JP5900111B2 - Secondary battery electrode forming composition, secondary battery electrode, and secondary battery - Google Patents

Description

  The present invention relates to a composition for forming a secondary battery electrode, an electrode obtained using the composition, and a secondary battery obtained using the electrode.

  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 have a large capacity. In addition, in a large-sized secondary battery for use in automobiles or the like, it is desired to realize a large-sized secondary battery instead of a conventional lead storage battery.

  In order to meet such demands, development of secondary batteries such as lithium ion secondary batteries and alkaline secondary batteries, for example, development of composite inks used for forming electrodes has been actively conducted. There is also an interest in a composition for forming an underlayer used for forming an underlayer of a composite material layer.

An important characteristic required for the composite ink used for forming the electrode and the composition for forming the underlayer includes uniformity in which the active material and the conductive assistant are appropriately dispersed.
This is because the dispersion state of the active material and conductive additive in the composite ink and the dispersion state of the conductive aid in the composition for forming the underlayer are determined by the distribution state of the active material and conductive aid in the mixture layer and the underlayer. This is because it is related to the distribution state of the conductive auxiliary agent, affects the physical properties of the electrode, and thus affects the battery performance.
Therefore, dispersion of the active material and the conductive auxiliary agent is an important issue. In particular, carbon materials with excellent electrical conductivity (conducting aids) have a strong cohesive force due to their large structure and specific surface area, and should be uniformly mixed and dispersed, whether in compound ink or in the composition for forming the underlayer. Is difficult.
And if the dispersibility and particle size control of the carbon material that is the conductive auxiliary agent is insufficient, the internal resistance of the electrode cannot be reduced because a uniform conductive network is not formed, and as a result, the performance of the electrode material is sufficient. The problem of being unable to withdraw.

  Moreover, when not only the conductive assistant but also the dispersion of the active material in the composite ink is insufficient, partial aggregation occurs in the composite layer formed from such a composite ink. In addition, resistance distribution occurs on the electrode due to partial aggregation, current concentration occurs when used as a battery, and problems such as partial heat generation and deterioration may occur.

  In addition, the composite ink and the composition for forming the underlayer are required to have appropriate fluidity to enable coating on the surface of the metal foil functioning as a current collector. Furthermore, in order to form a composite material layer or a base layer having a surface that is as flat as possible and having a uniform thickness, the composite ink or the base layer forming composition is required to have an appropriate viscosity.

  After the formation of the composite layer formed from the composite ink and the composition for forming the base layer, the metal foil as the base material is cut into pieces of a desired size and shape, or punched. It is pulled out. Therefore, the material layer and the base layer are required to have hardness that does not damage and softness that does not crack or peel off by cutting or punching.

In Patent Documents 1 to 4, an active material and a conductive material are mixed, and this mixture is kneaded with a cellulose-based thickener aqueous solution, and then an aqueous binder such as tetrafluoropolyethylene and latex is further added and further kneaded. It is disclosed that a composite ink is obtained. However, these composite inks have a problem that the dispersed state is insufficient and the flexibility is poor, and a desired electrode cannot be produced, so that good battery performance cannot be obtained.
In order to solve these problems, a method of using a dispersant in addition to the conventional material has been developed when preparing a composite ink (see Patent Document 5). A good dispersion state of the ink is insufficient, and a desired electrode and a secondary battery are often not obtained. In particular, a composite ink in which the further dispersibility of the conductive assistant is uniform is desired.

Japanese Patent Laid-Open No. 2-15855 Japanese Patent Laid-Open No. 9-082364 JP 2003-142102 A JP 2010-165493 A JP-T-2006-51679 gazette JP 2011-076910 A

  An object of the present invention is to provide an electrode forming composition for forming a secondary battery having excellent charge / discharge cycle characteristics, and an electrode forming composition having excellent dispersibility of an active material and a conductive additive. is there.

In the present invention, the dispersibility of the electrode active material (A) and the carbon material (B) as the conductive auxiliary agent can be improved by using the water-soluble resin type dispersant (C).
That is, the present invention neutralizes at least a part of the carboxyl group or amino group in the copolymer having at least one of the electrode active material (A) or the carbon material (B) as a conductive aid and the following structural unit. The composition for secondary battery electrode formation containing the resin type dispersing agent (C) formed by this, and an aqueous liquid medium (D).
Structural unit having an aromatic ring (c1): 5 to 70% by weight
Structural unit (c2) having a carboxyl group or an amino group: 15 to 60% by weight
Structural unit having a hydroxyl group (c3): 1 to 80% by weight
Other structural units (c4) other than the above (c1) to (c3): 0 to 79% by weight
(However, the total of the above (c1) to (c4) is 100% by weight)

Further, the present invention provides a current collector and a composite layer formed from the above-mentioned composition for forming a secondary battery electrode or an electrode base layer formed from the composition for forming a secondary battery electrode according to claim 1 . The present invention relates to an electrode for a secondary battery comprising at least one layer.

  Furthermore, the present invention relates to a secondary battery comprising a positive electrode, a negative electrode, and an electrolytic solution, wherein at least one of the positive electrode or the negative electrode is the secondary battery electrode.

  By using the resin-type dispersant, the dispersibility of the carbon material as the active material and the conductive auxiliary agent was improved, and the electrode-forming composition of the present invention was obtained. The composition for forming an electrode of the present invention can form a composite material layer and an underlayer excellent in flexibility and adhesion to a current collector, and can provide a secondary battery excellent in charge / discharge cycle characteristics.

The electrode for a secondary battery can be obtained by various methods.
For example, on the surface of a current collector such as a metal foil,
(1) an ink-like composition containing an active material and a liquid medium (hereinafter referred to as composite ink),
(2) a mixed ink containing an active material, a conductive additive and a liquid medium;
(3) a mixed ink containing an active material, a binder and a liquid medium;
(4) A mixed ink containing an active material, a conductive additive, 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 composite ink (1 ) To (4) or other composite inks to form a composite layer and obtain an electrode.

In any case, the fact that the dispersion state of the active material and the conductive additive affects the battery performance is described in detail in the background art section.
The water-soluble resin-type dispersant (C) relaxes the aggregation of the active material and functions as a dispersant for the carbon material that is a conductive additive.
Therefore, the composition for forming a secondary battery electrode of the present invention can be utilized as a composite ink that requires an active material or a composition for forming an underlayer that does not require an active material.
First, the water-soluble resin type dispersant (C) in the present invention will be described.
The water-soluble resin dispersant (C) in the present invention comprises a structural unit (c1) having an aromatic ring, a structural unit (c2) having a carboxyl group or an amino group, and a structural unit (c3) having a hydroxyl group. A copolymer obtained by neutralizing at least a part of a carboxyl group or an amino group in a copolymer as an essential component.

  The structural unit in the present invention refers to a portion derived from a monomer that is a raw material for a copolymer. The method for obtaining the copolymer having the structural units (c1) to (c4) is not particularly limited, and examples thereof include a method of copolymerizing monomers that form the structural units (c1) to (c4). . In this case, the weight ratio of the structural units (c1) to (c4) is the same as the weight ratio of the monomers used. Another method includes a method of modifying a copolymer obtained by polymerizing a derivative of a monomer that forms the structural units (c1) to (c4). In this case, the structural unit ( The weight ratio of c1) to (c4) is the weight ratio of each structural unit in the copolymer after modification.

First, the structural unit (c1) having an aromatic ring will be described.
Although it does not specifically limit as a monomer which forms the structural unit (c1) which has an aromatic ring, Styrene, (alpha) -methylstyrene, or a benzyl (meth) acrylate can be illustrated.

Next, the structural unit (c2) having a carboxyl group or an amino group will be described.
Although it does not specifically limit as a monomer which forms the structural unit (c2) which has a carboxyl group, Maleic acid, fumaric acid, itaconic acid, citraconic acid, or these alkyl or alkenyl monoester, phthalic acid beta- (meta ) Acryloxyethyl monoester, isophthalic acid β- (meth) acryloxyethyl monoester, terephthalic acid β- (meth) acryloxyethyl monoester, succinic acid β- (meth) acryloxyethyl monoester, acrylic acid, methacrylic acid Examples thereof include acid, crotonic acid, and cinnamic acid. In particular, methacrylic acid and acrylic acid are preferable.
The monomer for forming the structural unit (c2) having an amino group is not particularly limited, but dimethylaminoethyl (meth) acrylate, diethylaminoethyl (meth) acrylate, methylethylaminoethyl (meth) acrylate, dimethylamino Examples thereof include styrene and diethylaminostyrene. These structural units having a carboxyl group or an amino group may be used alone or in combination of two or more, and may be a combination of a structural unit having a carboxyl group and a structural unit having an amino group.

Next, the structural unit (c3) having a hydroxyl group will be described.
Although it does not specifically limit as a monomer which forms the structural unit (c3) which has a hydroxyl group, As a monomer which has a hydroxyl group, 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 4- Examples thereof include hydroxybutyl (meth) acrylate, glycerol mono (meth) acrylate, 4-hydroxystyrene, vinyl alcohol, allyl alcohol and the like.
Examples of the monomer that is a derivative of vinyl alcohol include vinyl esters such as vinyl acetate, vinyl propionate, and vinyl versatate. By copolymerizing these vinyl esters and saponifying the obtained copolymer, a structural unit (c3) having a hydroxyl group can be formed.
Examples of the saponification catalyst from polyvinyl ester to polyvinyl alcohol include alkali catalysts such as sodium hydroxide, potassium hydroxide and sodium carbonate, and acid catalysts such as hydrochloric acid and sulfuric acid.

Next, the structural unit (c4) other than the above (c1) to (c3) will be described.
Although it does not specifically limit as a monomer which forms other structural unit (c4), As an alkyl type (meth) acrylate, methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, butyl (meth) ) Alkyl (meth) acrylates having 1 to 22 carbon atoms such as acrylate, etc., and preferably having 2 to 10 carbon atoms, more preferably an alkyl group having 2 to 8 carbon atoms for the purpose of polarity control. Examples include group-containing acrylates or the corresponding methacrylates.

  Examples of nitrogen-containing monomers include monoalkylol (meth) acrylamides such as (meth) acrylamide, N-methylol (meth) acrylamide, and N-methoxymethyl- (meth) acrylamide, and N, N-di (methylol) acrylamide. Examples include acrylamide-based structural units such as N-methylol-N-methoxymethyl (meth) acrylamide and dialalkylol (meth) acrylamide such as N, N-di (methoxymethyl) acrylamide.

Furthermore, as other monomers, perfluoromethylmethyl (meth) acrylate, perfluoroethylmethyl (meth) acrylate, 2-perfluorobutylethyl (meth) acrylate, 2-perfluorohexylethyl (meth) acrylate, etc. Perfluoroalkyl alkyl (meth) acrylates having a C 1-20 perfluoroalkyl group;
Perfluoroalkyl such as perfluorobutylethylene, perfluorohexylethylene, perfluorooctylethylene, perfluorodecylethylene, and perfluoroalkyl group-containing vinyl monomers such as alkylene, vinyltrichlorosilane, vinyltris (βmethoxyethoxy) silane, vinyl Examples thereof include silanol group-containing vinyl compounds such as triethoxysilane and γ- (meth) acryloxypropyltrimethoxysilane and derivatives thereof, and a plurality of them can be used from these groups.

  Examples of the fatty acid vinyl compound include vinyl acetate, vinyl butyrate, vinyl propionate, vinyl hexanoate, vinyl caprylate, vinyl laurate, vinyl palmitate, and vinyl stearate.

  Examples of the alkyl vinyl ether compound include butyl vinyl ether and ethyl vinyl ether.

  Examples of the α-olefin compound include 1-hexene, 1-octene, 1-decene, 1-dodecene, 1-tetradecene, 1-hexadecene and the like.

  Examples of the vinyl compound include allyl compounds such as allyl acetate, allylbenzene, and allyl cyanide, vinyl cyanide, vinylcyclohexane, vinyl methyl ketone, styrene, α-methylstyrene, 2-methylstyrene, and chlorostyrene.

  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.

The ratio of the structural units constituting the copolymer in the resin-type dispersant (C) used in the present invention is as follows when the total of the structural units (c1) to (c4) is 100% by weight:
5 to 70% by weight of the structural unit (c1) having an aromatic ring,
15 to 60% by weight of the structural unit (c2) having a carboxyl group,
1 to 80% by weight of the structural unit (c3) having a hydroxyl group,
The other structural unit (c4) other than the above (c1) to (c3) is 0 to 79% by weight.
Preferably, (c1): 20 to 70% by weight, (c2): 15 to 45% by weight, (c3): 1 to 70% by weight, and (c4): 0 to 50% by weight.
More preferably, (c1): 30 to 70% by weight, (c2): 15 to 35% by weight, (c3): 1 to 40% by weight, (c4): 0 to 40% by weight.
Each structural unit may be of one type, or a plurality of types may be combined, and the structural ratio can be freely changed within the range of the total weight specified.

  It is presumed that the aromatic ring of the structural unit (c1) having an aromatic ring becomes a main adsorption site to the active material (A) and the conductive additive (B) described later.

The structural unit (c2) having a carboxyl group or an amino group and the structural unit (c3) having a hydroxyl group have a function of dissolving or dispersing the neutralized product of the copolymer in an aqueous liquid medium.
Then, the copolymer is adsorbed on the active material (A) or the conductive auxiliary agent (B) through the aromatic ring, and water is added by the hydroxyl group, and the neutralized and ionized carboxyl group or amino group is charged to repel the active material. It is considered that the dispersion state of the substance (A) and the conductive additive (B) in the aqueous liquid medium can be kept stable.

The molecular weight of the copolymer having the structural units (c1) to (c4) is not particularly limited, but the viscosity of the water-soluble resin type dispersant (C) in a 20% solid content aqueous solution is preferably 5 to 100,000 mPa · s. More preferably, it is 10 to 50,000 mPa · s. When the molecular weight of the water-soluble resin type dispersant (C) is lower than the predetermined range and the molecular weight of the water-soluble resin type dispersant (C) is higher than the predetermined range, There is a possibility of causing poor dispersion of the active material (A) or the carbon material (B) which is a conductive additive.
In addition, the viscosity in this invention is the value measured on 25 degreeC conditions using the B-type viscosity meter.

The copolymer is a copolymer having a structural unit (c3) having a hydroxyl group, and it is preferable that the constitutional ratio of the structural unit having a hydroxyl group in the copolymer is represented by the hydroxyl value as follows. That is, the hydroxyl value of the copolymer to be used is preferably in the range of 4 mgKOH / g to 900 mgKOH / g, and more preferably in the range of 20 mgKOH / g to 600 mgKOH / g.
When the hydroxyl value of the copolymer used in the present invention is lower than the above range, the dispersion stability of the dispersion tends to decrease and the viscosity tends to increase. In addition, when the hydroxyl value of the copolymer used in the present invention is higher than the above range, the adhesion of the copolymer to the pigment surface tends to decrease, and the storage stability of the dispersion tends to decrease.

  The hydroxyl value in the present invention is a value obtained by acetylating a hydroxyl group in a sample with acetic anhydride and titrating acetic acid that has not been used with a KOH solution and converting it to a solid content. Titration is based on the potentiometric titration method of JIS K 0070.

Similarly, the total acid value and amine value of the copolymer is preferably in the range of 50 mgKOH / g to 500 mgKOH / g, and more preferably in the range of 80 mgKOH / g to 400 mgKOH / g. .
If it is lower than the above range, the dispersion stability of the dispersion tends to decrease and the viscosity tends to increase. On the other hand, if it is higher than the above range, the adhesion of the copolymer to the pigment surface tends to decrease, and the storage stability of the dispersion tends to decrease.

  The acid value is a value obtained by converting the acid value (mg KOH / g) measured in accordance with the potentiometric titration method of JIS K 0070 into a solid content. The amine value is expressed in mg of potassium hydroxide equivalent to perchloric acid required to neutralize all basic nitrogen contained in 1 g of the sample. The measurement method is a value obtained by converting the solid content obtained by the potentiometric titration method described in JIS K 7237 (1995).

The water-soluble resin type dispersant (C) can be obtained by various production methods.
For example, the monomers forming the structural units (c1) to (c4) are copolymerized in an organic solvent that can be azeotroped with water. Thereafter, an aqueous liquid medium typified by water and a neutralizing agent are added to neutralize at least a part of the carboxyl group or amino group, the azeotropic solvent is distilled off, and a water-soluble resin-type dispersant (C aqueous solution) can be obtained.
As the organic solvent at the time of polymerization, any solvent that azeotropes with water may be used, but those having high solubility in the copolymer are preferable, and ethanol, 1-propanol, 2-propanol, and 1-butanol are preferable. Preferably 1-butanol.

Alternatively, the monomer derivatives forming the structural units (c1) to (c4) are copolymerized in an organic solvent that can be azeotroped with water. Thereafter, the catalyst is modified to the structural units (c1) to (c4) using a catalyst or the like, and an aqueous liquid medium represented by water and a neutralizing agent are added to neutralize at least a part of the carboxyl group or amino group. . It can be further distilled off azeotropic solvent, obtaining an aqueous solution of the water-soluble resin dispersant (C).

Alternatively, it is copolymerized in a hydrophilic organic solvent, neutralized by adding water and an amine or acetic acid to make it aqueous, and the hydrophilic organic solvent is not distilled off, but in an aqueous liquid medium containing the hydrophilic organic solvent and water, it can be a water-soluble resin dispersant (C) to obtain a solution prepared by dissolve.
In this case, the hydrophilic organic solvent used is preferably one having high solubility in the copolymer, preferably glycol ethers, diols, more preferably (poly) alkylene glycol monoalkyl ethers having 3 to 6 carbon atoms. Alkanediols are good.

The following are mentioned as a neutralizing agent used for neutralization of a copolymer.
For example, inorganic alkaline agents such as ammonia water, various organic amines such as dimethylaminoethanol, diethanolamine, and triethanolamine, alkali metal hydroxides such as sodium hydroxide, lithium hydroxide, and potassium hydroxide, organic acids and mineral acids Etc. can be used. The copolymer as described above is dispersed or dissolved in an aqueous liquid medium.

<Composite ink>
As described above, the composition for forming a secondary battery electrode of the present invention can be used as a mixture ink or a composition for forming an underlayer.
Therefore, a description will be given of a composite ink that essentially includes an active material, which is one of the preferred embodiments of the composition for forming a secondary battery electrode of the present invention. There exist positive mix ink or negative mix ink as compound ink, and as already demonstrated, there are various modes as shown in the following (1) to (4), respectively.
(1) A composite ink containing an active material (A), a water-soluble resin-type dispersant (C), and an aqueous liquid medium (D).
(2) A composite ink further containing a conductive additive (B) in (1).
(3) A composite ink further containing a binder in (1).
(4) The composite ink further containing the conductive additive (B) and a binder in (1).

The positive electrode active material for the lithium ion secondary battery is not particularly limited, but metal oxides capable of doping or intercalating lithium ions, metal compounds such as metal sulfides, and conductive polymers are used. be able to.
Examples thereof include transition metal oxides 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.
In addition, conductive polymers such as polyaniline, polyacetylene, polypyrrole, and polythiophene can also be used. Moreover, you may mix and use said inorganic compound and organic compound.

The negative electrode active material for the lithium ion secondary battery is not particularly limited as long as it can be doped or intercalated with lithium ions. For example, metal Li, alloys thereof such as tin alloys, silicon alloys, lead alloys, Li _x Fe ₂ O ₃ , Li _x Fe ₃ O ₄ , Li _x WO ₂ , lithium titanate, lithium vanadate, silicon Metal oxides such as lithium oxide, conductive polymers such as polyacetylene and poly-p-phenylene, amorphous carbonaceous materials such as soft carbon and hard carbon, artificial graphite such as highly graphitized carbon materials, or natural Examples thereof include carbonaceous powders such as graphite, carbon black, mesophase carbon black, resin-fired carbon materials, air-growth carbon fibers, and carbon fibers. These negative electrode active materials can be used alone or in combination.

  Moreover, a conventionally well-known thing can be suitably selected as a positive electrode active material and negative electrode active material for alkaline secondary batteries.

  The size of these active materials (A) is preferably in the range of 0.05 to 100 μm, and more preferably in the range of 0.1 to 50 μm. And it is preferable that the dispersed particle diameter of the active material (A) in compound-material ink is 0.5-20 micrometers. 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.).

Next, the carbon material (B) which is a conductive support agent will be described.
The carbon material (B), which is a conductive aid in the present invention, is not particularly limited as long as it is a conductive carbon material, but graphite, carbon black, conductive carbon fiber (carbon nanotube, carbon nanofiber) , Carbon fiber), fullerene and 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. If carbon black having a specific surface area of less than 20 m ² / g is used, it may be difficult to obtain sufficient conductivity, and carbon black of more than 1500 m ² / g may be difficult to obtain from commercially available materials. is there.

  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 in the composite ink of the carbon material (B), which is a conductive additive, be refined to 0.03 μm or more and 5 μm or less. It may be difficult to produce a composition having a dispersed particle size of the carbon material as the conductive aid of less than 0.03 μm. In addition, when a composition having a dispersed particle size of the carbon material as the conductive auxiliary agent exceeding 2 μm is used, there may be problems such as variations in the material distribution of the composite coating film and variations in the resistance distribution of the electrodes. .
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 BLACK100, 115, 205, etc. (manufactured by Colombian, furnace black), # 2350, # 2400B, # 2600B, # 30050B, # 3030B, # 3030B, # 3030B # 3350B, # 3400B, # 5400B etc. (Mitsubishi Chemical Co., Furnace Black), MONARCH1400, 1300, 900, VulcanXC- 2R, BlackPearls2000, etc. (Cabot, Furnace Black), Ensaco 250G, Ensaco 260G, Ensaco 350G, 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.

Next, the aqueous liquid medium (D) will be described.
As the aqueous liquid medium (D) used in the present invention, it is preferable to use water, but if necessary, for example, a liquid medium compatible with water in order to improve the coating property to the current collector. May be used.
Liquid media compatible with water include alcohols, glycols, cellosolves, amino alcohols, amines, ketones, carboxylic acid amides, phosphoric acid amides, sulfoxides, carboxylic acid esters, and phosphoric acid esters , Ethers, nitriles and the like, and may be used as long as they are compatible with water.

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 binders 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.

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

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 30 to 90% by weight of the solid content.
It is preferable that the active material (A) is contained as much as possible within the viscosity range that can be applied. For example, the proportion of the active material (A) in the solid ink solid content is 80 wt% or more and 99 wt% or less. Is preferred.
Moreover, it is preferable that the ratio of the resin type dispersing agent (C) which occupies for solid ink solid content is 0.1 to 15 weight%.
When the conductive auxiliary agent (B) is included, the proportion of the conductive auxiliary agent (B) in the solid ink solid content is preferably 0.1 to 15% by weight.
When the binder is included, the ratio of the binder to the solid material ink solid content is preferably 0.1 to 15% by weight.

Such a composite ink can be obtained by various methods.
The case of the mixed ink of (4) containing an active material (A), a conductive additive (B), a water-soluble resin type dispersant (C), a binder, and an aqueous liquid medium (D) will be described as an example. .
For example,
(4-1) An aqueous dispersion of an active material containing an active material (A), a water-soluble resin type dispersant (C), and an aqueous liquid medium (D) is obtained, and a conductive additive (B ) And a binder can be added to obtain a composite ink.
The conductive auxiliary agent (B) and the binder can be added simultaneously, or after the conductive auxiliary agent (B) is added, the binder may be added, or vice versa.
(4-2) An aqueous dispersion of a conductive additive containing the conductive additive (B), the water-soluble resin type dispersant (C) and the aqueous liquid medium (D) is obtained, and an active material (A ) And a binder can be added to obtain a composite ink.
The active material (A) and the binder can be added simultaneously, or after adding the active material (A), the binder may be added, or vice versa.
(4-3) An aqueous dispersion of the active material containing the active material (A), the water-soluble resin-type dispersant (C), the binder, and the aqueous liquid medium (D) is obtained, and a conductive auxiliary ( B) can be added to obtain a composite ink.
(4-4) An aqueous dispersion of the conductive additive containing the conductive additive (B), the water-soluble resin-type dispersant (C), the binder and the aqueous liquid medium (D) is obtained, and an active material ( A) can be added to obtain a composite ink.
(4-5) The active material (A), the conductive auxiliary agent (B), the water-soluble resin type dispersant (C), the binder, and the aqueous liquid medium (D) can be mixed almost simultaneously to obtain a mixed ink. .

(Disperser / Mixer)
As an apparatus used for obtaining the composite ink, a disperser or a mixer which is 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. Further, in the case of a positive or negative electrode active material in which particles are easily broken or crushed by a strong impact, a medialess disperser such as a roll mill or a homogenizer is preferable to a media type disperser.

<Underlayer forming composition>
As described above, the composition for forming a secondary battery electrode of the present invention can be used not only as a mixture ink but also as a composition for forming an underlayer.
The composition for base layer formation contains a conductive support agent (B), a water-soluble resin type dispersant (C), and an aqueous liquid medium (D). Furthermore, a binder can also be contained. About each component, it is the same as that of the case of compound ink.
The proportion of the carbon material (B) as a conductive additive in the total solid content of the composition used for the electrode underlayer is preferably 5% by weight or more and 95% by weight or less, and more preferably 10% by weight or more and 90% by weight or less. preferable. If the carbon material (B) as a conductive auxiliary agent is small, the conductivity of the underlayer may not be maintained. On the other hand, if the carbon material (B) as a conductive auxiliary agent is too much, the resistance of the coating film decreases. There is a case. Moreover, although the appropriate viscosity of electrode base layer ink is based on the coating method of electrode base layer ink, generally it is preferable to set it as 10 mPa * s or more and 30,000 mPa * s or less.

<Electrode>
Of the composition for forming a secondary battery electrode of the present invention, the composite ink can be applied and dried on a current collector to form a composite layer to obtain a secondary battery electrode.
Alternatively, the composition for forming an underlayer of the composition for forming a secondary battery electrode of the present invention is formed by forming an underlayer on the current collector, and providing a composite layer on the underlayer, for a secondary battery. An electrode can also be obtained. The composite material layer provided on the base layer may be formed using the above-described composite material inks (1) to (4) of the present invention, or may be formed using other composite material inks.

(Current collector)
The material and shape of the current collector used for the electrode are not particularly limited, and those suitable for various secondary batteries 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.

<Secondary battery>
A secondary battery can be obtained by using the above electrode for at least one of a positive electrode and a negative electrode.
Secondary batteries include alkaline secondary batteries, lead-acid batteries, sodium-sulfur secondary batteries, lithium-air secondary batteries, etc., as well as lithium ion secondary batteries, which are conventionally known for each secondary battery. 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, but are not limited thereto.

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 electrolyte solution may be a polymer electrolyte that is held in a polymer matrix and made into a gel. 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.

(Battery structure / configuration)
The structure of the lithium ion secondary battery using the composition of the present invention is not particularly limited, but is usually composed of a positive electrode and a negative electrode, and a separator provided as necessary, a paper type, a cylindrical type, a button type, It can be made into various shapes according to the purpose of use, such as 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 weight”.

(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 a mixture of 100.0 parts of styrene, 60.0 parts of acrylic acid, 40.0 parts of 4-hydroxybutyl acrylate, and 12.0 parts of V-601 (manufactured by Wako Pure Chemical Industries, Ltd.) 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, 0.6 parts 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 (1) solution. Got. Moreover, the acid value of the copolymer (1) was 219.1 (mgKOH / g).
Further, after cooling to room temperature, 74.2 parts of dimethylaminoethanol was added for neutralization. This is the amount that neutralizes 100% of acrylic acid. 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.
Diluted with water to obtain an aqueous solution of a nonvolatile content of 20% water-soluble resin dispersant (1). Moreover, the viscosity of the aqueous solution of the water-soluble resin type dispersant (1) having a nonvolatile content of 20% was 40 mPa · s.

(Synthesis Examples 2-22, 26-30)
The compounding compositions shown in Table 1 were synthesized in the same manner as in Synthesis Example 1 to obtain dispersants of Synthesis Examples 2-22 and 26-30.

(Synthesis Example 23)
In a reaction vessel equipped with a gas introduction tube, a thermometer, a condenser, and a stirrer, 200.0 parts of butanol was charged and replaced with nitrogen gas. The inside of the reaction vessel is heated to 55 ° C., and a mixture of 100.0 parts of styrene, 60.0 parts of acrylic acid, 78.2 parts of vinyl acetate, and 12.0 parts of V-601 (manufactured by Wako Pure Chemical Industries) is 2 hours. Over the course of the polymerization reaction. After completion of the dropwise addition, the mixture was further reacted at 110 ° C. for 3 hours, 0.6 parts of V-55 (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 (23) solution. Got. The acid value of the copolymer (23) was 219.1 (mgKOH / g).
Further, after cooling to room temperature, the inside of the reaction vessel was set to 40 ° C., and a 50% aqueous sodium hydroxide solution was added to saponify 100% vinyl acetate and neutralize 100% acrylic acid. Furthermore, sodium acetate was removed by post-treatment such as neutralization, precipitation, washing, and filtration to obtain a copolymer having the composition shown in Table 1. Then diluted with water to obtain an aqueous solution of a nonvolatile content of 20% water-soluble resin dispersant (23). Moreover, the viscosity of the aqueous solution of the water-soluble resin type dispersant (23) having a nonvolatile content of 20% was 40 mPa · s.

(Synthesis Examples 24 and 25)
Synthesis was performed in the same manner as in Synthesis Example 23 so that the weight ratio of the structural units shown in Table 1 was obtained, thereby obtaining dispersants of Synthesis Examples 24 and 25.

Ｓｔ：スチレン
ＢｚＭＡ：ベンジルメタクリレート
ＡＡ：アクリル酸
ＭＡＡ：メタクリル酸
ＤＭ：ジメチルアミノメタクリレート
４ＨＢＡ：４−ヒドロキシブチルアクリレート
２ＨＥＡ：２−ヒドロキシエチルアクリレート
ＶＡ：ビニルアルコール
ＢＭＡ：ブチルメタクリレート
ＤＭＡＥ：ジメチルアミノエタノール

St: Styrene BzMA: Benzyl methacrylate AA: Acrylic acid MAA: Methacrylic acid DM: Dimethylamino methacrylate 4HBA: 4-hydroxybutyl acrylate 2HEA: 2-hydroxyethyl acrylate VA: Vinyl alcohol BMA: Butyl methacrylate DMAE: Dimethylaminoethanol

[Example 1]
Conductive acetylene black as a carbon material is aid (Denka Black HS-100), 10 parts of a water solution of 10 parts of the water-soluble resin dispersant according to Synthesis Example (1) (1) (2 parts as solid content) Then, 80 parts of water was mixed in a mixer, and further dispersed in a sand mill to obtain a carbon material dispersion (1) for a secondary battery electrode.

[Example 2]
For a secondary battery electrode, 10 parts of acetylene black (DENKA BLACK HS-100) as a carbon material as a conductive aid, 10 parts of the dispersant described in Synthesis Example (2), and 80 parts of water are placed in a kneader and dispersed. A carbon material dispersion (2) was obtained.

[Examples 3 to 25], [Comparative Examples 1 to 9]
Carbon materials for secondary battery electrodes of Examples 3 to 25 in the same manner as the carbon material dispersion (1) for secondary battery electrodes, using the carbon material and the dispersant that are conductive assistants shown in Table 2 Dispersions (3) to (25) and carbon material dispersions (26) to (34) for secondary battery electrodes of Comparative Examples 1 to 9 were obtained and dispersed as a carbon material dispersion by the following method. I asked for a degree.

(Determining the degree of dispersion of carbon material dispersion for secondary battery electrode and composite ink)
The degree of dispersion of the carbon material dispersion for the secondary battery electrode and 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 for the carbon material dispersion. The numbers in the table indicate the size of the coarse particles. The smaller the value, the better the dispersibility and the more uniform the carbon material dispersion for secondary battery electrodes.

  As shown in Table 2, when the carbon material dispersions for secondary battery electrodes of the present invention of Examples 1 to 25 were used, the carbon material (B) as a conductive auxiliary agent was excellent in dispersibility and uniform secondary It became clear that it was a carbon material dispersion for battery electrodes. It can be seen that by using the resin type dispersant (C), a uniform carbon material dispersion for a secondary battery electrode excellent in dispersibility can be obtained even if the type of the conductive additive and the kneading method are different.

<Positive electrode mixture ink>, <Positive electrode>, <Coin-type battery>
[Example 26]
With respect to 50 parts of carbon material dispersion for secondary battery electrodes (1) prepared in Example 1 (5 parts as acetylene black solid content), 45 parts of LiFePO ₄ as a positive electrode active material, binder (polytetrafluoroethylene 30- J: Mitsui / DuPont Fluoro Chemical Co., Ltd., 60% aqueous dispersion) 8.3 parts and 50 parts of water were mixed to prepare a positive electrode material ink for a secondary battery electrode. The dispersity of the composite ink was determined in the same manner as the dispersity of the carbon material dispersion described above.
And after apply | coating this mixed-material ink for secondary battery electrodes for positive electrodes on the 20-micrometer-thick aluminum foil used as a collector using a doctor blade, it heat-drys under reduced pressure and the thickness of an electrode becomes 100 micrometers. Adjusted as follows.
Furthermore, the rolling process by a roll press was performed, the positive electrode from which thickness becomes 85 micrometers was produced, and the softness | flexibility and adhesiveness were evaluated with the following method.

Next, the obtained positive electrode was punched into a diameter of 16 mm, a working electrode, a metallic lithium foil counter electrode, a separator (porous polypropylene film) inserted between the working electrode and the counter electrode, and an electrolytic solution (ethylene carbonate and diethyl carbonate). 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 obtained by mixing 1: 1 at a volume ratio. The coin-type battery was used in a glove box substituted with argon gas, and a predetermined battery characteristic evaluation was performed after the coin-type battery was produced.

(Electrode flexibility)
The electrode produced above was formed into a strip shape and wound so that the current collector side was in contact with a metal rod having a diameter of 3 mm, and cracks on the electrode surface that occurred during winding were determined by visual observation. The one that does not crack is more flexible.
○: “No cracks (a level where there is no practical problem)”
○ △: “In rare cases, cracks are seen (there is a problem, but the usable level)”
Δ: “Partial cracks are seen”
×: “Overall cracks are seen”

(Electrode adhesion)
Using the knife, the incision from the surface of the electrode to the depth reaching the current collector was cut into 6 grids in the vertical and horizontal directions at intervals of 2 mm. An adhesive tape was applied to the cut and immediately peeled off, and the degree of the active material falling off was determined by visual judgment. The evaluation criteria are shown below.
○: “No peeling (practical level)”
○ △: “Slightly peeled (problem but usable level)”
Δ: “About half peel”
×: “Peeling at most parts”

(Charge / discharge storage characteristics)
About the obtained coin-type battery, charging / discharging measurement was performed using the charging / discharging apparatus (SM-8 by Hokuto Denko).
When the active material to be used was LiFePO ₄ , constant current charging was continued to a charge end voltage of 4.2 V at a charging current of 1.2 mA. After the battery voltage reached 4.2 V, constant current discharge was performed at a discharge current of 1.2 mA until the discharge end voltage of 2.0 V was reached. These charge / discharge cycles are defined as one cycle, and 5 cycles of charge / discharge are repeated, and the discharge capacity at the fifth cycle is defined as the initial discharge capacity. (The initial discharge capacity is assumed to be 100% maintenance rate).

Next, after charging in the same way as the 5th cycle, after storing for 100 hours in a 60 ° C. constant temperature bath, constant current discharge is performed at a discharge current of 1.2 mA until a discharge end voltage of 2.0 V is reached. (The closer to 100%, the better).
○: “Change rate is 95% or more. Particularly excellent.”
○ △: “Change rate is 90% or more and less than 95%. No problem at all”
Δ: “Change rate is 85% or more and less than 90%.
×: “Change rate is less than 85%.

Further, the active material to be used in the case of LiCoO _2, charging current 1.2 mA, charge end voltage 4.3 V, the discharge current 1.2 mA, except for using discharge end voltage 2.8V, if the LiFePO ₄ The charge / discharge storage characteristics can be measured in the same manner as above.
Further, when artificial graphite is used as the active material for the negative electrode (described later), the charge current is 1.5 mA, the charge end voltage is 0.1 V, the discharge current is 1.5 mA, and the discharge end voltage is 2.0 V. The charge / discharge storage characteristics can be measured as in the case of LiFePO ₄ .

[Examples 27 to 38, 40 to 51], [Comparative Examples 10 to 18]
As shown in Table 3, except that the carbon material dispersions (2) to (34) for secondary battery electrodes were used, a mixture ink for positive electrode secondary battery electrodes and a positive electrode were obtained in the same manner as in Example 26. Evaluation was performed in the same manner.

[Example 39], [Comparative Examples 19-22]
Carbon for secondary battery electrodes using 45 parts of LiFePO ₄ as a positive electrode active material, 8.3 parts of binder (polytetrafluoroethylene 30-J: manufactured by Mitsui DuPont Fluorochemical Co., Ltd., 60% aqueous dispersion) and 50 parts of water. A positive electrode secondary battery electrode mixture ink and a positive electrode were obtained in the same manner as in Example 26 except that the conductive auxiliary agent and dispersant shown in Table 3 were used instead of the material dispersion, and evaluation was similarly performed. did.

<Preparation of negative electrode for lithium secondary battery>
[Example 52]
With respect to 10 parts of carbon material dispersion for secondary battery electrodes (1) prepared in Example 1 (1 part as acetylene black solid content), 96 parts of artificial graphite as a negative electrode active material, binder (polytetrafluoroethylene 30- J: Mitsui / DuPont Fluoro Chemical Co., Ltd., 60% aqueous dispersion) 5 parts and 90 parts of water were mixed to prepare a secondary battery electrode mixture ink for negative electrode.
This negative electrode mixture ink was applied onto a copper foil having a thickness of 20 μm serving as a current collector using a doctor blade, and then dried by heating under reduced pressure so that the thickness of the electrode was adjusted to 100 μm. A rolling process using a roll press was performed to prepare a negative electrode having a thickness of 85 μm, and evaluation was performed in the same manner as in the case of the positive electrode. The charge / discharge retention characteristics were evaluated using an evaluation coin-type battery having a negative electrode as a working electrode and a metal lithium foil as a counter electrode.

[Examples 53 to 56] [Comparative Examples 23 to 25]
As shown in Table 3, Example 52 was used except that the carbon material dispersions (4), (6), (20), (23), (26), (27), and (30) for secondary battery electrodes were used. In the same manner as above, a composite ink for a negative electrode for a secondary battery electrode and a negative electrode were obtained and evaluated in the same manner.

[Example 57], [Comparative Examples 26 and 27]
Dispersion of carbon material for secondary battery electrode using 96 parts of artificial graphite as negative electrode active material, 5 parts of binder (polytetrafluoroethylene 30-J: manufactured by Mitsui DuPont Fluorochemicals Co., Ltd., 60% aqueous dispersion) and 90 parts of water In the same manner as in Example 52 except that the conductive aid and dispersant shown in Table 3 were used instead of using the body, a negative electrode secondary battery electrode mixture ink and a negative electrode were obtained and evaluated in the same manner.

As shown in Table 3, when the ink mixture for secondary battery electrodes of the present invention is used, the carbon material or the active material, which is a conductive auxiliary agent, is uniformly dispersed in the ink mixture. The balance between the property and the adhesiveness is achieved, and also in the battery characteristics, a decrease in discharge capacity after 100 hours at 60 ° C. is suppressed.
As for this, when the carbon material or active material, which is a conductive auxiliary agent, is not sufficiently dispersed in the mixture ink, a uniform conductive network as an electrode is not formed. It is considered that resistance distribution due to mechanical aggregation occurs, and current concentration occurs when used as a battery, so that deterioration is accelerated.
In addition, when the dispersion control of the carbon material or the active material that is the conductive auxiliary agent is insufficient, the flexibility and adhesion of the electrode tend to be insufficient. In particular, when the dispersion control of the carbon material that is a conductive additive is insufficient, the tendency is remarkable.
Therefore, when the composite ink for secondary battery electrodes of the present invention is used, the carbon material or the active material as the conductive auxiliary agent is uniformly dispersed in the composite ink, so that the improvement is possible. Conceivable.

[Example 58]
As a positive electrode active material, 45 parts of LiFePO _{4, 5} parts of a binder (polytetrafluoroethylene 30-J: manufactured by Mitsui DuPont Fluorochemical Co., Ltd., 60% aqueous dispersion) and 50 parts of water are used. except for using aqueous solution 10 parts of the water-soluble resin dispersant (1) (2 parts as solid content) in the same manner as in example 26, to give a secondary battery positive electrode mixture member inks, and the positive electrode, similarly evaluated.

[Examples 59 and 60, Comparative Examples 28 and 29]
Except for using the dispersant shown in Table 4 or 2 parts of hydroxyethyl cellulose, a mixture ink for a positive electrode of a secondary battery and a positive electrode were obtained and evaluated in the same manner as in Example 58.

[Example 61]
As the negative electrode active material, 94 parts of artificial graphite, 7 parts of binder (polytetrafluoroethylene 30-J: manufactured by Mitsui DuPont Fluorochemical Co., Ltd., 60% aqueous dispersion) and 90 parts of water were used, and described in Synthesis Example (1). aqueous solution 10 parts of an amphoteric water-soluble resin dispersant (1) (2 parts as solids) was used in the same manner as in example 52, to give secondary battery negative electrode mixture member inks, and the negative electrode, similar Evaluated.

[Examples 62 and 63, Comparative Examples 30 and 31]
Except using the dispersing agent shown in Table 4, or 2 parts of hydroxyethylcellulose, it carried out similarly to Example 61, and obtained the mixed-material ink for secondary battery negative electrodes, and the negative electrode, and evaluated similarly.

[Example 64]
Conductive acetylene black as a carbon material is aid (Denka Black HS-100) 10 parts of aqueous solution of 5 parts of the water-soluble resin dispersant according to Synthesis Example (1) (1) (1 parts as solid content) , 4 parts of binder (polytetrafluoroethylene 30-J: manufactured by Mitsui DuPont Fluorochemical Co., Ltd., 60% aqueous dispersion) and 81 parts of water are mixed in a mixer, and further dispersed in a sand mill for secondary treatment. A composition for forming a base layer for a battery electrode was obtained, and the degree of dispersion was measured with a grind gauge.
And after applying this composition for base layer formation on the 20-micrometer-thick aluminum foil used as a collector using a doctor blade, it heat-dried and formed the base layer so that thickness might be set to 8 micrometers.
Subsequently, after applying the mixed material ink for secondary battery positive electrode of Example 35 on the said base layer, it dried under reduced pressure, the positive electrode was obtained similarly to Example 35, and evaluated similarly.
[Example 65, Comparative Example 32]
Except having used the dispersing agent shown in Table 4, or 1 part of hydroxyethyl cellulose, it carried out similarly to Example 64, and obtained the composition for base layer formation for secondary battery electrodes, and evaluated similarly.
Subsequently, after applying the mixture ink for secondary battery positive electrode shown in Table 4 on the said foundation layer, it heat-dried under reduced pressure, the positive electrode was obtained similarly to Example 64 below, and evaluated similarly.

As shown in Table 4, when the composition for forming a secondary battery electrode of the present invention was used, as a result of sufficient dispersion control in the composite ink even without the presence of a conductive auxiliary agent, an electrode was obtained. Since the uniform conductive network at the time was formed, it was considered that the flexibility and adhesion of the electrode were balanced, and the battery capacity was also suppressed from lowering the discharge capacity after 60 ° C. and 100 hours. In addition, since no conductive assistant is used, the ratio of the active material contained in the composite ink can be increased, which is thought to lead to an improvement in battery capacity.
Furthermore, when the composition for forming a secondary battery electrode of the present invention is used for the underlayer, it is better than the evaluation results of Example 35 and Comparative Example 11 in which the underlayer is not used. I understand. This is presumably because the composition for forming a secondary battery electrode of the present invention made the contact portion between the current collector and the composite material layer more uniform and strong. However, in Comparative Example 32, the dispersion state of the composition for forming the secondary battery electrode for the underlayer was insufficient, and even when the electrode was used, the result was inferior to the evaluation result of Example 35. . This is presumably because the state of close contact between the current collector and the composite material layer was inadequate, resulting in a non-uniform state as an electrode as compared with the case where the base layer was not used.

Claims (3)

A water-soluble resin obtained by neutralizing at least part of a carboxyl group or an amino group in a copolymer having the following structural units with at least one of an electrode active material (A) or a carbon material (B) as a conductive additive. The composition for secondary battery electrode formation containing a type | mold dispersing agent (C) and an aqueous liquid medium (D).
Structural unit having an aromatic ring (c1): 5 to 70% by weight
Structural unit (c2) having a carboxyl group or an amino group: 15 to 60% by weight
Structural unit having a hydroxyl group (c3): 1 to 80% by weight
Other structural units (c4) other than the above (c1) to (c3): 0 to 79% by weight
(However, the total of the above (c1) to (c4) is 100% by weight) At least one layer of a current collector and a composite layer formed from the composition for forming a secondary battery electrode according to claim 1 or an electrode underlayer formed from the composition for forming a secondary battery electrode according to claim 1. A secondary battery electrode comprising:   A secondary battery comprising a positive electrode, a negative electrode, and an electrolyte solution, wherein at least one of the positive electrode or the negative electrode is a secondary battery electrode according to claim 2.