JP2019083158A - Electrode and manufacturing method thereof, and cell - Google Patents

Abstract

To provide an electrode contributing to improvement of battery characteristics such as charge/discharge speed of secondary cells, and to provide a cell excellent in battery characteristics such as charge/discharge speed.SOLUTION: In an electrode containing conductive resin particles, the conductive resin particles are resin particles containing a conductive composite, the conductive composite contains π-conjugated electroconductive polymer and polyanion, and at least one kind of amine compound, selected from a group consisting of primary amine, secondary amine and tertiary amine, is added to a partial anion group of the polyanion. The inventive battery has the above-mentioned electrode.SELECTED DRAWING: None

Description

  The present invention relates to an electrode containing a π-conjugated conductive polymer, a method for producing the same, and a battery.

In recent years, secondary batteries that can be charged and discharged, particularly lithium ion batteries, are widely used. For example, lithium ion batteries are widely used in electronic devices such as mobile phones, smartphones, notebook personal computers, and tablet terminals. Moreover, a lithium ion battery or a nickel hydrogen battery is used as a battery of an electric vehicle. In addition, since the amount of power generation fluctuates in solar power generation or wind power generation, the generated power is temporarily stored in the secondary battery for the purpose of fixing the amount of power transmitted from the solar power generation plant or the wind power generation plant. Sometimes.
In secondary batteries, particularly lithium ion batteries, carbon materials are widely used as negative electrode materials (for example, Patent Document 1).

International Publication No. 2016/104024

However, in the conventional secondary battery, for example, battery characteristics such as the charge and discharge rate may not be sufficient, and in particular, the charge rate may be a problem in practical use. In addition, the battery characteristics may not be sufficient in batteries other than the secondary battery.
An object of the present invention is to provide an electrode which contributes to improvement of battery characteristics such as charge and discharge speed and a method of manufacturing the same. An object of the present invention is to provide a battery excellent in battery characteristics such as charge and discharge rate.

The present invention includes the following aspects.
[1] An electrode containing conductive resin particles,
The conductive resin particles are resin particles containing a conductive complex,
The electrode, wherein the conductive complex includes a π-conjugated conductive polymer and a polyanion, and an amine compound is added to an anion group of a part of the polyanion.
[2] The electrode according to [1] or [2], wherein the conductive resin particles include particles having a particle diameter in the range of 0.3 μm to 20 μm.
[3] The electrode according to [2], wherein the conductive resin particles have a particle diameter of not less than 50% and not less than 0.3 μm and not more than 20 μm.
[4] The electrode according to any one of [1] to [3], further containing a carbon material.
[5] The electrode according to any one of [1] to [4], wherein the π-conjugated conductive polymer is poly (3,4-ethylenedioxythiophene).
[6] The electrode according to any one of [1] to [5], wherein the polyanion is polystyrene sulfonic acid.
The battery which has an electrode as described in any one of [7] [1]-[6].
[8] The battery according to [7], which is a secondary battery.
[9] The battery according to [7] or [8], which is a lithium ion battery.
[10] The battery according to any one of [7] to [9], which uses the electrode as a negative electrode.

[11] A precipitation step of adding an amine compound to an aqueous dispersion of a conductive complex containing a π-conjugated conductive polymer and a polyanion, and depositing the conductive complex to form a precipitate;
A recovery step of recovering the precipitate;
A pulverizing step of pulverizing the collected precipitate so as to form particles having a particle diameter in the range of 0.3 μm to 20 μm to form conductive resin particles;
A forming step of forming the conductive resin particles;
A method of manufacturing an electrode, comprising:
[12] The method for producing an electrode according to [11], wherein the precipitate is pulverized so that particles having a particle diameter in the range of 0.3 μm to 20 μm are formed in the pulverizing step.
[13] In the pulverizing step, the precipitate is wet pulverized in a dispersion medium to obtain a conductive resin particle dispersion liquid in which the conductive resin particles are dispersed in the dispersion medium, as described in [11] or [12]. Of manufacturing electrodes.
[14] The method for producing an electrode according to [13], wherein the dispersion medium is at least one selected from the group consisting of ethyl acetate, butyl acetate, heptane, toluene, and diethylene glycol diethyl ether.
[15] The method for producing an electrode according to [13] or [14], wherein the dispersion medium is removed from the conductive resin particle dispersion in the forming step.
[16] The method for producing an electrode according to [15], wherein a carbon material is added to the conductive resin particle dispersion liquid before the forming step.
[17] The method for producing an electrode according to any one of [11] to [16], wherein the π-conjugated conductive polymer is poly (3,4-ethylenedioxythiophene).
[18] The method for producing an electrode according to any one of [11] to [17], wherein the polyanion is polystyrene sulfonic acid.
[19] In the molding step, the conductive resin particle dispersion is coated on a substrate and dried to form an electrode containing the conductive resin particles on the surface of the substrate, [11] The manufacturing method of the electrode as described in any one of-[18].

The electrode of the present invention contributes to the improvement of battery characteristics such as charge and discharge speed.
According to the method for producing an electrode of the present invention, it is possible to easily produce an electrode which contributes to the improvement of battery characteristics such as charge and discharge speed.
The battery of the present invention is excellent in battery characteristics such as charge and discharge speed.

<Electrode>
One aspect of the electrode of the present invention will be described.
The electrode of this aspect includes conductive resin particles containing a conductive complex.
There is no restriction | limiting in particular as a shape of an electrode, A membrane form may be sufficient and solid shape, such as rod shape and columnar shape, may be sufficient. When the electrode is in the form of a film, the average thickness is preferably 0.01 μm to 1000 μm, and more preferably 0.1 μm to 100 μm. If the average thickness of the film-like electrode is equal to or more than the lower limit value, battery characteristics of a battery such as a secondary battery can be further improved, and if less than the upper limit value, the battery can be easily thinned. The average thickness of the electrode is a value obtained by observing the cross section of the electrode using a microscope or an electron microscope, measuring the thickness at 10 or more locations, and averaging the measured values.
The electrodes may be supported by a substrate such as a film or substrate.
The electrode may be a positive electrode or a negative electrode.

(Conductive resin particles)
The conductive resin particles in this aspect preferably contain particles having a particle diameter in the range of 0.3 μm to 20 μm, and preferably contain particles having a particle diameter in the range of 0.3 μm to 10 μm. The particle size is a value measured using a dynamic light scattering particle size distribution measuring apparatus using a dynamic light scattering method. If the particle diameter of the conductive resin particles is equal to or more than the lower limit value, the conductivity of the electrode becomes higher, and the battery characteristics of the battery can be enhanced. When the particle diameter of the conductive resin particles is equal to or less than the upper limit value, the gaps between the particles can be reduced, so that it is possible to suppress the decrease in conductivity due to the insulating gaps.
The content of particles having a particle diameter in the range of 0.3 μm to 20 μm is preferably 50% or more, more preferably 70% or more, and 80% or more in the conductive resin particles in this aspect. Is more preferred. Furthermore, in the conductive resin particles in this aspect, the content of particles having a particle diameter in the range of 0.3 μm to 10 μm is preferably 50% or more, more preferably 70% or more, and 80% It is more preferable that it is more than.
If the ratio of particles in the particle diameter range is equal to or more than the lower limit value, the battery characteristics of the battery can be further improved.
The proportion of particles in the particle diameter range is a value determined from the number frequency of particle diameters when the particle diameter is measured using a dynamic light scattering particle size distribution measuring apparatus.

The conductive resin particles in this aspect contain a conductive composite. The conductive complex in the present embodiment includes a π-conjugated conductive polymer and a polyanion. The polyanion is coordinated to the π-conjugated conductive polymer, and the anion group of the polyanion is doped to the π-conjugated conductive polymer, thereby forming a conductive complex having conductivity.
In the polyanion, all the anionic groups are not doped to the π-conjugated conductive polymer, and have excess anionic groups. In this aspect, at least one amine compound selected from the group consisting of primary amines, secondary amines and tertiary amines is added to at least a part of the above-mentioned surplus anionic groups. Thereby, the conductive complex is hydrophobized.

[Π-conjugated conductive polymer]
The π-conjugated conductive polymer is not particularly limited as long as it has the effect of the present invention as long as it is an organic polymer having a π-conjugated system as the main chain, and, for example, polypyrrole conductive polymer, polythiophene type Conductive polymers, polyacetylene-based conductive polymers, polyphenylene-based conductive polymers, polyphenylene vinylene-based conductive polymers, polyaniline-based conductive polymers, polyacene-based conductive polymers, polythiophene-vinylene-based conductive polymers, These copolymers etc. are mentioned. From the viewpoint of stability in air, polypyrrole-based conductive polymers, polythiophenes and polyaniline-based conductive polymers are preferable, and from the viewpoint of conductivity, polythiophene-based conductive polymers are more preferable.

Examples of polythiophene-based conductive polymers include polythiophene, poly (3-methylthiophene), poly (3-ethylthiophene), poly (3-propylthiophene), poly (3-butylthiophene), poly (3-hexylthiophene) Poly (3-heptylthiophene), poly (3-octylthiophene), poly (3-decylthiophene), poly (3-dodecylthiophene), poly (3-octadecylthiophene), poly (3-bromothiophene), poly (3-chlorothiophene), poly (3-iodothiophene), poly (3-cyanothiophene), poly (3-phenylthiophene), poly (3,4-dimethylthiophene), poly (3,4-dibutylthiophene) , Poly (3-hydroxythiophene), poly (3-methoxythiophene), poly ( -Ethoxythiophene), poly (3-butoxythiophene), poly (3-hexyloxythiophene), poly (3-heptyloxythiophene), poly (3-octyloxythiophene), poly (3-decyloxythiophene), poly (3-dodecyloxythiophene), poly (3-octadecyloxythiophene), poly (3,4-dihydroxythiophene), poly (3,4-dimethoxythiophene), poly (3,4-diethoxythiophene), poly ( 3,4-dipropoxythiophene), poly (3,4-dibutoxythiophene), poly (3,4-dihexyloxythiophene), poly (3,4-diheptyloxythiophene), poly (3,4-dioctyl) Oxythiophene), poly (3,4-didecyloxythiophene), poly (3, -Didodecyloxythiophene), poly (3,4-ethylenedioxythiophene), poly (3,4-propylenedioxythiophene), poly (3,4-butylenedioxythiophene), poly (3-methyl-4) -Methoxythiophene), poly (3-methyl-4-ethoxythiophene), poly (3-carboxythiophene), poly (3-methyl-4-carboxythiophene), poly (3-methyl-4-carboxyethylthiophene), Poly (3-methyl-4-carboxybutylthiophene) is mentioned.
Examples of polypyrrole-based conductive polymers include polypyrrole, poly (N-methylpyrrole), poly (3-methylpyrrole), poly (3-ethylpyrrole), poly (3-n-propylpyrrole) and poly (3-butyl) Pyrrole), poly (3-octylpyrrole), poly (3-decylpyrrole), poly (3-dodecylpyrrole), poly (3,4-dimethylpyrrole), poly (3,4-dibutylpyrrole), poly (3 -Carboxypyrrole), poly (3-methyl-4-carboxypyrrole), poly (3-methyl-4-carboxyethylpyrrole), poly (3-methyl-4-carboxybutylpyrrole), poly (3-hydroxypyrrole) , Poly (3-methoxypyrrole), poly (3-ethoxypyrrole), poly (3-butoxypyrrole), poly (3-hexene) Oxy pyrrole), poly (3-methyl-4-hexyloxy-pyrrole) and the like.
Examples of polyaniline conductive polymers include polyaniline, poly (2-methylaniline), poly (3-isobutylaniline), poly (2-anilinesulfonic acid) and poly (3-anilinesulfonic acid).
Among the π-conjugated conductive polymers, poly (3,4-ethylenedioxythiophene) is particularly preferable in terms of conductivity and heat resistance.
The π conjugated conductive polymer contained in the conductive complex may be one type or two or more types.

[Polyanion]
The polyanion is a polymer having two or more monomer units having an anionic group in the molecule. The anion group of this polyanion functions as a dopant for the π conjugated conductive polymer to improve the conductivity of the π conjugated conductive polymer.
The anion group of the polyanion is preferably a sulfo group or a carboxy group.
Specific examples of such polyanions include polystyrene sulfonic acid, polyvinyl sulfonic acid, polyallyl sulfonic acid, polyacrylic sulfonic acid, polymethacrylic sulfonic acid, poly (2-acrylamido-2-methylpropane sulfonic acid) and polyisoprene sulfone. Polymers having sulfonic acid groups such as acid, polysulfoethyl methacrylate, poly (4-sulfobutyl methacrylate), polymethacryloxybenzene sulfonic acid, etc., polyvinyl carboxylic acid, polystyrene carboxylic acid, polyallyl carboxylic acid, polyacrylic carboxylic acid And polymers having carboxylic acid groups such as polymethacrylic carboxylic acid, poly (2-acrylamido-2-methylpropane carboxylic acid), polyisoprene carboxylic acid, and polyacrylic acid. These homopolymers may be sufficient and 2 or more types of copolymers may be sufficient.
Among these polyanions, a polymer having a sulfonic acid group is preferable, and polystyrene sulfonic acid is more preferable, because the conductivity can be further increased.
The said polyanion may be used individually by 1 type, and may use 2 or more types together.
The mass average molecular weight of the polyanion is preferably 20,000 or more and 1,000,000 or less, and more preferably 100,000 or more and 500,000 or less. The mass average molecular weight of the polyanion was measured using gel permeation chromatography (GPC), and the elution time was measured, and the molecular weight based on mass based on the calibration curve of elution time versus molecular weight previously obtained from polystyrene standard substances of known molecular weight. It is

In this embodiment, the hydrophobic substituent is formed by adding an amine compound to a part of the anion group of the polyanion. By forming a hydrophobic substituent on the polyanion with an amine compound, the lipophilicity of the conductive complex can be increased, and the dispersibility of the conductive complex in water can be reduced. Therefore, the conductive resin particles in this aspect can be easily produced by the method for producing conductive resin particles described later.
Although detailed analysis of the conductive complex is not always easy, it is speculated that the reaction between the anion group of the polyanion and the amine compound forms a hydrophobic substituent represented by -HNR ¹ R ² R ³ Ru. The R ¹ , R ² and R ³ are substituents derived from an amine compound described later. For example, at least one of R ¹ , R ² and R ³ is a hydrocarbon group (however, at least one of hydrogen atoms of the hydrocarbon group may be substituted with an alkyl group, an aryl group, a hydroxy group or the like). It is. Of R ¹ , R ² and R ³ , those which are not hydrocarbon groups are hydrogen atoms.
The hydrophobic substituent is bonded to the oxygen atom of the anionic group.

The amine compound is preferably at least one selected from the group consisting of primary amines, secondary amines and tertiary amines. An amine compound may be used individually by 1 type, and may use 2 or more types together.
Examples of primary amines include aniline, toluidine, benzylamine, ethanolamine and the like.
Examples of secondary amines include diethanolamine, dimethylamine, diethylamine, dipropylamine, diphenylamine, dibenzylamine, dinaphthylamine and the like.
Examples of tertiary amines include triethanolamine, trimethylamine, triethylamine, tripropylamine, tributylamine, trihexylamine, trihexylamine, trioctylamine, triphenylamine, tribenzylamine, trinaphthylamine and the like.
Among the amine compounds, a tertiary amine is preferable because at least one of trihexylamine and trioctylamine is more preferable because the conductive resin particles in this aspect can be easily produced.

  The content ratio of the polyanion in the conductive complex is preferably in the range of 1 part by mass to 1000 parts by mass with respect to 100 parts by mass of the π-conjugated conductive polymer, and 10 parts by mass to 700 parts by mass Is more preferably 100 parts by mass or more and 500 parts by mass or less. If the content rate of the polyanion is at least the lower limit value, the doping effect on the π-conjugated conductive polymer tends to be strong, and the conductivity becomes higher. On the other hand, when the content of the polyanion is equal to or less than the upper limit value, the π-conjugated conductive polymer can be sufficiently contained, so sufficient conductivity can be secured.

[High conductivity agent]
The conductive resin particles in this aspect may contain a high conductivity agent in order to further improve the conductivity of the conductive resin particles. Here, the above-mentioned π conjugated conductive polymer, polyanion and amine compound are not classified as high conductivity agents.
The high conductivity agent includes saccharides, nitrogen-containing aromatic cyclic compounds, compounds having two or more hydroxy groups, compounds having one or more hydroxy groups and one or more carboxy groups, compounds having an amide group, The compound is preferably at least one compound selected from the group consisting of a compound having an imide group and a lactam compound.
The high conductivity agent contained in the conductive resin particles may be one type, or two or more types.
The content ratio of the high conductivity agent in the conductive resin particles is preferably 1 part by mass or more and 10000 parts by mass or less, and 10 parts by mass or more and 5000 parts by mass or less with respect to 100 parts by mass of the conductive complex. More preferably, it is 100 to 2500 parts by mass. If the content ratio of the high conductivity agent in the conductive resin particles is not less than the lower limit value, the conductivity improvement effect by the addition of the high conductivity agent is sufficiently exhibited, and if it is less than the above upper limit value, π conjugated system conductivity It is possible to prevent the decrease in conductivity due to the decrease in polymer concentration.

[Other additives]
The conductive resin particles in this aspect may contain other known additives.
The additive is not particularly limited as long as the effects of the present invention can be obtained, and, for example, a surfactant, an antifoaming agent, a coupling agent, an antioxidant, a UV absorber and the like can be used. However, the additive comprises a compound other than the above-described π-conjugated conductive polymer, polyanion and high conductivity agent.
Examples of the surfactant include nonionic, anionic and cationic surfactants. From the viewpoint of storage stability, nonionic surfactants are preferable. In addition, a polymeric surfactant such as polyvinyl pyrrolidone may be added.
As an antifoamer, silicone resin, polydimethylsiloxane, silicone oil etc. are mentioned.
As a coupling agent, the silane coupling agent etc. which have a vinyl group or an amino group are mentioned.
Examples of the antioxidant include phenol-based antioxidants, amine-based antioxidants, phosphorus-based antioxidants, sulfur-based antioxidants, saccharides and the like.
Examples of UV absorbers include benzotriazole UV absorbers, benzophenone UV absorbers, salicylate UV absorbers, cyanoacrylate UV absorbers, oxanilide UV absorbers, hindered amine UV absorbers, benzoate UV absorbers, etc. Can be mentioned.
When the conductive resin particles contain the above-mentioned additive, the content ratio thereof is appropriately determined according to the type of the additive, but for example, 0.001 parts by mass or more to 5 parts by mass with respect to 100 parts by mass of the conductive complex It can be made into the range of mass part or less.

(Carbon material)
The electrode of this aspect may contain a carbon material in addition to the conductive resin particles. Examples of the carbon material include carbon black, graphite, carbon fiber, carbon nanofiber, carbon nanotube and the like. A carbon material may be used individually by 1 type, and may use 2 or more types together.
The content of the carbon material in the electrode of the present embodiment is 0.01% by mass or more and 100000% by mass, where the total amount of the conductive resin particles and the carbon material is 100% by mass, from the viewpoint of further improving the battery characteristics of the battery. % Is preferably 0.1% by mass or more and 10000% by mass or less, and more preferably 1% by mass or more and 1000% by mass or less.

(Metal particles)
The electrode of this aspect may contain metal particles in addition to the conductive resin particles. Examples of the metal particles include silver particles, copper particles, gold particles, aluminum particles and the like. The metal particles may be used alone or in combination of two or more.
The content of the metal particles in the electrode of this embodiment is preferably 0% by mass or more and 50% by mass or less, and 0% by mass or more and 30% or less, when the total amount of the conductive resin particles and the carbon material is 100% by mass. It is more preferable that it is mass% or less, and it is more preferable that it is 0 mass% or more and 10 mass% or less. Since the metal has a high density, the battery tends to be heavy when the content of metal particles contained in the electrode is high. Therefore, the metal particle content is preferably low.

(Other ingredients)
The electrode of this embodiment may contain at least one selected from the group consisting of inorganic compounds (excluding carbon and metal particles) and polymers (excluding conductive resin particles). Some inorganic compounds and polymers function as binders.
Examples of the inorganic compound include silica, silica-alumina, glass, calcium carbonate, calcium hydroxide, talc, alumina, titania, zirconia, magnesium hydroxide, aluminum hydroxide, hydrotalcite, mica and the like. The said inorganic compound may be used individually by 1 type, and may use 2 or more types together.
Examples of the polymer include acrylic resin, polyester, polyamide, polyurethane, polystyrene, polyethylene, polypropylene, cellulose, carboxymethylcellulose, styrene-butadiene copolymer, polybutadiene and the like. The said polymer may be used individually by 1 type, and may use 2 or more types together.
The inorganic compound and the polymer may be in the form of particles or amorphous.
The content of the inorganic compound and the polymer in the electrode of the present embodiment is preferably 0% by mass or more and 50% by mass or less, when the total amount of the conductive resin particles and the carbon material is 100% by mass, 0 It is more preferable that it is mass% or more and 30 mass% or less, and it is still more preferable that it is 0 mass% or more and 10 mass% or less. Since the inorganic compound and the polymer are insulating, when the content of the inorganic compound and the polymer contained in the electrode increases, the conductivity of the electrode tends to decrease. Therefore, the content of the inorganic compound and the polymer is preferably small.

(Conductive resin particle dispersion)
In the present embodiment, the conductive resin particles may be dispersed in a dispersion medium to form a conductive resin particle dispersion. The conductive resin particle dispersion can form an electrode by coating. Moreover, when wet pulverization is applied in the manufacturing method of the conductive resin particle mentioned later, it is obtained as a conductive resin particle dispersion liquid.

The conductive resin particle dispersion liquid in this aspect contains the conductive resin particles and a dispersion medium.
Examples of the dispersion medium used in this embodiment include water, an organic solvent, and a mixture of water and an organic solvent.
Examples of the organic solvent include ester solvents, ether solvents, hydrocarbon solvents, nitrogen atom-containing solvents, alcohol solvents, ketone solvents and the like.
Examples of ester solvents include ethyl acetate, propyl acetate, butyl acetate and the like.
Examples of the ether solvents include diethyl ether, dimethyl ether, ethylene glycol, propylene glycol, propylene glycol dialkyl ether, diethylene glycol diethyl ether and the like.
Examples of hydrocarbon solvents include hexane, cyclohexane, pentane, heptane, octane, decane, dodecane, benzene, toluene, xylene, ethylbenzene, propylbenzene, isopropylbenzene and the like.
As a nitrogen atom containing solvent, N-methyl pyrrolidone, dimethyl acetamide, dimethylformamide etc. are mentioned, for example.
As an alcohol solvent, for example, methanol, ethanol, 1-propanol, 2-propanol, 2-methyl-2-propanol, 1-butanol, 2-butanol, 2-methyl-1-propanol, allyl alcohol, propylene glycol monomethyl Ether, ethylene glycol monomethyl ether and the like can be mentioned.
Examples of the ketone-based solvent include diethyl ketone, methyl propyl ketone, methyl butyl ketone, methyl isopropyl ketone, methyl isobutyl ketone, methyl amyl ketone, diisopropyl ketone, methyl ethyl ketone, acetone, diacetone alcohol and the like.
The organic solvents may be used alone or in combination of two or more.
Among the dispersion media, at least one selected from the group consisting of ester solvents, hydrocarbon solvents, ether solvents, and N-methylpyrrolidone when wet grinding is applied in the method for producing conductive resin particles described later. Preferred are the solvents of the species. Furthermore, among the dispersion media, at least one selected from the group consisting of ethyl acetate, butyl acetate, heptane, toluene, and diethylene glycol diethyl ether is more preferable. When the above-mentioned preferred solvent is used in wet grinding, conductive resin particles can be easily formed and the conductive complex can be stabilized.

  The content of the conductive resin particles in the conductive resin particle dispersion in this aspect is preferably 0.1% by mass to 80% by mass with respect to the total mass of the conductive resin particle dispersion, and 0.5% by mass More than 50 mass% is more preferable, and 1 mass% or more and 30 mass% or less is more preferable. If the content of the conductive resin particles in the conductive resin particle dispersion is equal to or more than the lower limit value, a thick conductive layer can be easily formed by one coating. If the content of the conductive resin particles in the conductive resin particle dispersion is not more than the above upper limit, the dispersibility of the conductive resin particles in the conductive resin particle dispersion can be increased.

  The conductive resin particle dispersion in this aspect is selected from the group consisting of carbon materials, metal particles, inorganic compounds (excluding carbon materials and metal particles), and polymer particles (excluding conductive resin particles). May be contained.

(Method of manufacturing electrode)
The method of manufacturing the electrode of this aspect has a precipitation step, a recovery step, a grinding step, and a forming step. As described later, when wet grinding is applied in the grinding step, the conductive resin particles are obtained in the state of the conductive resin particle dispersion dispersed in the dispersion medium, and the conductive resin particle dispersion is obtained in the molding step. It shape | molds and obtains an electrode.

[Precipitation process]
The precipitation step is a step of adding an amine compound to an aqueous dispersion of a conductive complex containing a π-conjugated conductive polymer and a polyanion, and depositing the conductive complex to form a precipitate.
When an amine compound is added to the aqueous dispersion, some of the anion groups of the polyanion constituting the conductive complex, specifically, anion groups that do not participate in the doping of the π-conjugated conductive polymer An amine compound is added to eliminate the anion group. Thereby, the conductive complex is hydrophobized.
However, the amine compound may not be added to all of the anion groups not involved in the doping to the π-conjugated conductive polymer, and a part of the anion groups not involved in the doping may remain.
The hydrophobized conductive complex can not be dispersed in the aqueous dispersion medium, and thus precipitates to form a precipitate.

The amine compound to be added to the aqueous dispersion of the conductive complex is at least one selected from the group consisting of primary amines, secondary amines and tertiary amines.
The addition amount of the amine compound is preferably 1 part by mass or more and 100000 parts by mass or less, more preferably 10 parts by mass or more and 50000 parts by mass or less, 50 parts by mass with respect to 100 parts by mass of the conductive complex. More preferably, it is at least 10000 parts by mass. If the addition amount of the amine compound is equal to or more than the lower limit value, the hydrophobicity of the conductive complex can be sufficiently improved, and if it is equal to or less than the upper limit value, the conductivity decrease of the conductive resin particles can be prevented.

The conductive polymer aqueous dispersion to which the amine compound is added in the precipitation step is a dispersion in which a conductive complex containing a π-conjugated conductive polymer and a polyanion is contained in an aqueous dispersion medium. Here, the aqueous dispersion medium contains water and may contain a water-soluble organic solvent. Examples of the water-soluble organic solvent include alcohol solvents, ketone solvents and ester solvents. The water-soluble organic solvent may be used alone or in combination of two or more.
The content of water in the aqueous dispersion medium is preferably 50% by mass or more, more preferably 80% by mass or more, and 100% by mass.
The conductive polymer aqueous dispersion can be obtained, for example, by chemical oxidation polymerization of a monomer forming a π-conjugated conductive polymer in an aqueous solution of polyanion. The conductive polymer aqueous dispersion may be a commercially available one.
A known catalyst may be applied to the chemical oxidative polymerization. For example, catalysts and oxidants can be used. Examples of the catalyst include transition metal compounds such as ferric chloride, ferric sulfate, ferric nitrate, cupric chloride and the like. Examples of the oxidizing agent include persulfates such as ammonium persulfate, sodium persulfate, potassium persulfate and the like. The oxidant can return the reduced catalyst to its original oxidation state.
The content of the conductive complex contained in the conductive polymer aqueous dispersion is preferably 0.1% by mass to 10% by mass, based on the total mass of the conductive polymer dispersion, and 0.3% by mass. % Or more and 5% by mass or less is preferable, and 0.5% by mass or more and 4% by mass or less is more preferable.

  Before, simultaneously with or after the addition of the amine compound to the conductive polymer water dispersion, an organic solvent may be added. As the organic solvent, a water-soluble organic solvent is preferable. Examples of the water-soluble organic solvent include alcohol solvents, ketone solvents and ester solvents. When the water-soluble organic solvent is contained, one kind may be used alone, or two or more kinds may be used in combination.

  Before, during or after the addition of the amine compound to the conductive polymer aqueous dispersion, heating may be performed.

[Collection process]
The recovery step is a step of recovering the precipitate composed of the hydrophobized conductive complex.
As a method for separating and recovering the precipitate from the aqueous dispersion medium, for example, known separation methods such as filtration, precipitation, extraction and the like can be applied. Among these separation methods, filtration is preferable, and it is preferable to perform filtration using a coarse filter to such an extent that the polyanion used to form the conductive complex passes along with the filtrate. According to this filtration method, it is possible to separate the precipitate and the excess polyanion by leaving the excess polyanion not forming the conductive complex on the filtrate side while fractionating the precipitate. By removing the excess polyanion, the conductivity of the precipitate can be enhanced.

  As a filter used for filtration, filter paper used in the field of chemical analysis is preferable. As this filter paper, for example, a filter paper made by Advantec, a retention particle diameter of 7 μm, etc. may be mentioned. Here, the retained particle diameter of the filter paper is a measure of the coarseness of the eye, and it can be determined by the leaked particle diameter when naturally filtering barium sulfate or the like defined in JIS P 3801 [filter paper (for chemical analysis)]. The retention particle diameter of the filter paper can be, for example, 2 μm or more and 20 μm or less. The retention particle diameter is preferably 5 μm or more and 10 μm or less because it can be easily separated by permeating excess polyanion.

[Crushing process]
The grinding step is a step of grinding the collected precipitates. In the pulverizing step, it is preferable to pulverize the precipitate so that particles having a particle diameter in the range of 0.3 μm to 20 μm are formed.
As a method of grinding the precipitate, for example, a grinding method of grinding using a mortar, a method of grinding using a grinder and the like can be mentioned. As a grinder, a homogenizer, a ball mill, a roller mill, a jet mill, a hammer mill etc. can be used, for example.
In pulverizing the precipitate, wet pulverization may be applied in which the precipitate is pulverized in the dispersion medium, or dry pulverization in which the precipitate is pulverized without the dispersion medium may be applied. Wet grinding is preferable in that the conductive resin particles having a particle diameter in the range of 0.3 μm to 20 μm can be easily produced. When wet grinding is applied to the precipitate deposited using an amine compound, the conductive resin particles are obtained in the state of being dispersed in a dispersion medium.
The dispersion medium used in wet pulverization is the same as the dispersion medium contained in the conductive resin particle dispersion. The preferred dispersion medium used in wet grinding is at least one selected from the group consisting of ethyl acetate, butyl acetate, heptane, toluene and diethylene glycol diethyl ether. By using these preferable dispersion media, conductive resin particles having a particle diameter in the range of 0.3 μm to 20 μm can be more easily produced.
In either dry grinding or wet grinding, particles having a particle diameter of 20 μm or less are difficult to be formed if the grinding is insufficient, and when excessively crushed, the particle diameter of the particles may be less than 0.3 μm. Therefore, it is preferable to form conductive resin particles in the range of 0.3 μm to 20 μm in particle diameter by appropriately selecting the pulverizing conditions and the specification of the pulverizer.

[Molding process]
The molding step is a step of molding the conductive resin particles. This molding provides an electrode.
When wet pulverization is applied in the pulverizing step, since the conductive resin particles are obtained in the state of a dispersion liquid, in the molding step, the conductive resin particle dispersion liquid is used for molding.
Examples of a method of forming the conductive resin particle dispersion include a method of applying a conductive resin particle dispersion to a metal foil or film, and removing the dispersion medium by drying to form a film-like electrode. . As a metal foil, copper foil, an aluminum foil etc. are mentioned, for example, As a film, a polyethylene terephthalate film etc. are mentioned, for example. The coating of the conductive resin particle dispersion may be performed using a known coater.
As another forming method of the conductive resin particle dispersion, for example, a method of filling the conductive resin particle dispersion in a mold and removing the dispersion medium by drying may be mentioned to form a three-dimensional electrode.
When wet grinding is applied in the grinding step and the carbon material is contained in the electrode, the carbon material may be added to the conductive resin particle dispersion before the molding step. Even when the conductive resin particle dispersion liquid contains a carbon material, the conductive resin particle dispersion liquid may be molded by removing the dispersion medium.
After applying wet grinding in the grinding step, the electrode contains at least one selected from the group consisting of metal particles, inorganic compounds (excluding carbon and metal particles) and polymers (excluding conductive resin particles). In the case of forming the conductive resin particle dispersion, at least one selected from the group consisting of metal particles, inorganic compounds, and polymers may be added to the conductive resin particle dispersion before forming. Even when the conductive resin particle dispersion liquid contains at least one selected from the group consisting of metal particles, inorganic compounds and polymers, the conductive resin particle dispersion liquid may be molded by removing the dispersion medium.

When dry pulverization is applied in the pulverizing step, a method of filling the mold with conductive resin particles and pressurizing the same to form an electrode may be mentioned.
In the case where dry grinding is applied in the grinding step and the carbon material is contained in the electrode, the conductive resin particles are mixed with the carbon material, and the obtained mixture is filled in a mold before the molding step. The pressure may be applied to form an electrode.
After applying dry grinding in the grinding step, the electrode contains at least one selected from the group consisting of metal particles, inorganic compounds (excluding carbon and metal particles) and polymers (excluding conductive resin particles). In the case of forming the conductive resin particles, at least one selected from the group consisting of metal particles, inorganic compounds and polymers is mixed with the conductive resin particles before filling, and the obtained mixture is filled in a mold and added. The electrodes may be formed by pressing.

(Action effect)
Since the electrode of this aspect contains the said conductive resin particle containing the electroconductive composite hydrophobized by the amine compound, the electroconductivity of an electrode tends to become high. Therefore, battery characteristics (for example, charge and discharge speed, capacity retention rate, capacity development rate, and the like in the secondary battery) including the electrode of the present embodiment can be improved.
When the electrode of this embodiment contains a carbon material together with the conductive resin particles, the conductivity of the electrode is higher. In particular, when conductive resin particles containing 50% by mass or more of particles having a particle diameter of 0.3 μm or more and 20 μm or less are used in combination with a carbon material, the combined effect is more exhibited. Therefore, the conductivity of the electrode can be further improved, and the battery characteristics of the battery can be further improved.

<Battery>
One aspect of the battery of the present invention has the electrode of the above aspect.
One embodiment of the battery of this aspect will be described. However, the battery of this aspect is not limited to the following embodiment.
The battery of the present embodiment is a lithium ion secondary battery having a positive electrode, a negative electrode, a separator, an electrolytic solution, and a container. The positive electrode, the negative electrode and the separator in the present embodiment are in the form of a film.

The material constituting the cathode, for _{example, LiCoO 2, LiNiO 2, LiMn} 2 O 4, LiFePO 4 , and the like.
It is preferable that a positive electrode current collector, which is a conductor, be connected to the positive electrode. When the positive electrode current collector is connected to the positive electrode, for example, an aluminum foil may be used as the positive electrode current collector, and the positive electrode may be formed in a film shape on one surface of the aluminum foil.

In the present embodiment, the electrode of the above aspect is used as the negative electrode.
It is preferable that a negative electrode current collector, which is a conductor, be connected to the negative electrode. When the negative electrode current collector is connected to the negative electrode, for example, a copper foil may be used as the negative electrode current collector, and the negative electrode may be formed in a film shape on one surface of the copper foil.

The separator is disposed between the positive electrode and the negative electrode.
As a separator, for example, a porous sheet or non-woven fabric of resin is used. As resin which comprises a separator, a polypropylene, polyethylene, polyvinylidene fluoride, polyester, a polyamide etc. are mentioned, for example.

The electrolytic solution is a solution in which an electrolyte is dissolved in a solvent for the electrolytic solution, and a known one can be used.
Examples of the solvent for the electrolytic solution include alcohol solvents, lactone solvents, amide solvents, nitrile solvents, water and the like. One solvent may be used alone, or two or more solvents may be used in combination.
Examples of alcohol solvents include ethylene glycol, diethylene glycol, propylene glycol, 1,4-butanediol, glycerin and the like.
Examples of lactone solvents include γ-butyrolactone, γ-valerolactone, δ-valerolactone and the like.
Examples of the amide solvents include N-methylformamide, N, N-dimethylformamide, N-methylacetamide, N-methylpyrrolidinone and the like.
Examples of nitrile solvents include acetonitrile, 3-methoxypropionitrile and the like.
Examples of the electrolyte include LiPF ₆ , LiBF ₄ , LiSbF ₆ , LiAsF ₆ , LiClO ₄ , LiBr ₄ , LiIO ₄ , LiAlCl _{4 and the} like. An electrolyte may be used individually by 1 type, and may use 2 or more types together.

The container contains the positive electrode, the negative electrode, the separator, and the electrolytic solution. Inside the container, a plurality of laminates arranged in the order of a positive electrode, a separator, a negative electrode, and a separator are stacked. Inside the container, a unit consisting of [positive electrode, separator, negative electrode, separator] is repeatedly laminated. In addition, the inside of the container is filled with an electrolytic solution.
The first lead wire is connected to the positive electrode or the positive electrode current collector. The end of the first lead wire not connected to the positive electrode or the positive electrode current collector is drawn to the outside of the container and connected to the terminal.
The second lead wire is connected to the negative electrode or the negative electrode current collector. The end of the second lead wire which is not connected to the negative electrode or the negative electrode current collector is drawn to the outside of the container and connected to the terminal.

The lithium ion secondary battery of the present embodiment uses the electrode of the above aspect as a negative electrode. Since the electrode of the above aspect has high conductivity, the battery characteristics of the secondary battery can be improved. Therefore, for example, the charging time of the secondary battery can be shortened.
In the present embodiment, when the negative electrode contains the carbon material together with the conductive resin particles, the conductivity of the negative electrode is further enhanced. In particular, when conductive resin particles containing 50% by mass or more of particles having a particle diameter of 0.3 μm or more and 20 μm or less are used in combination with a carbon material, the combined effect is more exhibited. Therefore, the conductivity of the negative electrode can be further improved, and the battery characteristics of the secondary battery can be further improved.

  Although the above embodiment is a lithium ion secondary battery, the battery of this aspect may be another secondary battery other than a lithium ion secondary battery, a primary battery, a fuel cell, etc. It may be In addition, an electrode may be used as a positive electrode.

(Production Example 1)
Dissolve 206 g of sodium styrene sulfonate in 1000 ml of ion-exchanged water, add 1.14 g of an ammonium persulfate oxidizing agent solution previously dissolved in 10 ml of water while stirring at 80 ° C. for 20 minutes, and add the solution to 12 Stir for hours.
1000 ml of sulfuric acid diluted to 10% by mass was added to the obtained sodium styrene sulfonate-containing solution, and 1000 ml of a solvent of the polystyrene sulfonic acid-containing solution was removed using an ultrafiltration method. To the residue, 2000 ml of deionized water was added, about 2000 ml of solvent was removed using ultrafiltration, and the polystyrenesulfonic acid was washed with water. This ultrafiltration operation was repeated three times.
Water in the obtained solution was removed under reduced pressure to obtain colorless solid polystyrene sulfonic acid.

(Production Example 2)
A solution of 14.2 g of 3,4-ethylenedioxythiophene and 36.7 g of polystyrene sulfonic acid obtained in Production Example 1 dissolved in 2000 ml of ion-exchanged water was mixed at 20 ° C. The mixed solution thus obtained is kept at 20 ° C. and 29.64 g of ammonium persulfate dissolved in 200 ml of ion-exchanged water and 8.0 g of a ferric sulfate oxidation catalyst solution are slowly added while stirring. The reaction was allowed to stir for 3 hours.
To the resulting reaction solution, 2000 ml of ion exchanged water was added, and about 2000 ml of solvent was removed using ultrafiltration. This operation was repeated three times. Next, 200 ml of sulfuric acid diluted to 10% by mass and 2000 ml of ion exchanged water were added to the obtained solution, and about 2000 ml of solvent was removed using ultrafiltration. To the residue, 2000 ml of ion exchanged water was added, about 2000 ml of solvent was removed using ultrafiltration, and polystyrene sulfonate-doped poly (3,4-ethylenedioxythiophene) (PEDOT-PSS) was washed with water. This operation was repeated eight times to obtain a PEDOT-PSS aqueous dispersion having a solid concentration of 1.2% by mass. PEDOT-PSS contained in this PEDOT-PSS aqueous dispersion is not particles having a particle diameter of 0.3 μm or more, and is not hydrophobized by an amine compound.

(Production Example 3)
A solution of 2.5 g of 3,4-ethylenedioxythiophene and a solution of 12.5 g of the polystyrene sulfonic acid of Preparation Example 1 in 500 ml of deionized water was mixed at 30 ° C.
The mixed solution thus obtained is kept at 30 ° C., and while stirring, 5.5 g of ammonium persulfate dissolved in 44.35 ml of ion exchanged water and 0.15 g of a ferric sulfate oxidation catalyst solution are slowly added. The reaction was allowed to stir for 8 hours. Thereby, 2.7 mass% polystyrenesulfonic acid dope poly (3, 4- ethylene dioxythiophene) water dispersion (PEDOT-PSS water dispersion) was obtained.
A mixed solution of 53.0 g of trioctylamine and 500 g of isopropanol was added to 565.0 g of the aqueous dispersion of PEDOT-PSS to precipitate a trioctylamine adduct of PEDOT-PSS. The precipitated trioctylamine adduct of PEDOT-PSS was separated by filtration and washed with 100 g of water, and then washed with 100 g of acetone to take out 18.8 g of the trioctylamine adduct of PEDOT-PSS as a solid.

(Production Example 4)
A solution of 2.5 g of 3,4-ethylenedioxythiophene and a solution of 12.5 g of the polystyrene sulfonic acid of Preparation Example 1 in 500 ml of deionized water was mixed at 30 ° C.
The mixed solution thus obtained is kept at 30 ° C., and while stirring, 5.5 g of ammonium persulfate dissolved in 44.35 ml of ion exchanged water and 0.15 g of a ferric sulfate oxidation catalyst solution are slowly added. The reaction was allowed to stir for 8 hours. Thereby, 2.7 mass% polystyrenesulfonic acid dope poly (3, 4- ethylene dioxythiophene) water dispersion (PEDOT-PSS water dispersion) was obtained.
A mixed solution of 40.4 g of trihexylamine and 500 g of isopropanol was added to 565.0 g of the aqueous dispersion of PEDOT-PSS to precipitate a trihexylamine adduct of PEDOT-PSS. The precipitated trihexylamine adduct of PEDOT-PSS was separated by filtration and washed with 100 g of water, and then washed with 100 g of acetone to take out the trihexylamine adduct of PEDOT-PSS as a solid 16.7 g.

Example 1
200 g of ethyl acetate was added to 18.8 g of the trioctylamine adduct of PEDOT-PSS obtained in Preparation Example 3, and a PEDOT-PSS trichloride was added for 10 minutes with a stirring number of 7000 rpm using a homogenizer (L4RT manufactured by SILVERSON). The octylamine adduct was ground. Thus, an ethyl acetate dispersion of conductive resin particles consisting of a trioctylamine adduct of PEDOT-PSS was obtained. The particle size distribution of the obtained dispersion was measured using a dynamic light scattering particle size distribution measuring apparatus (FPAR 1000, manufactured by Otsuka Electronics Co., Ltd.). The measurement results are shown in Table 1. The particle size distribution of the organic solvent dispersion of PEDOT-PSS amine adduct was also measured in the following examples.
The conductive resin particle dispersion is described in No. Using a bar coater of 12, apply to a polyethylene terephthalate film (Lumirror T-60 manufactured by Toray Industries, Inc., average thickness 60 μm) and dry at 100 ° C. for 1 minute to form an electrode, thereby obtaining an electrode film. The

(Example 2)
An electrode film was obtained in the same manner as in Example 1 except that ethyl acetate added to 18.8 g of the trioctylamine adduct of PEDOT-PSS was changed to butyl acetate.

(Example 3)
An electrode film was obtained in the same manner as in Example 1 except that ethyl acetate added to 18.8 g of the trioctylamine adduct of PEDOT-PSS was changed to diethylene glycol diethyl ether (denoted as "DEGDE" in the table). The

(Example 4)
An electrode film was obtained in the same manner as in Example 1, except that the ethyl acetate added to 18.8 g of the trioctylamine adduct of PEDOT-PSS was changed to toluene.

(Example 5)
An electrode film was obtained in the same manner as in Example 1 except that ethyl acetate added to 18.8 g of the trioctylamine adduct of PEDOT-PSS was changed to isopropanol.

(Example 6)
An electrode film was obtained in the same manner as in Example 1 except that ethyl acetate added to 18.8 g of the trioctylamine adduct of PEDOT-PSS was changed to methyl ethyl ketone.

(Example 7)
An electrode film was obtained in the same manner as in Example 1 except that ethyl acetate added to 18.8 g of the trioctylamine adduct of PEDOT-PSS was changed to heptane.

(Example 8)
An electrode was prepared in the same manner as in Example 1 except that 18.8 g of the trioctylamine adduct of PEDOT-PSS obtained in Preparation Example 3 was changed to 16.7 g of the trihexylamine adduct of PEDOT-PSS obtained in Preparation Example 4 I got a film.

(Comparative example 1)
Using a PEDOT-PSS aqueous dispersion of Preparation Example 2 instead of an ethyl acetate dispersion of conductive resin particles consisting of a trioctylamine adduct of PEDOT-PSS, and coating it on a polyethylene terephthalate film as in Example 1 An electrode film was obtained.

(Example 9)
10 g of ethyl acetate dispersion of conductive resin particles comprising trioctylamine adduct of PEDOT-PSS of Example 1 with carbon paste (Lion Specialty Chemicals, Inc., FD-7006H, dispersion medium: N-methylpyrrolidone, Solid content concentration: 10% by mass) was added. The dispersion obtained is referred to no. Using a bar coater of 12, apply to a polyethylene terephthalate film (Lumirror T-60 manufactured by Toray Industries, Inc., average thickness 60 μm) and dry at 120 ° C. for 1 minute to form an electrode, thereby obtaining an electrode film. The

(Example 10)
An electrode film was obtained in the same manner as in Example 9 except that the ethyl acetate dispersion of the conductive resin particles of Example 1 was changed to the butyl acetate dispersion of the conductive resin particles of Example 2.

(Example 11)
An electrode film was obtained in the same manner as in Example 9 except that the ethyl acetate dispersion liquid of the conductive resin particles of Example 1 was changed to diethylene glycol diethyl ether of the conductive resin particles of Example 3.

(Example 12)
An electrode film was obtained in the same manner as in Example 9 except that the ethyl acetate dispersion of the conductive resin particles of Example 1 was changed to the toluene dispersion of the conductive resin particles of Example 4.

(Example 13)
An electrode film was obtained in the same manner as in Example 9 except that the ethyl acetate dispersion of the conductive resin particles of Example 1 was changed to the isopropanol dispersion of the conductive resin particles of Example 5.

(Example 14)
An electrode film was obtained in the same manner as in Example 9 except that the ethyl acetate dispersion of the conductive resin particles of Example 1 was changed to the methyl ethyl ketone dispersion of the conductive resin particles of Example 6.

(Example 15)
An electrode film was obtained in the same manner as in Example 9 except that the ethyl acetate dispersion of the conductive resin particles of Example 1 was changed to the heptane dispersion of the conductive resin particles of Example 7.

(Example 16)
An electrode film was obtained in the same manner as in Example 9 except that the ethyl acetate dispersion of the conductive resin particles of Example 1 was changed to the ethyl acetate dispersion of the conductive resin particles of Example 8.

(Comparative example 2)
In Example 9, using the aqueous dispersion of PEDOT-PSS of Preparation Example 2 instead of the ethyl acetate dispersion of conductive resin particles consisting of a trioctylamine adduct of PEDOT-PSS, the coating is carried out in the same manner as Example 9. However, the dispersion gelled. Therefore, it could not be applied to the film.

(Comparative example 3)
An electrode film was obtained in the same manner as in Example 9, except that 10 g of ethyl acetate dispersion of conductive resin particles consisting of a trioctylamine adduct of PEDOT-PSS was changed to 10 g of ethyl acetate.

<Evaluation>
[Surface resistance]
The surface resistance value of the electrode film of each example was measured according to JIS K 7194 using a resistivity meter (Hiresta manufactured by Mitsubishi Chemical Analytic Co., Ltd.) under the condition of an applied voltage of 10 V. The measurement results of the surface resistance value are shown in Tables 1 and 2.
It is assumed that the higher the surface resistance of the electrode film, that is, the higher the conductivity of the electrode film, the better the battery characteristics when the electrode film is used as an electrode of a secondary battery. For example, it is assumed that the higher the conductivity of the electrode film, the faster the charge and discharge speed when the electrode film is used as an electrode of a secondary battery.

The conductive particles in each example contained particles with a particle diameter range of 0.3 μm to 20 μm and a particle diameter of 0.3 μm to 20 μm in the main peak of the particle size distribution. Moreover, in the conductive particles in each example, the content of particles having a particle diameter of 0.3 μm or more and 20 μm or less was 80% or more.
In addition, the electroconductive particle in each Example consists only of the particle | grains in the particle diameter range of the main peak, and the particle | grains of particle diameter over 20 micrometers, and the particle | grains of the other particle diameter range were not confirmed.

The electrode films of Examples 1 to 8 including conductive resin particles consisting of an amine compound adduct of PEDOT-PSS in the electrode had low surface resistance. On the other hand, the electrode film of Comparative Example 1 in which PEDOT-PSS contained in the electrode was not hydrophobized by the amine compound had a high surface resistance value. From this, it is surmised that the secondary batteries using the electrode films of Examples 1 to 8 are superior to the secondary batteries using the electrode film of Comparative Example 1 in battery characteristics such as charge and discharge speed.
The electrode films of Examples 9 to 16 containing conductive resin particles consisting of amine adducts of PEDOT-PSS and carbon in the electrode were the same as those of Comparative Example 3 containing carbon in the electrode and no conductive resin particles. Also, the surface resistance value was low. From this, it is surmised that the secondary battery using the electrode film of Examples 9-16 is superior to the secondary battery using the electrode film of Comparative Example 3 in battery characteristics such as charge and discharge speed.

Claims (19)

An electrode containing conductive resin particles, wherein
The conductive resin particles are resin particles containing a conductive complex,
The electrode, wherein the conductive complex includes a π-conjugated conductive polymer and a polyanion, and an amine compound is added to an anion group of a part of the polyanion.   The electrode according to claim 1, wherein the conductive resin particles include particles having a particle diameter in a range of 0.3 μm to 20 μm.   The electrode according to claim 2, wherein the conductive resin particles have a content of particles having a particle diameter in the range of 0.3 μm to 20 μm of 50% or more.   The electrode according to any one of claims 1 to 3, further comprising a carbon material.   The electrode according to any one of claims 1 to 4, wherein the π-conjugated conductive polymer is poly (3,4-ethylenedioxythiophene).   The electrode according to any one of claims 1 to 5, wherein the polyanion is polystyrene sulfonic acid.   The battery which has an electrode as described in any one of Claims 1-6.   The battery according to claim 7, which is a secondary battery.   The battery according to claim 7, which is a lithium ion battery.   The battery according to any one of claims 7 to 9, wherein the electrode is used as a negative electrode. a precipitation step of adding an amine compound to an aqueous dispersion of a conductive complex containing a π-conjugated conductive polymer and a polyanion, and depositing the conductive complex to form a precipitate;
A recovery step of recovering the precipitate;
A pulverizing step of pulverizing the collected precipitate so as to form particles having a particle diameter in the range of 0.3 μm to 20 μm to form conductive resin particles;
A forming step of forming the conductive resin particles;
A method of manufacturing an electrode, comprising:   The method according to claim 11, wherein in the pulverizing step, the precipitate is pulverized so that particles having a particle diameter in the range of 0.3 μm to 20 μm are formed.   The method of producing an electrode according to claim 11 or 12, wherein in the pulverizing step, the precipitate is wet pulverized in a dispersion medium to obtain a conductive resin particle dispersion liquid in which the conductive resin particles are dispersed in the dispersion medium. .   The method for producing an electrode according to claim 13, wherein the dispersion medium is at least one selected from the group consisting of ethyl acetate, butyl acetate, heptane, toluene, and diethylene glycol diethyl ether.   The manufacturing method of the electrode of Claim 13 or 14 which removes a dispersion medium from the said conductive resin particle dispersion liquid in the said formation process.   The manufacturing method of the electrode of Claim 15 which adds a carbon material to the said conductive resin particle dispersion liquid before the said formation process.   The manufacturing method of the electrode as described in any one of Claims 11-16 whose said (pi) conjugated system conductive polymer is poly (3, 4- ethylene dioxythiophene).   The manufacturing method of the electrode as described in any one of Claims 11-17 whose said polyanion is a polystyrene sulfonic acid.   The conductive resin particle dispersion liquid is coated on a substrate in the forming step, and dried to form an electrode containing the conductive resin particle on the surface of the substrate. The manufacturing method of the electrode as described in any one.