Various evaluations were then carried out in the same manner as in Example 1. The results are shown in Table 1.

[0097] (Comparative Example 2) When preparing the conductive material dispersion, CNT(C) (specific surface area: 390 m) was used instead of CNT(A). 2 A positive electrode slurry, a positive electrode, a negative electrode, and a lithium ion secondary battery were produced in the same manner as in Example 1, except that a 100% sintered body (0.1% wt. / g) was used. Various evaluations were then carried out in the same manner as in Example 1. The results are shown in Table 1.

[0098] (Comparative Example 3) A conductive material dispersion (X) was prepared in the same manner as in Example 1, except that the peripheral speed when mixing the various components in preparing the conductive material dispersion was changed to 4 m / s. The volume average particle diameter (D90) of the CNTs in the obtained conductive material dispersion (X) was 70 μm. A positive electrode slurry, a positive electrode, a negative electrode, and a lithium ion secondary battery were produced in the same manner as in Example 1, except that the conductive material dispersion (X) was used instead of the conductive material dispersion (A). Various evaluations were then performed in the same manner as in Example 1. The results are shown in Table 1.

[0099] [Table 1]

[0100] In Table 1, "LCO" stands for lithium cobalt oxide (LiCoO2), "NCM" is a ternary active material (LiNi 0.5 Co 0.2 Mn 0.3 O2), "CNT" stands for carbon nanotube, "PVdF" stands for polyvinylidene fluoride, "ST" stands for styrene "H-BD" indicates a 1,3-butadiene hydride unit; "BD" indicates butadiene; "AN" stands for acrylonitrile "MAA" stands for methacrylic acid.

[0101] From Table 1, as a conductive material, 2 / g or more 1300m 2 When a conductive material dispersion containing CNTs of 0.1 wt. / g or less, a hydrogenated acrylonitrile-butadiene copolymer having a weight-average molecular weight of 200,000 or less as a dispersant, and a solvent is used (Examples 1 to 8), in which the volume average particle diameter (D90) of the conductive material (CNTs) in the conductive material dispersion is 50 μm or less, a positive electrode slurry excellent in slurry stability and coating uniformity can be prepared, and the output characteristics and cycle characteristics of a lithium ion secondary battery including a positive electrode produced using the positive electrode slurry can be improved. On the other hand, when a conductive material dispersion liquid containing no dispersant was used (Comparative Example 1), the specific surface area of ​​the conductive material (CNT) in the conductive material dispersion liquid was 800 m 2 / g (Comparative Example 2), and when the volume average particle diameter (D90) of the conductive material (CNT) in the conductive material dispersion exceeds 50 μm (Comparative Example 3), it is found that the resulting positive electrode slurry is inferior in at least one of the slurry stability and coating uniformity, or the resulting lithium ion secondary battery is inferior in either the output characteristics or the cycle characteristics. [Industrial Applicability]

[0102] According to the present invention, it is possible to provide a method for producing a slurry for a positive electrode of a secondary battery, which can enable the secondary battery to exhibit excellent output characteristics and properties, and a conductive material dispersion liquid that can be suitably used for producing the slurry for a positive electrode of the secondary battery. Furthermore, the present invention can provide a method for producing a positive electrode for a secondary battery that can be used to produce a secondary battery having excellent output characteristics and cycle characteristics. According to the present invention, a method for manufacturing a secondary battery having excellent output characteristics and cycle characteristics can be provided.

Claims

1. A conductive material dispersion liquid containing a conductive material, a dispersant, and a solvent, The conductive material has a specific surface area of ​​800 m ２ / g or more 1300m ２ / g or less of carbon nanotubes, the volume average particle diameter (D90) of the carbon nanotubes in the conductive material dispersion is 50 μm or less; the dispersant is a hydrogenated acrylonitrile-butadiene copolymer; The weight average molecular weight of the hydrogenated acrylonitrile-butadiene copolymer is 200,000 or less.

2. 2. The conductive material dispersion according to claim 1, wherein the hydrogenated acrylonitrile-butadiene copolymer has an iodine value of 25 mg / 100 mg or less.

3. 3. The conductive material dispersion according to claim 1, wherein the content of the dispersant in the conductive material dispersion is 50 parts by mass or more and 400 parts by mass or less per 100 parts by mass of the conductive material.

4. A method for producing a slurry for a non-aqueous secondary battery positive electrode, comprising mixing a positive electrode active material, a binder, and the conductive material dispersion liquid according to any one of claims 1 to 3 to obtain a slurry for a non-aqueous secondary battery positive electrode.

5. 5. The method for producing a slurry for a non-aqueous secondary battery positive electrode according to claim 4, wherein the content of the conductive material in the slurry for a non-aqueous secondary battery positive electrode is less than 0.1 parts by mass per 100 parts by mass of the positive electrode active material.

6. 6. The method for producing a slurry for a non-aqueous secondary battery positive electrode according to claim 4 or 5, wherein the content of the binder in the slurry for a non-aqueous secondary battery positive electrode is 0.1 parts by mass or more and 6 parts by mass or less per 100 parts by mass of the positive electrode active material.

7. A method for producing a positive electrode for a non-aqueous secondary battery, comprising forming a positive electrode mixture layer using the slurry for a non-aqueous secondary battery positive electrode obtained by the method according to any one of claims 4 to 6.

8. A method for producing a non-aqueous secondary battery, using a positive electrode for a non-aqueous secondary battery obtained by the method according to claim 7.

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