JP2017188283A - Composition for power storage device electrode formation, power storage device electrode, and power storage device - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a composition for electrode formation, which is superior in suitability to coating an electrode, which is arranged for forming a power storage device superior in charge and discharge characteristics, and which is effective in easing the aggregation of an organic active material.SOLUTION: The above problem is solved by a composition for power storage device electrode formation, which comprises an organic active material and a cationic dispersant. The composition for power storage device electrode formation further comprises a carbon material as a conductive assistant. Also, the above problem is solved by an electrode for a power storage device, which comprises a current collector, and a mixture layer formed from the composition for power storage device electrode formation.SELECTED DRAWING: None

Description

  The present invention relates to a composition for forming an electricity storage device electrode, an electricity storage device electrode, and an electricity storage device.

  In recent years, small portable electronic devices such as digital cameras and mobile phones have been widely used. These electronic devices have always been required to minimize the volume and reduce the weight, and the batteries to be mounted are also required to be small, light and large capacity. In addition to automobile applications, battery applications such as stationary applications are expanding, and the required performance is increasing year by year. Furthermore, in applications where high output is required, a capacitor or the like may be used, and this also requires improved performance.

  In order to meet such demands, attention has been paid to the use of organic compounds as power storage materials. Organic compounds can be designed with a wider variety of molecules than inorganic compounds. For this reason, when an organic compound is used as a power storage material, a power storage device having various characteristics can be realized by molecular design.

  In addition, unlike metal oxides that have been used as conventional power storage materials, organic compounds do not use precious metal elements or harmful heavy metal elements, so stable supply of raw materials can be expected, and safety in terms of disposal and recycling Improvement can be expected.

  Examples of using organic compounds as power storage materials include, for example, conductive polymers such as polyaniline and polythiophene (Patent Document 1), compounds having stable radicals (Patent Document 2), and organic sulfur compounds containing sulfide bonds (Patent Document) 3). In addition, many materials are summarized as a review by Yanliang Liang et al. (Non-patent Document 1).

  However, in such an organic compound serving as a power storage material, partial aggregation often occurs in the formed mixture layer. This is because, for example, it is insoluble in the composite ink used for electrode formation, and the dispersibility is insufficient in the composite ink. In that case, a uniform coating film cannot be obtained due to aggregates during electrode coating. In addition, a resistance distribution occurs on the electrode due to partial aggregation, and current may concentrate when used as an electricity storage device, resulting in problems such as promoting partial heat generation and deterioration.

  In general, an organic compound is an insulator. Therefore, for example, when an oxidation-reduction reaction for charge accumulation is performed as a battery, if aggregation occurs, electrons cannot be transferred to the inside of the aggregate and become unreacted, and the discharge capacity can be extracted. There may not be. Alternatively, even when the electrolytic solution does not penetrate into the aggregate, the above problem may occur due to insufficient supply of ions related to the oxidation-reduction reaction.

JP-A-61-124070 JP 2004-207249 A JP 2001-273901 A

Adv. EnergyMatter. (2012), 2,742-769.

  An object of the present invention is an electrode forming composition for forming an electricity storage device having excellent electrode coatability and excellent charge / discharge characteristics, and an electrode forming composition that is effective in reducing aggregation of an organic active material. Is to provide.

In the present invention, aggregation of the organic active material can be alleviated by using a cationic dispersant.
That is, this invention relates to the composition for electrical storage device electrode formation containing an organic active material and a cationic dispersing agent.

  Moreover, this invention relates to the said composition for electrical storage device electrode formation containing the carbon material which is a conductive support agent further.

Moreover, this invention relates to the electrode for electrical storage devices which comprises the electrical power collector and the composite material layer formed from the said any composition for electrical storage device electrodes formation.

  The present invention also relates to an electricity storage device including a positive electrode, a negative electrode, and an electrolyte, wherein at least one of the positive electrode or the negative electrode is the electrode for the electricity storage device.

  Since the dispersibility of the organic active material and its stability were improved by using the cationic dispersant, the composition for forming an electrode of the present invention could be obtained. The composition for electrode formation of the present invention can form a composite material layer with little aggregation, and can provide an electricity storage device having excellent charge / discharge characteristics.

The electrode for an electricity storage device can be obtained by various methods.
For example, on the surface of a current collector such as a metal foil,
(1) A composition for forming an electricity storage device electrode containing an active material and a cationic dispersant and a liquid medium (hereinafter referred to as composite ink),
(2) a composite ink containing an active material, a cationic dispersant, a conductive aid, and a liquid medium;
(3) a mixed ink containing an active material, a cationic dispersant, a binder and a liquid medium;
(4) A composite ink containing an active material, a cationic dispersant, a conductive aid, a binder, and a liquid medium,
It can be used to form a composite layer and obtain an electrode.

  Alternatively, an underlayer is formed on the surface of the current collector of the metal foil using a composition for forming an underlayer containing a conductive additive and a liquid medium, and the above-mentioned composite ink (1 ) To (4) or other composite inks to form a composite layer and obtain an electrode.

In either case, the fact that the dispersion state of the active material affects the performance of the electricity storage device has been described in detail in the section of the background art.
First, the cationic dispersant in the present invention will be described. The cationic dispersant is a polymeric dispersant or surfactant containing a cyclic amino group, a partially or completely neutralized skeleton, and a quaternary ammonium salt.

  The cationic dispersant is adsorbed on the organic active material and has a function of improving the dispersibility and stability of the organic active material. Examples of the cationic dispersant include polymer dispersants and surfactants, and compounds generally known as dispersants can be used. The cationic dispersant is preferably a polymer system in consideration of the dispersibility of the organic active material and its stability.

  Examples of polymeric cationic dispersants include homopolymers of polymerizable monomers such as N, N-dimethylaminoethyl (meth) acrylate, N, N-diethylamino (meth) acrylate, vinylpyridine, and acids thereof. A neutralized material is mentioned.

The high molecular weight cationic dispersant may be a copolymer or an acid neutralized product thereof. The ratio of the monomers constituting the copolymer that is the polymeric cationic dispersant used in the present invention is, when the total of the monomers is 100% by mass,
10 to 70% by mass of an ethylenically unsaturated monomer (a1) having a cyclic amino group and a partially or completely neutralized skeleton and a quaternary ammonium salt,
0 to 70% by mass of an ethylenically unsaturated monomer (a2) having an aromatic or aliphatic skeleton,
It is preferable that the other monomer (a3) other than (a1) and (a2) is 0 to 90% by mass.
More preferably, they are (a1): 15-60 mass%, (a2): 20-70 mass%, (a3): 0-50 mass%.

The ethylenically unsaturated monomer (a1) having a cyclic amino group and a partially or completely neutralized skeleton and a quaternary ammonium salt will be described.
Examples of the monomer having a cyclic amino group include N, N-dimethylaminoethyl (meth) acrylate, N, N-diethylamino (meth) acrylate, methylethylaminoethyl (meth) acrylate, N, N-dimethylamino. Propyl (meth) acrylate, allylamine, aminostyrene, dimethylaminostyrene, diethylaminostyrene, vinylpyridine, and examples of monomers having two ethylenically unsaturated groups in one molecule include diallylamine and diallylmethylamine. Can do.

  Monomers having a quaternary ammonium salt include N- (meth) acryloyloxyethyl-N, N, N-trimethylammonium chloride, N- (meth) acryloyloxyethyl-N-ethyl-N, N-dimethylammonium. Monoethyl sulfate, N- [3- {N ′-(meth) acryloyloxyethyl-N ′, N′-diethylammonium} -2-hydroxypropyl] -N, N, N-triethylammonium chloride, N- (meta ) Acryloylaminopropyl-N, N, N-trimethylammonium chloride, N- (meth) acryloylaminopropyl-N-ethyl-N, N-dimethylammonium monoethyl sulfate, N- [3- {N ′-(meth)] Acryloylaminopropyl-N ′, N′-dimethylammonium} 2-hydroxypropyl] -N, N, N- trimethylammonium chloride, and the like.

Next, the ethylenically unsaturated monomer (a2) having an aromatic or aliphatic skeleton will be described.
Examples of the monomer having an aromatic ring include styrene, α-methylstyrene, and benzyl (meth) acrylate.

  Aliphatic skeletons include saturated or unsaturated hydrocarbon groups, and aliphatic groups that are saturated or unsaturated hydrocarbons bonded by one or more heteroatoms. Among them, saturated hydrocarbon groups or ether bonds are preferred. Saturated aliphatic groups having are preferred.

  Examples of the saturated hydrocarbon group include a chain saturated hydrocarbon group and a cyclic saturated hydrocarbon group.

Specific examples of the monomer having a chain saturated hydrocarbon group include 1 to 22 carbon atoms such as methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, and butyl (meth) acrylate. And an alkyl group-containing acrylate having a C 2-12 alkyl group, more preferably a C 2-8 alkyl group, or a corresponding methacrylate. These alkyl groups may be branched, and specific examples include isopropyl (meth) acrylate, isobutyl (meth) acrylate, tertiary butyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, 2-butylhexyl (meth) ) Acrylate and the like.
Moreover, fatty acid vinyl compounds such as vinyl acetate, vinyl butyrate, vinyl propionate, vinyl hexanoate, vinyl caprylate, vinyl laurate, vinyl palmitate, vinyl stearate and the like can be mentioned.
Furthermore, α-olefin compounds such as 1-hexene, 1-octene, 1-decene, 1-dodecene, 1-tetradecene, 1-hexadecene and the like can be mentioned.

  Examples of the monomer having a cyclic saturated hydrocarbon group include isobornyl (meth) acrylate, dicyclopentanyl (meth) acrylate, cyclohexyl (meth) acrylate, trimethylcyclohexyl (meth) acrylate, 1-adamantyl (meth) acrylate, and the like. Can be mentioned.

Examples of the saturated aliphatic group having an ether bond include a polyoxyalkylene structure, and examples of the monomer having a polyoxyalkylene structure include diethylene glycol mono (meth) acrylate, polyethylene glycol mono (meth) acrylate, and polypropylene glycol mono (meta). ) Acrylate, etc. Mono-acrylate or monomethacrylate having a hydroxyl group at the end and a polyoxyalkylene chain, methoxyethylene glycol (meth) acrylate, methoxydiethylene glycol (meth) acrylate, methoxypolyethylene glycol (meth) acrylate, methoxypolypropylene Glycol (meth) acrylate and other monoacrylates having an alkoxy group at the end and having a polyoxyalkylene chain There is an acrylate. Examples of the alkyl vinyl ether compound include butyl vinyl ether and ethyl vinyl ether.
Further, a cyclic compound such as glycidyl (meth) acrylate, tetrahydrofurfuryl (meth) acrylate, or the like may be used.

Next, the monomer (a3) other than the above (a1) and (a2) will be described.
Examples of the monomer having a hydroxyl group include 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate, glycerol mono (meth) acrylate, 4-hydroxystyrene, and vinyl alcohol. And allyl alcohol.
Examples of the monomer that is a derivative of vinyl alcohol include vinyl esters such as vinyl acetate, vinyl propionate, and vinyl versatate. A hydroxyl group can be formed by copolymerizing these vinyl esters and saponifying the obtained copolymer with sodium hydroxide or the like.

  Examples of nitrogen-containing monomers other than amino groups include N-vinyl-2-pyrrolidone, (meth) acrylamide, N-vinylacetamide, N-methylol (meth) acrylamide, and N-methoxymethyl- (meth) acrylamide. Examples thereof include monoalkylol (meth) acrylamide, N, N-di (methylol) acrylamide, N-methylol-N-methoxymethyl (meth) acrylamide, N, N-di (methoxymethyl) acrylamide and the like.

  Furthermore, as other monomers, perfluoromethylmethyl (meth) acrylate, perfluoroethylmethyl (meth) acrylate, 2-perfluorobutylethyl (meth) acrylate, 2-perfluorohexylethyl (meth) acrylate, etc. Perfluoroalkylalkyl (meth) acrylates having a C 1-20 perfluoroalkyl group; perfluoroalkyls such as perfluorobutylethylene, perfluorohexylethylene, perfluorooctylethylene, perfluorodecylethylene, alkylenes, etc. Perfluoroalkyl group-containing vinyl monomers, vinyltrichlorosilane, vinyltris (βmethoxyethoxy) silane, vinyltriethoxysilane, γ- (meth) acryloxypropyltrimethoxysilane, etc. Such as Nord group-containing vinyl compounds and derivatives thereof can be cited, it is possible to use a plurality of these groups.

  Examples of the ethynyl compound include acetylene, ethynylbenzene, ethynyltoluene, 1-ethynyl-1-cyclohexanol and the like. These can be used alone or in combination of two or more.

  In addition, the mass average molecular weight of the polymer dispersant is preferably 1000 to 100,000, and more preferably 5,000 to 50,000, from the viewpoint of good dispersibility of the organic active material.

  Examples of the cationic surfactant include trimethylammonium chloride, dodecyltrimethylammonium chloride, dodecyltrimethylammonium bromide, distearyldimethylammonium chloride, hexadecyltrimethylammonium bromide, 1-dodecylpyridinium chloride, and the like.

  A neutralizing agent may be added to the cationic dispersant. By neutralizing part or all of the basic functional group of the cationic dispersant, the salt of the basic functional group is easily dissociated in an aqueous medium, and is more easily charged. For this reason, the conductive carbon surface and the positive and negative electrode active material surfaces on which the neutralized cationic dispersant is adsorbed are charged, and dispersibility is further improved by the repulsion.

  Examples of the acid used for this neutralization include inorganic acids such as sulfuric acid, hydrochloric acid, phosphoric acid, nitric acid, hydrobromic acid, hydroiodic acid, and carboxylic acids, phosphonic acids, sulfonic acids, aromatic hydroxy groups, etc. An organic acid containing

  In addition, the amount of acid used for the cationic dispersant having a basic functional group is preferably 0.1 to 10 equivalents of the basic functional group of the cationic dispersant to be used, more preferably 0.8. 8 to 1.2 equivalents.

(Active material)
The active material used in the composite ink will be described below. The organic active material used in the present invention is one in which an organic molecule itself causes a redox reaction, or one in which a charge / discharge reaction of a battery can be caused by the organic molecule functioning as a charge carrier.

  The organic active material is not particularly limited, but is a conductive polymer such as polyaniline, polyacetylene, polypyrrole, polythiophene, 1,4-benzoquinone, 2,5-dimethoxy-1,4-benzoquinone, 9,10-anthraquinone, Quinone compounds such as phenanthrenequinone, 5,7,12,14-pentacentetron and their polymer compounds, carbonyl compounds such as naphthalenetetracarboxylic dianhydride, perylenetetracarboxylic dianhydride, dilithium rosinate and polymer compounds thereof Thiocarbonyl compounds such as rubeanic acid and polymer compounds thereof, stable radical compounds such as 2,2,6,6-tetramethylpiperidine-N-oxyl and polymer compounds thereof, indigo, indigo carmine, triquinoxalinylene, trioxoto Angyuren, and heterocyclic compound or the polymer compound such as tetrathiafulvalene can also be used.

  An organic secondary battery as an electricity storage device is a secondary battery using an organic active material as a positive electrode or a negative electrode. The configuration of the secondary battery will be described later.

  The positive electrode active material for the organic secondary battery is selected from the organic active materials described above. Further, an inorganic active material may be mixed, or an organic active material and an inorganic active material may be combined and used.

Examples of the inorganic active material include oxides of transition metals such as Fe, Co, Ni, and Mn, composite oxides with lithium, and inorganic compounds such as transition metal sulfides. Specifically, transition metal oxide powders such as MnO, V ₂ O ₅ , V ₆ O ₁₃ , TiO ₂ , layered structure lithium nickelate, lithium cobaltate, lithium manganate, spinel structure lithium manganate, etc. Examples thereof include composite oxide powders of lithium and transition metals, lithium iron phosphate materials that are phosphate compounds having an olivine structure, and transition metal sulfide powders such as TiS ₂ and FeS.

As an anode active material for an organic secondary battery, a material capable of doping or intercalating lithium ions is desirable. For example, metal Li, alloys thereof such as tin alloy, silicon alloy, lead alloy, Li _x Fe ₂ O ₃ , Li _x Fe ₃ O ₄ , Li _x WO ₂ (where x is a number, 0 <X ≦ 2), metal oxide inorganic compounds such as lithium titanate, lithium vanadate, lithium siliconate, etc., conductive polymer organic active materials such as polyacetylene, poly-p-phenylene, soft Amorphous carbonaceous materials such as carbon and hard carbon, artificial graphite such as highly graphitized carbon materials, or carbonaceous powder such as natural graphite, carbon black, mesophase carbon black, resin-fired carbon material, gas-grown carbon fiber, Examples thereof include carbon-based materials such as carbon fibers. These negative electrode active materials can be used alone or in combination.
Different organic active materials may be used in combination as a negative electrode active material.

(Conductive aid)
Next, the carbon material that is a conductive aid will be described.
The carbon material that is a conductive aid in the present invention is not particularly limited as long as it is a carbon material having conductivity, but graphite, carbon black, conductive carbon fiber (carbon nanotube, carbon nanofiber, carbon fiber). ), Fullerene or the like can be used alone or in combination of two or more. From the viewpoint of conductivity, availability, and cost, it is preferable to use carbon black.

  Carbon black is a furnace black produced by continuously pyrolyzing a gas or liquid raw material in a reactor, especially ketjen black using ethylene heavy oil as a raw material. Channel black that has been rapidly cooled and precipitated, thermal black obtained by periodically repeating combustion and thermal decomposition using gas as a raw material, and particularly various types such as acetylene black using acetylene gas as a raw material, or 2 More than one type can be used in combination. Ordinarily oxidized carbon black, hollow carbon and the like can also be used.

  The oxidation treatment of carbon is performed by treating carbon at a high temperature in the air or by secondary treatment with nitric acid, nitrogen dioxide, ozone, etc., for example, such as phenol group, quinone group, carboxyl group, carbonyl group. This is a treatment for directly introducing (covalently bonding) an oxygen-containing polar functional group to the carbon surface, and is generally performed to improve the dispersibility of carbon. However, since it is common for the conductivity of carbon to fall, so that the introduction amount of a functional group increases, it is preferable to use the carbon which has not been oxidized.

As the specific surface area of the carbon black used increases, the number of contact points between the carbon black particles increases, which is advantageous in reducing the internal resistance of the electrode. Specifically, the specific surface area (BET) determined from the amount of nitrogen adsorbed is 20 m ² / g or more and 1500 m ² / g or less, preferably 50 m ² / g or more and 1500 m ² / g or less, more preferably 100 m ^2. / G or more and 1500 m ² / g or less are desirable.

  Further, the particle size of the carbon black to be used is preferably 0.005 to 1 μm, particularly preferably 0.01 to 0.2 μm in terms of primary particle size. However, the primary particle diameter here is an average of the particle diameters measured with an electron microscope or the like.

It is desirable that the dispersed particle size of the carbon material, which is a conductive additive, in the mixed ink is refined to 0.03 μm or more and 5 μm or less.
The dispersed particle size referred to here is a particle size (D50) that is 50% when the volume ratio of the particles is integrated from the fine particle size distribution in the volume particle size distribution. A particle size distribution meter such as a dynamic light scattering type particle size distribution meter ("Microtrack UPA" manufactured by Nikkiso Co., Ltd.).

  Examples of commercially available carbon black include Toka Black # 4300, # 4400, # 4500, # 5500 (Tokai Carbon Co., Furnace Black), Printex L and the like (Degussa Co., Furnace Black), Raven 7000, 5750, 5250, 5000 ULTRA III, 5000 ULTRA, etc., Conductex SC ULTRA, Conductex 975 ULTRA, etc., PUER BLACK 100, 115, 205 etc. # 3350B, # 3400B, # 5400B etc. (Mitsubishi Chemical Co., Furnace Black), MONARCH1400, 1300, 900, VulcanXC-7 R, BlackPearls2000, etc. (Cabot, Furnace Black), Ensaco250G, Ensaco260G, Ensaco350G, SuperP-Li (manufactured by TIMCAL), Ketjen Black EC-300J, EC-600JD (manufactured by Akzo), Denka Black, Denka Black HS Examples of graphite such as -100, FX-35 (manufactured by Denki Kagaku Kogyo Co., Ltd., acetylene black) include natural graphite such as artificial graphite, flake graphite, lump graphite, and earth graphite, but are not limited thereto. They may be used in combination of two or more.

  As the conductive carbon fibers, those obtained by firing from petroleum-derived raw materials are preferable, but those obtained by firing from plant-derived raw materials can also be used. For example, VGCF manufactured by Showa Denko Co., Ltd. manufactured with petroleum-derived raw materials can be mentioned.

The composite ink may further contain a binder.
The binder in the present invention is used for binding particles such as a conductive additive and other active materials, and the effect of dispersing these particles in a solvent is small.

  Examples of the binder include acrylic resins, polyurethane resins, polyester resins, phenol resins, epoxy resins, phenoxy resins, urea resins, melamine resins, alkyd resins, formaldehyde resins, silicone resins, fluororesins, carboxymethylcellulose and other cellulose resins, styrene -Synthetic rubbers such as butadiene rubber and fluorine rubber, conductive resins such as polyaniline and polyacetylene, and the like, and polymer compounds containing fluorine atoms such as polyvinylidene fluoride, polyvinyl fluoride, and tetrafluoroethylene. Further, a modified product, a mixture, or a copolymer of these resins may be used. These binders can be used alone or in combination.

  When an aqueous liquid medium is used, a binder generally called an aqueous emulsion can also be used. The aqueous emulsion is one in which the binder resin is dispersed in the form of fine particles without being dissolved in water.

  The emulsion to be used is not particularly limited, and examples thereof include (meth) acrylic emulsions, nitrile emulsions, urethane emulsions, diene emulsions (such as SBR), and fluorine emulsions (such as PVDF and PTFE). Unlike the water-soluble polymer, the emulsion preferably has excellent binding properties between particles and flexibility (film flexibility).

Examples of the liquid medium used in the present invention include alcohols, glycols, cellosolves, amino alcohols, amines, ketones, carboxylic acid amides, phosphoric acid amides, sulfoxides, carboxylic acid esters, phosphorus Examples include acid esters, ethers, nitriles, and water.
Among these, it is preferable to use a polar solvent having a relative dielectric constant of 15 or more. The relative dielectric constant is one of the indices indicating the strength of the polarity of the solvent, and is described in Asahara et al., “Solvent Handbook” (Kodansha Scientific Co., Ltd., 1990).

  Furthermore, a film forming aid, an antifoaming agent, a leveling agent, a preservative, a pH adjusting agent, a viscosity adjusting agent, and the like can be blended in the composite ink as necessary.

<Composite ink>
The composite ink for an electricity storage device essentially includes an active material and a liquid medium, and contains a conductive additive and a binder as necessary.

The composite ink is prepared so that the cationic dispersant is contained by the following method, for example, but is not limited thereto.
(1) An aqueous dispersion of an organic active material containing an organic active material, a cationic dispersant, and an aqueous liquid medium is obtained, and a conductive auxiliary agent and a binder are added to the aqueous dispersion to obtain a composite ink. it can.
The conductive auxiliary agent and the binder can be added simultaneously, or after adding the conductive auxiliary agent, the binder may be added, or vice versa.
(2) An aqueous dispersion of a conductive additive containing a conductive additive, a cationic dispersant, and an aqueous liquid medium can be obtained, and an organic active material and a binder can be added to the aqueous dispersion to obtain a composite ink. .
The organic active material and the binder can be added simultaneously, or after adding the organic active material, the binder may be added, or vice versa.
(3) An aqueous dispersion of an organic active material containing an organic active material, a cationic dispersant, a binder, and an aqueous liquid medium can be obtained, and a conductive additive can be added to the aqueous dispersion to obtain a composite ink.
(4) An aqueous dispersion of a conductive additive containing a conductive additive, a cationic dispersant, a binder and an aqueous liquid medium can be obtained, and an organic active material can be added to the aqueous dispersion to obtain a composite ink.
(5) A mixed ink can be obtained by almost simultaneously mixing an organic active material, a conductive additive, a cationic dispersant, a binder, and an aqueous liquid medium.

  The active material is preferably contained as much as possible. For example, the proportion of the active material in the solid material solid content is preferably 30% by mass or more and 99% by mass or less. When the conductive assistant is included, the proportion of the conductive assistant in the solid ink solid content is preferably 0.1 to 85% by mass. When the binder is included, the ratio of the binder to the solid material ink solid content is preferably 0.1 to 25% by mass.

  Although it depends on the coating method, the viscosity of the composite ink is preferably 100 mPa · s or more and 30,000 mPa · s or less in the range of 5 to 90% by mass of the solid content.

(Disperser / Mixer)
As an apparatus used for obtaining the composition for forming an electrode of the present invention, a disperser or a mixer usually used for pigment dispersion or the like can be used.

  For example, mixers such as dispersers, homomixers, or planetary mixers; homogenizers such as “Clearmix” manufactured by M Technique, or “fillmix” manufactured by PRIMIX; paint conditioner (manufactured by Red Devil), ball mill, sand mill (Shinmaru Enterprises "Dynomill", etc.), Attritor, Pearl Mill (Eirich "DCP Mill", etc.), or Coball Mill, etc .; Media type dispersers; Wet Jet Mill (Genus, "Genus PY", Sugino Media-less dispersers such as “Starburst” manufactured by Machine, “Nanomizer” manufactured by Nanomizer, etc., “Claire SS-5” manufactured by M Technique, or “MICROS” manufactured by Nara Machinery; or other roll mills, etc. Although The present invention is not limited to these. Moreover, as the disperser, it is preferable to use a disperser that has been subjected to a metal contamination prevention treatment from the disperser.

  For example, when using a media-type disperser, a disperser in which the agitator and vessel are made of a ceramic or resin disperser, or the surface of the metal agitator and vessel is treated with tungsten carbide spraying or resin coating. Is preferably used. As the media, it is preferable to use glass beads, ceramic beads such as zirconia beads or alumina beads. Moreover, also when using a roll mill, it is preferable to use a ceramic roll. Only one type of dispersion device may be used, or a plurality of types of devices may be used in combination.

<Electrode>
Of the composition for forming an electricity storage device electrode of the present invention, a composite ink can be applied and dried on a current collector to form a composite material layer, whereby an electrode for an electricity storage device can be obtained.
Alternatively, an electrode for an electricity storage device can be obtained by forming a base layer on the current collector and providing a composite layer on the base layer.

(Current collector)
The material and shape of the current collector used for the electrode are not particularly limited, and those suitable for various power storage devices can be appropriately selected.
For example, examples of the material for the current collector include metals and alloys such as aluminum, copper, nickel, titanium, and stainless steel. In the case of a lithium ion battery, aluminum is particularly preferable as the positive electrode material, and copper is preferable as the negative electrode material.
As the shape, a flat plate foil is generally used, but a roughened surface, a perforated foil shape, and a mesh current collector can also be used.

There is no restriction | limiting in particular as a method of apply | coating a mixture ink and the composition for base layer formation on a collector, A well-known method can be used.
Specific examples include die coating method, dip coating method, roll coating method, doctor coating method, knife coating method, spray coating method, gravure coating method, screen printing method or electrostatic coating method, and the like. Examples of methods that can be used include standing drying, blower dryers, hot air dryers, infrared heaters, and far-infrared heaters, but are not particularly limited thereto.
Moreover, you may perform the rolling process by a lithographic press, a calender roll, etc. after application | coating. The thickness of the electrode mixture layer is generally 1 μm or more and 500 μm or less, preferably 10 μm or more and 300 μm or less. When the underlayer is provided, the total thickness of the underlayer and the composite layer is generally 1 μm or more and 500 μm or less, preferably 10 μm or more and 300 μm or less.

<Power storage device>
(Battery configuration)
Using at least one of the positive electrode and the negative electrode, an electrode provided with a composite material layer made of the composition for forming an electricity storage device electrode of the present invention, an electricity storage device such as a secondary battery or a capacitor can be obtained. The electricity storage device includes a positive electrode, a negative electrode, and an electrolyte. The positive electrode and the negative electrode are disposed so as to face each other with a separator or the like interposed therebetween.

Secondary batteries include lithium ion secondary batteries, sodium ion secondary batteries, magnesium ion secondary batteries, sodium sulfur secondary batteries, lithium air secondary batteries, etc. Known electrolytes, separators, and the like can be used as appropriate.
Examples of the capacitor include a lithium ion capacitor, and conventionally known electrolytic solutions, separators, and the like can be used as appropriate.

(Electrolyte)
A case of a lithium ion secondary battery will be described as an example. As the electrolytic solution, an electrolyte containing lithium dissolved in a non-aqueous solvent is used.
As electrolytes, LiBF ₄ , LiClO ₄ , LiPF ₆ , LiAsF ₆ , LiSbF ₆ , LiCF ₃ SO ₃ , Li (CF ₃ SO ₂ ) ₂ N, LiC ₄ F ₉ SO ₃ , Li (CF ₃ SO ₂ ) ₃ C , LiI, LiBr, LiCl, LiAlCl, LiHF ₂ , LiSCN, or LiBPh ₄ (where Ph is a phenyl group), but is not limited thereto.
In addition, when lithium is not involved in charge / discharge, the electrolytes other than the above include tetraethylammonium tetrafluoroborate (TEABF ₄ ), triethylmethylammonium tetrafluoroborate (TEMABF ₄ ), triethylmethylammonium bis (trifluoro) Examples include (romethanesulfonyl) imide (TEMAFSI), tetraethylammonium bis (trifluoromethanesulfonyl) imide (TEATFSI), and tetrafluoroborate spiro- (1,1 ′)-bipyrrolidinium (SBP-BF ₄ ). Also, 1-ethyl-3-methylimidazolium tetrafluoroborate (EMI-BF ₄ ), diethylmethyl (2-methoxyethyl) ammonium tetrafluoroborate (DEME-BF ₄ ), trimethylpropylammonium bis (trifluoromethanesulfonyl) An ionic liquid such as imide (TMPA-TFSI) or butylmethylpyrrolidinium bis (trifluoromethanesulfonyl) imide (BMP-TFSI) can also be used.

The non-aqueous solvent is not particularly limited.
Carbonates such as ethylene carbonate, propylene carbonate, butylene carbonate, dimethyl carbonate, ethyl methyl carbonate, and diethyl carbonate;
Lactones such as γ-butyrolactone, γ-valerolactone, and γ-octanoic lactone;
Glymes such as tetrahydrofuran, 2-methyltetrahydrofuran, 1,3-dioxolane, 4-methyl-1,3-dioxolane, 1,2-methoxyethane, 1,2-ethoxyethane, and 1,2-dibutoxyethane;
Esters such as methyl formate, methyl acetate, and methyl propionate;
Sulfoxides such as dimethyl sulfoxide and sulfolane; and
Nitriles such as acetonitrile are exemplified. These solvents may be used alone or in combination of two or more.

  Furthermore, the electrolytic solution may be a gelled polymer electrolyte held in a polymer matrix. Examples of the polymer matrix include, but are not limited to, an acrylate resin having a polyalkylene oxide segment, a polyphosphazene resin having a polyalkylene oxide segment, and a polysiloxane having a polyalkylene oxide segment.

(separator)
Examples of the separator include, but are not limited to, a polyethylene nonwoven fabric, a polypropylene nonwoven fabric, a polyamide nonwoven fabric and those obtained by subjecting them to a hydrophilic treatment.

(Storage device (battery) structure)
The structure of a lithium ion secondary battery, a lithium ion capacitor, or an air secondary battery as an electricity storage device using the composition of the present invention is not particularly limited. Usually, a positive electrode and a negative electrode, and a separator provided as necessary It can be made into various shapes according to the purpose of use, such as a paper type, a cylindrical type, a coin type, and a laminated type.

  EXAMPLES The present invention will be described more specifically with reference to the following examples. However, the following examples do not limit the scope of rights of the present invention. In the examples and comparative examples, “part” represents “part by mass”. Unless otherwise specified, “dispersant” means “cationic dispersant”.

[Synthesis Example 1]
A reaction vessel equipped with a gas introduction tube, a thermometer, a condenser, and a stirrer was charged with 200.0 parts of n-butanol and replaced with nitrogen gas. The reaction vessel was heated to 110 ° C., and 60.0 parts of dimethylaminoethyl methacrylate, 100.0 parts of styrene, 40.0 parts of 4-hydroxybutyl acrylate, and V-601 (manufactured by Wako Pure Chemical Industries, Ltd.) as a polymerization initiator. ) 12.0 parts of the mixture was added dropwise over 2 hours to carry out the polymerization reaction. After completion of the dropwise addition, the mixture was further reacted at 110 ° C. for 3 hours, then 0.6 part of V-601 (manufactured by Wako Pure Chemical Industries, Ltd.) was added, and the reaction was further continued at 110 ° C. for 1 hour to obtain a copolymer solution. Obtained.
Furthermore, after cooling to room temperature, 13.9 parts of hydrochloric acid was added and neutralized. This is the amount that neutralizes 100% of dimethylaminoethyl methacrylate. Furthermore, after adding 400 parts of water and making it aqueous, it heated to 100 degreeC, butanol was azeotroped with water, and butanol was distilled off.
Dilution with water gave an aqueous solution of a dispersant having a nonvolatile content of 20%. Further, the viscosity of the aqueous solution of the dispersant having a nonvolatile content of 20% was 30 mPa · s.

[Synthesis Example 2]
In a reaction vessel equipped with a gas introduction tube, a thermometer, a condenser, and a stirrer, 200.0 parts of N-methyl-2-pyrrolidone (NMP) was charged and replaced with nitrogen gas. The reaction vessel was heated to 110 ° C., and 60.0 parts of dimethylaminoethyl methacrylate, 80.0 parts of styrene, 60.0 parts of 4-hydroxybutyl acrylate, and V-601 (manufactured by Wako Pure Chemical Industries, Ltd.) 12.0 Part of the mixture was added dropwise over 2 hours to conduct a polymerization reaction. After completion of the dropwise addition, the mixture was further reacted at 110 ° C. for 3 hours, then 0.6 parts of V-601 (manufactured by Wako Pure Chemical Industries, Ltd.) was added as a polymerization initiator, and the reaction was further continued at 110 ° C. for 1 hour. A polymer solution was obtained.
Dilution with NMP gave an NMP solution of a dispersant with a nonvolatile content of 20%. The viscosity of the dispersant solution having a nonvolatile content of 20% was 40 mPa · s.

[Synthesis Examples 3 to 7]
Except having changed into the composition shown in Table 1, each was synthesize | combined by the method similar to the synthesis example 1, and the cationic dispersing agent of the synthesis examples 3-7 was obtained.

ＤＭ：ジメチルアミノエチルメタクリレート
４ＶＰ：４−ビニルピリジン
ＤＡＣ：Ｎ，Ｎ−ジメチルアミノエチルアクリレートの塩化メチルによる４級化物
Ｓｔ：スチレン
ＢｚＭＡ：ベンジルメタクリレート
４ＨＢＡ：４−ヒドロキシブチルアクリレート
ＢＡ：ブチルアクリレート
ＰＭＥ−４００：メトキシポリエチレングリコールモノメタクリレート（日油社製）

DM: dimethylaminoethyl methacrylate 4VP: 4-vinylpyridine DAC: quaternized product of N, N-dimethylaminoethyl acrylate with methyl chloride St: styrene BzMA: benzyl methacrylate 4HBA: 4-hydroxybutyl acrylate BA: butyl acrylate PME-400 : Methoxypolyethylene glycol monomethacrylate (manufactured by NOF Corporation)

[Synthesis Example 8]
A reaction vessel equipped with a stirrer, a thermometer, a dropping funnel, and a reflux condenser was charged with 40 parts of ion-exchanged water and 0.2 part of ADEKA rear soap SR-10 (manufactured by ADEKA) as a surfactant. 48.5 parts of methacrylate, 50 parts of butyl acrylate, 1 part of acrylic acid, 0.5 part of 3-methacryloxypropyltrimethoxysilane, 53 parts of ion-exchanged water, and ADEKA rear soap SR-10 (manufactured by ADEKA) as a surfactant An additional 1% of the pre-emulsion, premixed with 1.8 parts, was added. After raising the internal temperature to 70 ° C. and sufficiently substituting with nitrogen, 10% of 10 parts of a 5% aqueous solution of potassium persulfate was added to initiate polymerization. After maintaining the reaction system at 70 ° C. for 5 minutes, the remaining pre-emulsion and the remaining 5% aqueous solution of potassium persulfate were added dropwise over 3 hours while maintaining the internal temperature at 70 ° C., and stirring was further continued for 2 hours. . After confirming that the conversion rate exceeded 98% by solid content measurement, the temperature was cooled to 30 ° C. 25% aqueous ammonia was added to adjust the pH to 8.5, and the solid content was adjusted to 50% with ion-exchanged water to obtain an aqueous emulsion binder.

[Example 1]
21 parts of organic active material 9,10-anthraquinone, 3 parts of the aqueous solution of Synthesis Example 1 as a dispersant (0.6 parts as solids) and 66.6 parts of water are mixed in a mixer and further mixed with a sand mill. 5.4 parts of acetylene black (DENKA BLACK HS-100: manufactured by Denki Kagaku Kogyo Co., Ltd.) and a binder (polytetrafluoroethylene 30-J: Mitsui DuPont) 4 parts of a fluorochemical company, 60% aqueous dispersion) were mixed to prepare a composite ink for an electricity storage device electrode. The degree of dispersion as a composite ink was determined by the following method.

[Example 2]
21 parts of the organic active material 9,10-anthraquinone, 3 parts of the NMP solution of Synthesis Example 2 which is the dispersant (0.6 parts as solids), 40.6 parts of NMP are placed in a kneader, and further dispersed. 5.4 parts of furnace black (Mitsubishi Carbon # 3050B: manufactured by Mitsubishi Chemical Corporation) as a carbon material as a conductive additive, binder (KF polymer # 7208: manufactured by Kureha Battery Materials Japan, 8% NMP system) Dispersion) 30 parts were mixed to prepare a composite ink for an electricity storage device electrode. The degree of dispersion as a composite ink was determined by the following method.

[Examples 3 to 9, Comparative Examples 1 and 2]
Except having changed into the dispersing agent, conductive support agent, and binder which are shown in Table 2, it is the same method as Example 1, it is the material ink for electrical storage device electrodes of Examples 3-9, and the electrical storage device of Comparative Examples 1 and 2. The electrode mixture ink was obtained, and the degree of dispersion as the mixture ink was determined by the following method.

(Determination of dispersion degree of compound ink)
The degree of dispersion of the composite ink was determined by determination with a grind gauge (according to JIS K5600-2-5).
The evaluation results are shown in Table 2. The numbers in the table indicate the size of the coarse particles, and the smaller the value, the better the dispersibility and the more uniform composite ink.

[Example 10]
21 parts of 3,4,9,10-perylenetetracarboxylic dianhydride which is an organic active material, 3 parts (0.6 parts as solid content) of the aqueous solution of Synthesis Example 1 which is a dispersant, and 66.6 parts of water Are mixed in a mixer, and further dispersed in a sand mill. Further, 5.4 parts of acetylene black (DENKA BLACK HS-100) as a carbon material as a conductive auxiliary agent and a binder (polytetrafluoroethylene 30-J). : Mitsui DuPont Fluoro Chemical Co., Ltd., 60% aqueous dispersion) 4 parts are mixed to obtain a composite ink for an electricity storage device electrode, and the degree of dispersion as a composite ink is determined in the same manner as in Example 1. It was.

[Example 11]
21 parts of 3,4,9,10-perylenetetracarboxylic dianhydride which is an organic active material, 3 parts of NMP solution of Synthesis Example 2 which is a dispersant (0.6 parts as solid content), 40.6 parts of NMP 5.4 parts of acetylene black (Denka Black HS-100) as a carbon material as a conductive aid, binder (KF polymer # 7208: manufactured by Kureha Battery Materials Japan) , 8% NMP dispersion) 30 parts were mixed to obtain a composite ink for an electricity storage device electrode, and the degree of dispersion as a composite ink was determined in the same manner as in Example 1.

[Examples 12 to 18, Comparative Examples 3 and 4]
Except having changed into the dispersing agent shown in Table 3, the conductive support agent, and the binder, it was the same method as Example 10, and the electrical storage device electrode compound ink of Examples 12-18 and the electrical storage device of Comparative Examples 3 and 4 were used. The electrode mixture ink was obtained, and the degree of dispersion as the mixture ink was determined in the same manner as in Example 1.

<Positive electrode>, <Coin-type battery>
After applying the ink mixture for electricity storage device electrodes of Examples 1 to 18 and Comparative Examples 1 to 4 onto an aluminum foil having a thickness of 20 μm to be a current collector using a doctor blade, it was dried by heating under reduced pressure. The thickness was adjusted to 70 μm.

Next, as an electricity storage device, a working electrode obtained by punching the obtained positive electrode to a diameter of 16 mm, a metal lithium foil counter electrode, a separator (porous polyolefin film) inserted between the working electrode and the counter electrode, and an electrolyte (ethylene) A coin-type battery comprising a non-aqueous electrolyte solution in which LiPF ₆ was dissolved at a concentration of 1 M in a mixed solvent in which carbonate and diethyl carbonate were mixed at a ratio of 1: 1 (volume ratio) was produced. The coin-type battery was formed in a glove box substituted with argon gas, and after the coin-type battery was produced, the battery characteristics of the following charge / discharge characteristics and charge / discharge cycle characteristics were evaluated.

(Charge / discharge characteristics)
About the obtained coin-type battery, charging / discharging measurement was performed using the charging / discharging apparatus (SM-8 by Hokuto Denko).
Constant current charging was continued up to a charge end voltage of 4.2 V at a charging current of 60 mA / g. After the battery voltage reached 4.2 V, constant current discharge was performed at a discharge current of 60 mA / g until the final discharge voltage of 1.5 V was reached. These charge / discharge cycles are defined as one cycle, and three cycles of charge / discharge are repeated. The discharge capacity at the third cycle is defined as the initial discharge capacity.
When the active material used is 9,10-anthraquinone, as charge / discharge characteristics, Examples 1 to 9 and Comparative Example 2 obtain the percentage (%) of the initial discharge capacity of each battery with respect to the initial discharge capacity of Comparative Example 1. It was. The results are shown in Table 2.

  Moreover, when the active material to be used is 3,4,9,10-perylenetetracarboxylic dianhydride, Examples 10 to 18 and Comparative Example 4 represent the initial discharge capacity of Comparative Example 3 as charge / discharge characteristics. The percentage (%) of the initial discharge capacity of the battery was determined. The results are shown in Table 3.

(Charge / discharge cycle characteristics)
Each of the above charge / discharge cycles was performed 30 times, and the discharge capacity maintenance ratio (percentage of the 30th discharge capacity with respect to the initial discharge capacity) was calculated (the closer to 100%, the better). The results are shown in Tables 2 and 3.
○: “Maintenance rate is 85% or more. Very good.”
○ △: “Maintenance rate is 75% or more and less than 85%. Good”.
Δ: “Maintenance rate is 65% or more and less than 75%. Usable.”
×: “Maintenance rate is less than 65%.

  As shown in Tables 2 and 3, when the composite ink containing the electrode forming composition of the present invention was prepared, the dispersibility of the organic active material in the composite ink was improved, and the aggregation was eliminated. Electrode coatability is obtained. In addition, the electrode for an electricity storage device of the present invention is considered to have reduced discharge capacity, which is considered to be caused by aggregation of organic active materials, for example, in battery characteristics, and further improved charge / discharge cycle characteristics.

Claims (4)

The composition for electrical storage device electrode formation containing an organic active material and a cationic dispersing agent. Furthermore, the composition for electrical storage device electrode formation of Claim 1 containing the carbon material which is a conductive support agent. An electrode for an electricity storage device, comprising a current collector and a composite layer formed from the composition for forming an electricity storage device electrode according to claim 1. The electrical storage device which comprises a positive electrode, a negative electrode, and electrolyte, Comprising: At least one of the said positive electrode or the said negative electrode is an electrode for electrical storage devices of Claim 3.