JP5880544B2 - Aqueous composition for secondary battery electrode formation, secondary battery electrode, and secondary battery - Google Patents

Description

  The present invention relates to an aqueous 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 batteries for automobiles and 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 when the active material and the conductive additive are dispersed. This is because the dispersion state of the active material and the conductive auxiliary in the composition ink and the underlayer forming composition is the distribution state of the active material and the conductive auxiliary in the composite layer and the distribution state of the conductive auxiliary in the underlayer. This is because it affects the physical properties of the electrode and the battery performance.

  Therefore, dispersion of the active material and the conductive auxiliary agent is an important issue. In particular, carbon materials (conducting aids) with excellent conductivity have a strong cohesive force due to their large structure and specific surface area, and evenly mix and disperse, whether in mixed 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. This partial aggregation causes a resistance distribution on the electrode, and as a result, current concentration occurs when used as a battery, which may cause problems such as partial heat generation and deterioration.

  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 base layer is cut into pieces of a desired size and shape together with the metal foil as the base material, It is punched 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.

  Furthermore, since the composite material layer and the base layer are exposed to the electrolytic solution in the battery, the composite material layer and the base layer may be collapsed and peeled off from the current collector. Therefore, elution resistance in the electrolytic solution is also required for the composite material layer and the underlayer.

  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 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.

  Moreover, in order to solve these problems, the method of using a dispersing agent in addition to the conventional material at the time of preparation of compound ink is also developed (refer patent documents 5-8). However, even in the use of these dispersants, the good dispersion state of the mixture ink is insufficient, and the desired electrode and secondary battery are often not obtained. A composite ink is desired. In particular, when an aqueous medium is used, it is difficult to solve these conventional problems.

Japanese Patent Laid-Open No. 2-15855 Japanese Patent Laid-Open No. 9-082364 JP 2003-142102 A JP 2010-165493 A Japanese Patent No. 32113944 Japanese Patent No. 4147994 Japanese Patent No. 4468306 WO2010 / 013786

  The object of the present invention is to improve the dispersibility and rheological properties of the active material and conductive additive in the electrode-forming composition, and to adhere the layer formed from the electrode-forming composition to the current collector. It is to improve the strength of the coating film, the flexibility of the coating film, and the elution resistance of the electrolytic solution, and further to improve the battery cycle test performance.

  This invention solves the said subject by using the cationic dispersing agent (A) excellent in the dispersibility of an electrode active material and a conductive support agent.

[1] An aqueous composition for forming a secondary battery electrode, comprising at least one of a carbon material that is an electrode active material or a conductive additive, a cationic dispersant (A), and water,
The cationic dispersant (A) has at least one of an aliphatic amine or an aromatic amine as a cationic site, has an amine value of 110 to 1000 mgKOH / g, a hydroxyl value of 0 to 400 mgKOH / g, and a weight An aqueous composition for forming a secondary battery electrode, having an average molecular weight of 5000 or more.

[2] The composition according to [1] above, wherein the cationic dispersant (A) is a copolymer obtained by copolymerizing the following monomers.
Ethylenically unsaturated monomer having an aromatic ring (a1): 0 to 30% by weight
Ethylenically unsaturated monomer having an aliphatic amino group or an aromatic amino group (a2): 30 to 80% by weight
Ethylenically unsaturated monomers (a3) other than (a1) to (a2): 0 to 70% by weight
(However, the total of the above (a1) to (a3) is 100% by weight.)

[3] The composition according to [1] or [2], further including a cellulose-based thickener (B).

[4] The composition according to any one of [1] to [3], further including a binder composition (C).

[5] The composition according to [4] above, wherein the binder composition (C) contains crosslinked resin fine particles.

[6] The composition according to [5] above, wherein the cross-linked resin fine particles are resin fine particles obtained by emulsion polymerization of the following monomers in water in the presence of a surfactant with a radical polymerization initiator.
(C1) From the group consisting of an ethylenically unsaturated monomer (c1) having a monofunctional or polyfunctional alkoxysilyl group and a monomer (c2) having two or more ethylenically unsaturated groups in one molecule At least one monomer selected: 0.1 to 5% by weight
(C2) Ethylenically unsaturated monomers (c3) other than the monomers (c1) to (c2): 95 to 99.9% by weight
(However, the total of (c1) to (c3) is 100% by weight.)

[7] The composition according to [6] above, wherein the ethylenically unsaturated monomer (c3) has the following composition.
Ethylenically unsaturated monomer (c4) having a monofunctional or polyfunctional epoxy group, ethylenically unsaturated monomer (c5) having a monofunctional or polyfunctional amide group, and ethylene having a monofunctional or polyfunctional hydroxyl group At least one monomer selected from the group consisting of polymerizable unsaturated monomers (c6): 0.1 to 20% by weight
Ethylenically unsaturated monomers (c7) other than the monomers (c1), (c2), (c4) to (c6): 75 to 99.8% by weight
(However, the total of (c1) to (c3) is 100% by weight.)

[8] The composition according to [7] above, wherein the ethylenically unsaturated monomer (c7) has the following composition.
At least one monomer selected from the group consisting of an ethylenically unsaturated monomer (c8) having an alkyl group having 8 to 18 carbon atoms and an ethylenically unsaturated monomer (c9) having a cyclic structure: 30 ~ 95 wt%
Ethylenically unsaturated monomers other than the above (c1) to (c6), (c8) and (c9): 0 to 69.8% by weight
(However, the total of (c1) to (c3) is 100% by weight.)

[9] The binder composition (C) is at least one selected from the group consisting of an uncrosslinked epoxy group-containing compound, an uncrosslinked amide group-containing compound, an uncrosslinked hydroxyl group-containing compound, and an uncrosslinked oxazoline group-containing compound. The composition according to any one of the above [5] to [8], further comprising two uncrosslinked compounds (D).

[10] The composition according to any one of [1] to [9], wherein the cellulosic thickener (B) is hydroxyalkyl cellulose.

[11] An electrode for a secondary battery comprising a current collector and at least one of a composite material layer or an electrode underlayer formed from the composition described in [1] to [10] above.

[12] A secondary battery comprising a positive electrode, a negative electrode, and an electrolytic solution, wherein at least one of the positive electrode and the negative electrode is the electrode for a secondary battery according to the above [11].

[13] A lithium secondary battery comprising a positive electrode, a negative electrode, and an electrolytic solution, wherein at least one of the positive electrode and the negative electrode is the secondary battery electrode according to [11].

  According to a preferred embodiment of the present invention, an electrode-forming composition having excellent rheological properties and a dispersed state can be obtained. Furthermore, by preparing a composite material layer and an underlayer with this electrode forming composition, the adhesion to the current collector, the strength of the coating film, the flexibility of the coating film, and the resistance to electrolytic solution elution are improved. Cycle test performance can be improved.

  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 a composite ink), or (2) an active material, a conductive auxiliary agent, and a liquid A composite ink containing a medium, (3) a composite ink containing an active material, a binder and a liquid medium, and (4) a composite ink containing an active material, a conductive additive, a binder and a liquid medium. An electrode can be obtained by forming a composite layer using

  Alternatively, an electrode 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, as described above, the dispersion state of the active material and the conductive additive and the electrolytic solution elution resistance of the electrode mixture layer and the base layer influence the battery performance. The cationic dispersant (A) relaxes the aggregation of the active material or functions as a dispersant for the carbon material that is a conductive additive. Therefore, the aqueous composition for forming a secondary battery electrode of the present invention can be used as a composite ink that requires an active material or a composition for forming an underlayer that does not require an active material.

<Cationic dispersant (A)>
First, the cationic dispersant (A) in the present invention will be described. Hereinafter, the dispersant (A) may be abbreviated. The cationic dispersant (A) in the present invention has at least one of an aliphatic amine or an aromatic amine as a cationic site, has an amine value of 110 to 1000 mgKOH / g, and a hydroxyl value of 0 to 400 mgKOH / g. Yes, a resin-type dispersant having a weight average molecular weight of 5000 or more.

  The cationic dispersant (A) having an aliphatic amine or an aromatic amine is not particularly limited as long as it is a resin having an aliphatic amine or an aromatic amine. For example, it has an aliphatic amino group or an aromatic amino group. It is obtained by polymerizing or condensing a monomer, and is preferably obtained by polymerizing an ethylenically unsaturated monomer (a2) having an aliphatic amino group or an aromatic amino group. One type of monomer having an aliphatic amino group or aromatic amino group may be used, or a plurality of types may be used in combination.

  In addition, as the cationic dispersant (A) in the present invention, an ethylenically unsaturated monomer (a1) having an aromatic ring and an ethylenically unsaturated monomer having an aliphatic amino group or an aromatic amino group ( A resin type dispersant obtained by copolymerizing a2) and an ethylenically unsaturated monomer (a3) other than (a1) and (a2) can be used. Here, the monomer (a1) or (a3) is an optional component.

  The ethylenically unsaturated monomer constituting the cationic dispersant (A) in the present invention is a monomer having one ethylenically unsaturated group in one molecule unless otherwise specified.

<About the monomer (a1)>
The ethylenically unsaturated monomer (a1) having an aromatic ring is not particularly limited as long as it is a monomer having an aromatic ring, but styrene, α-methylstyrene or benzyl (meth) acrylate can be exemplified. .

<About monomer (a2)>
The ethylenically unsaturated monomer (a2) having an aliphatic amino group or an aromatic amino group is not particularly limited as long as it is a monomer having an aliphatic amino group or an aromatic amino group. For example, as a monomer having one ethylenically unsaturated group in one molecule, dimethylaminoethyl (meth) acrylate, diethylaminoethyl (meth) acrylate, methylethylaminoethyl (meth) acrylate, N , N-dimethylaminopropyl (meth) acrylate, allylamine, examples of the monomer having two ethylenically unsaturated groups in one molecule include diallylamine, diallylmethylamine and the like, and aromatic amino groups Aminostyrene, dimethylaminostyrene, diethylaminos It can be exemplified Len like.

<About monomer (a3)>
Next, the other monomer (a3) other than the above (a1) to (a2) will be described.
Examples of (meth) acrylate compounds include alkyl (meth) acrylates and alkylene glycol (meth) acrylates.

  More specifically, examples of the alkyl-based (meth) acrylate include alkyl (meth) acrylate having 1 to 22 carbon atoms such as methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, and butyl (meth) acrylate. ) When there is an acrylate and the purpose is to adjust the polarity, an alkyl group-containing acrylate having an alkyl group having 2 to 10 carbon atoms, more preferably 2 to 8 carbon atoms, or a corresponding methacrylate is preferable.

  Examples of the alkylene glycol-based (meth) acrylate include a monoacrylate having a hydroxyl group at the terminal and having a polyoxyalkylene chain, such as diethylene glycol mono (meth) acrylate and polyethylene glycol mono (meth) acrylate, or a corresponding monoacrylate. Such as methacrylate, methoxyethylene glycol (meth) acrylate, methoxydiethylene glycol (meth) acrylate, monoacrylate having an alkoxy group at the end and having a polyoxyalkylene chain, or the corresponding monomethacrylate, phenoxyethylene glycol Examples thereof include polyoxyalkylene-based acrylates having a phenoxy or aryloxy group at the terminal, such as (meth) acrylates, or corresponding methacrylates.

  Examples of hydroxyl-containing unsaturated compounds other than those described above include 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate, glycerol mono (meth) acrylate, and 4-hydroxyvinylbenzene. Etc.

  Examples of nitrogen-containing unsaturated compounds other than the above include acrylamide-based unsaturated compounds, and monoalkylols such as (meth) acrylamide, N-methylol (meth) acrylamide, N-methoxymethyl- (meth) acrylamide (meta) ) Acrylamide, dialalkylol (meth) acrylamide such as N, N-di (methylol) acrylamide, N-methylol-N-methoxymethyl (meth) acrylamide, N, N-di (methoxymethyl) acrylamide and the like.

  Further, as other unsaturated compounds, for example, as perfluoroalkyl group-containing vinyl monomers, perfluoromethylmethyl (meth) acrylate, perfluoroethylmethyl (meth) acrylate, 2-perfluorobutylethyl (meth) acrylate, 2- Perfluoroalkylalkyl (meth) acrylates having a C1-C20 perfluoroalkyl group such as perfluorohexylethyl (meth) acrylate; and perfluorobutylethylene, perfluorohexylethylene, perfluorooctylethylene, perfluoro And perfluoroalkylalkylenes such as decylethylene, etc. In addition, silanol group-containing vinyl compounds include vinyltrichlorosilane, vinyltris (βmethoxyethoxy) silane, vinyltril. Tokishishiran, .gamma. (meth) acryloxy propyl trimethoxy silane and the like, more can be mentioned their derivatives etc., may be used a plurality of 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, allyl alcohol, allylbenzene, and allyl cyanide, vinyl cyanide, vinylcyclohexane, vinyl methyl ketone, styrene, α-methylstyrene, 2-methylstyrene, chlorostyrene, and the like. It is done.

  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.

<Constitution ratio of monomers (a1) to (a3)>
The ratio of the ethylenically unsaturated monomers constituting the copolymer in the cationic dispersant (A) used in the present invention is the case where the total of the monomers (a1) to (a3) is 100% by weight In addition,
0 to 30% by weight of an ethylenically unsaturated monomer (a1) having an aromatic ring,
30 to 80% by weight of an ethylenically unsaturated monomer (a2) having an amino group,
It is preferable that the other monomer (a3) other than the (a1) to (a2) is 0 to 70% by weight.
More preferably,
0 to 30% by weight of an ethylenically unsaturated monomer (a1) having an aromatic ring,
50-80 wt% of ethylenically unsaturated monomer (a2) having an amino group,
The other monomer (a3) other than (a1) to (a2) is 0 to 50% by weight.

<Amine number of dispersant>
The cationic dispersant (A) is produced by polymerizing or condensing a monomer having an amino group, and the composition ratio of the monomer having a cationic functional group in the entire molecule of the cationic dispersant (A). Is represented by the amine value as follows. That is, the amine value of the cationic dispersant (A) used is preferably in the range of 110 mgKOH / g or more and less than 1000 mgKOH / g, and more preferably in the range of 250 mgKOH / g or more and less than 1000 mgKOH / g.

  When the amine value of the cationic dispersant (A) 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, when the amine value is higher than the above range, the adhesion of the cationic dispersant (A) to the pigment surface is lowered, and the storage stability of the dispersion tends to be lowered.

  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).

<Hydroxyl value of dispersant>
The hydroxyl value of the cationic dispersant (A) is preferably 0 mgKOH / g or more and 400 mgKOH / g or less, and more preferably 0 mgKOH / g or more and 250 mgKOH / g or less. When the hydroxyl value is 400 mgKOH / g or more, the interaction between molecules in the aqueous medium becomes stronger, and the viscosity of the dispersant solution becomes higher than necessary, so that the dispersibility of the conductive carbon or the active material is deteriorated. There is.

<Molecular weight of dispersant>
The weight average molecular weight of the cationic dispersant (A) is preferably 5000 or more. More preferably, it is 30000 or more. Moreover, the upper limit is preferably 1500,000 or less, and more preferably 800,000 or less. When the weight average molecular weight is less than 5,000, there is a possibility of causing poor dispersion of the carbon material that is the electrode active material or the conductive auxiliary agent, and when it is less than 30,000, there is a possibility that deterioration of the electrolyte dissolution property may be caused.

<Method for producing dispersant>
The cationic dispersant (A) can be obtained by various production methods. For example, the monomers (a1) to (a3) are polymerized 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 amino groups, the azeotropic solvent is distilled off, and an aqueous solution of the cationic dispersant (A) or An aqueous dispersion can be obtained.

  As an organic solvent at the time of polymerization, any solvent that azeotropes with water may be used, but those having high solubility in the resulting dispersant resin are preferable, and ethanol, 1-propanol, 2-propanol, and 1-butanol are preferable. 1-butanol is more preferable.

  Alternatively, the above monomers are polymerized in a hydrophilic organic solvent, and then neutralized and aqueousized by adding water and a neutralizing agent (the hydrophilic organic solvent is not distilled off). A solution in which the cationic dispersant (A) is dissolved or dispersed in an aqueous liquid medium containing can be obtained.

  In this case, the hydrophilic organic solvent used is preferably one having high solubility in the resulting dispersant resin, preferably glycol ethers, diols, more preferably (poly) alkylene glycol monoalkyl ether, carbon number. 3-6 alkanediols are preferred.

  As a neutralizing agent used for neutralization in the manufacturing process, for example, an organic acid or an inorganic acid can be used.

<About the neutralizing agent>
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

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

<About the function as a dispersant>
It is presumed that the hydrophobic part, which is a constituent part of the cationic dispersant, becomes a main adsorption part to the active material and carbon material described later. In particular, when an aromatic ring is included as a hydrophobic portion, it is considered that the adsorptive power to an active material or a carbon material is improved. The ethylenically unsaturated monomer (a2) having an aliphatic amino group or an aromatic amino group is considered to have a function of dissolving or dispersing the dispersant resin or a neutralized product thereof in an aqueous liquid medium. The active material and the carbon material are acted on (for example, adsorbed) by a dispersant resin via a hydrophobic portion (for example, an aromatic ring) and neutralized, whereby the active material is subjected to charge repulsion of ionized amino groups. It is considered that the dispersion state of the carbon material and the carbon material in the aqueous liquid medium can be kept stable.
The amino group possessed by the cationic dispersant (A) is preferably an aliphatic amino group. One reason for this is thought to be that aliphatic amines have a higher pKa and higher basicity, and thus have a higher function of dissolving or dispersing the dispersant in the aqueous liquid medium. Another reason is that in the case of an aromatic amino group, since the aromatic ring and the amino group are present in the vicinity, the acting force on the active material and the carbon material (for example, adsorption) and the dissolving power or dispersion force in the aqueous liquid medium Is considered to be inferior to the aliphatic amino group.

<Cellulose-based thickener (B)>
Although it does not specifically limit as a cellulose thickener (B), For example, carboxymethylcellulose (CMC), carboxyethylcellulose, hydroxyethylcellulose (HEC), hydroxypropylcellulose (HPC), ethylhydroxyethylcellulose (EHEC), hydroxymethyl, for example. Examples include ethyl cellulose, hydroxyhydroxypropyl methyl cellulose, methyl cellulose (MC), and hydroxyalkyl methyl cellulose.

  Cellulose in pulp is a polysaccharide to which anhydroglucose monomer units are bonded, and has three hydroxy groups in one glucose monomer unit. The substituent that is substituted with one or more of the hydroxy groups can be selected without any particular limitation, but is a hydrophilic substituent in order to be a water-soluble cellulose-based thickener (B). It is preferable. A carboxyalkyl group and a hydroxyalkyl group are preferable, and a hydroxyalkyl group is particularly preferable.

  The number of substituents substituted on the hydroxy group in cellulose is not particularly limited, but it is preferable that 0.5 or more of the three hydroxy groups of one glucose monomer unit are substituted. Moreover, the average degree of polymerization of the cellulosic thickener (B) can be selected without any particular limitation.

<Effect of combined use of dispersant (A) and cellulose thickener (B)>
As one of the effects of the dispersant (A), the added dispersant (A) acts (for example, adsorbs) on the surface of the carbon material and the surface of the active material, so that the carbon material surface and the surface of the active material material are wetted with the solvent. It is considered that the dispersion state and rheological properties are improved by solving the aggregation of the carbon material and the active material.

  Further, when the dispersant (A) is used in combination with the cellulose-based thickener (B), the dispersibility and rheological properties by the dispersant (A) and the thickening effect by the cellulose-based thickener (B) are impaired. It can function without being disintegrated and exhibit even higher dispersion stability. At this time, the dispersant (A) is more likely to act (for example, adsorb) on the surface of the carbon material and the active material, so that it exhibits a dispersibility improving effect and a rheological property improving effect, and the cellulose-based thickener (B) Is considered to exert a thickening effect mainly.

  Cellulosic thickener (B) can be used in combination with dispersant (A) regardless of whether it is anionic or nonionic, but considering the dispersibility improvement effect and rheological property improvement effect of compound ink In this case, the nonionic cellulose thickener (B) is more preferable. This is because the nonionic cellulose-based thickener (B) has a lower effect on the surface of the carbon material and the active material surface, and thus the dispersion effect, so that when used in combination with the dispersant (A), the function is further separated. It seems to work.

  Moreover, the dispersing agent (A) having a charge has high hydrophilicity and is compatible with the cellulose-based thickener (B). Therefore, it is possible to form a composite ink coating film without phase separation of the dispersant (A) and the cellulose-based thickener (B) during the drying process of the composite ink. It is considered that the mixing of is more uniform and the coating becomes stronger. As a result, the strength of the composite material layer is increased, and it is considered that cracking when the composite material layer is thickened is improved (flexibility is improved).

<Binder composition (C)>
Next, the binder composition (C) will be described. In the present invention, it is preferable to include cross-linked resin fine particles. The crosslinked resin fine particles are resin fine particles having an internal cross-linked structure (three-dimensional cross-linked structure), and it is important that the fine particles are cross-linked inside the particles. When the cross-linked resin fine particles have a cross-linked structure, the electrolytic solution elution resistance can be improved, and the effect can be enhanced by adjusting the cross-linking inside the particles. Further, when the cross-linked resin fine particles contain a specific functional group, it is possible to contribute to adhesion with the current collector or the electrode. Furthermore, the composition for secondary battery electrode formation excellent in flexibility can be obtained by adjusting the quantity of a crosslinked structure and a functional group. Furthermore, the flexibility of the binder can also be adjusted by adding a crosslinking agent and utilizing crosslinking between particles (crosslinking between particles). In this case, since the leakage of the cross-linking agent component to the electrolytic solution and variations in electrode production may occur, it is necessary to use the cross-linking agent to such an extent that the resistance to the electrolytic solution is not impaired.

  Examples of the crosslinked resin fine particles used in the electrode-forming composition of the present invention include resin fine particles obtained by emulsion polymerization of an ethylenically unsaturated monomer in water in the presence of a surfactant with a radical polymerization initiator. Is mentioned. Such crosslinked resin fine particles are preferably obtained by emulsion polymerization of an ethylenically unsaturated monomer containing the following monomers (C1) and (C2) in the following proportions.

(C1) From the group consisting of an ethylenically unsaturated monomer (c1) having a monofunctional or polyfunctional alkoxysilyl group and a monomer (c2) having two or more ethylenically unsaturated groups in one molecule At least one monomer selected: 0.1 to 5% by weight
(C2) Ethylenically unsaturated monomers (c3) other than the monomers (c1) to (c2): 95 to 99.9% by weight
(However, the total of (c1) to (c3) is 100% by weight.)

  Of the ethylenically unsaturated monomers constituting the crosslinked resin fine particles, (c1) and (c3) indicate monomers having one ethylenically unsaturated group in one molecule unless otherwise specified. .

<About the monomer group (C1)>
The functional group (alkoxysilyl group, ethylenically unsaturated group) possessed by the monomer contained in the monomer group (C1) is a self-crosslinking reactive functional group, and is mainly used for particle internal crosslinking during particle synthesis. Has the effect of forming. Electrolytic solution resistance can be improved by sufficiently carrying out internal crosslinking of the particles. Therefore, it is possible to obtain crosslinked resin fine particles by using a monomer contained in the monomer group (C1). In addition, by sufficiently carrying out particle crosslinking, the resistance to electrolytic solution can be improved.

  Examples of the ethylenically unsaturated monomer (c1) having a monofunctional or polyfunctional alkoxysilyl group include γ-methacryloxypropyltrimethoxysilane, γ-methacryloxypropyltriethoxysilane, and γ-methacryloxypropyltributoxy. Silane, γ-methacryloxypropylmethyldimethoxysilane, γ-methacryloxypropylmethyldiethoxysilane, γ-acryloxypropyltrimethoxysilane, γ-acryloxypropyltriethoxysilane, γ-acryloxypropylmethyldimethoxysilane, γ- Methacryloxymethyltrimethoxysilane, γ-acryloxymethyltrimethoxysilane, vinyltrimethoxysilane, vinyltriethoxysilane, vinyltributoxysilane, vinylmethyldimethoxysilane, etc. .

  Examples of the monomer (c2) having two or more ethylenically unsaturated groups in one molecule include allyl (meth) acrylate, 1-methylallyl (meth) acrylate, and 2-methylallyl (meth) acrylate. 1-butenyl (meth) acrylate, 2-butenyl (meth) acrylate, 3-butenyl (meth) acrylate, 1,3-methyl-3-butenyl (meth) acrylate, 2- (meth) acrylate 2- Chloroallyl, 3-chloroallyl (meth) acrylate, o-allylphenyl (meth) acrylate, 2- (allyloxy) ethyl (meth) acrylate, allyl lactyl (meth) acrylate, citronellyl (meth) acrylate, (meth) Geranyl acrylate, rosinyl (meth) acrylate, cinnamyl (meth) acrylate, diallyl maleate, diallyl itaconic acid (Meth) acrylic acid esters containing ethylenically unsaturated groups such as vinyl (meth) acrylate, vinyl crotonate, vinyl oleate, vinyl linolenate, 2- (2′-vinyloxyethoxy) ethyl (meth) acrylate ; Ethylene glycol di (meth) acrylate, triethylene glycol di (meth) acrylate, tetraethylene glycol di (meth) acrylate, trimethylolpropane tri (meth) acrylate, pentaerythritol tri (meth) acrylate, diacryl Multifunctional (meth) acrylic acid esters such as 1,1,1-trishydroxymethylethane acid, 1,1,1-trishydroxymethylethane triacrylate, 1,1,1-trishydroxymethylpropanetriacrylic acid Divinylbenzene, divinyl adipate, etc. Vinyls; diallyl isophthalate, diallyl phthalate, etc. diallyl such as diallyl maleate and the like.

  The purpose of the alkoxysilyl group or ethylenically unsaturated group in the monomer (c1) or monomer (c2) is to introduce a cross-linked structure into the particle by self-condensation or polymerization mainly during the polymerization. However, a part of it may remain inside or on the surface after polymerization. The remaining alkoxysilyl group or ethylenically unsaturated group contributes to interparticle crosslinking of the binder composition. In particular, an alkoxysilyl group is preferable because it has an effect of improving adhesion to the current collector.

  In the present invention, the monomer classified into the monomer group (C1) is used in an amount of 0.1 to 5% by weight in the whole ethylenically unsaturated monomer (100% by weight in total) used for emulsion polymerization. It is characterized by this, Preferably it is 0.5 to 3 weight%. When the monomer classified into the monomer group (C1) is less than 0.1% by weight, the particles are not sufficiently crosslinked, and the resistance to the electrolytic solution is deteriorated. On the other hand, if it exceeds 5% by weight, there will be a problem in the polymerization stability at the time of emulsion polymerization, or even if it can be polymerized, there will be a problem in the storage stability.

<About monomer group (C2)>
In addition to the monomer (c1) and the monomer (c2) described above, the crosslinked resin fine particles used in the binder composition include a monomer group (C2) other than the monomers (c1) and (c2). The monomer (c3) having an ethylenically unsaturated group can be obtained by emulsion polymerization at the same time.

  The monomer (c3) is not particularly limited as long as it is a monomer having an ethylenically unsaturated group other than the monomers (c1) and (c2). For example, a monofunctional or polyfunctional epoxy Ethylenically unsaturated monomer (c4) having a group, ethylenically unsaturated monomer (c5) having a monofunctional or polyfunctional amide group, and an ethylenically unsaturated monomer having a monofunctional or polyfunctional hydroxyl group At least one monomer selected from the group consisting of (c6), and a monomer having an ethylenically unsaturated group other than the monomers (c1), (c2), (c4) to (c6) ( c7) can be used.

  By using the monomers (c4) to (c6), an epoxy group, an amide group, or a hydroxyl group can be left in the particles or on the surface of the cross-linked resin fine particles, whereby adhesion to the current collector is achieved. The physical properties such as can be improved. In the monomers (c4) to (c6), the functional group tends to remain inside or on the surface of the particles even after the particle synthesis, and the adhesion effect to the current collector is large even in small amounts. Moreover, a part of them may be used for the crosslinking reaction, and by adjusting the degree of crosslinking of these functional groups, it is possible to balance the resistance to electrolytic solution and the adhesion.

  Examples of the ethylenically unsaturated monomer (c4) having a monofunctional or polyfunctional epoxy group include glycidyl (meth) acrylate and 3,4-epoxycyclohexyl (meth) acrylate.

  Examples of the monomer ethylenically unsaturated (c5) having a monofunctional or polyfunctional amide group include, for example, primary amide group-containing ethylenically unsaturated monomers such as (meth) acrylamide; N-methylolacrylamide, N, Alkylol (meth) acrylamides such as N-di (methylol) acrylamide, N-methylol-N-methoxymethyl (meth) acrylamide; N-methoxymethyl- (meth) acrylamide, N-ethoxymethyl- (meth) acrylamide, Monoalkoxy (meth) acrylamides such as N-propoxymethyl- (meth) acrylamide, N-butoxymethyl- (meth) acrylamide, N-pentoxymethyl- (meth) acrylamide; N, N-di (methoxymethyl) acrylamide N-ethoxymethyl-N-methoxyme Rumethacrylamide, N, N-di (ethoxymethyl) acrylamide, N-ethoxymethyl-N-propoxymethylmethacrylamide, N, N-di (propoxymethyl) acrylamide, N-butoxymethyl-N- (propoxymethyl) meta Acrylamide, N, N-di (butoxymethyl) acrylamide, N-butoxymethyl-N- (methoxymethyl) methacrylamide, N, N-di (pentoxymethyl) acrylamide, N-methoxymethyl-N- (pentoxymethyl) ) Dialkoxy (meth) acrylamides such as methacrylamide; dialkylamino (meth) acrylamides such as N, N-dimethylaminopropyl acrylamide and N, N-diethylaminopropyl acrylamide; N, N-dimethylacrylamide; , N- dialkyl such as diethyl acrylamide (meth) acrylamides; and containing keto groups, such as diacetone (meth) acrylamide (meth) acrylamides and the like.

  Examples of the ethylenically unsaturated monomer (c6) having a monofunctional or polyfunctional hydroxyl group include 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate, Examples include 2- (meth) acryloyloxyethyl-2-hydroxyethylphthalic acid, glycerol mono (meth) acrylate, 4-hydroxyvinylbenzene, 1-ethynyl-1-cyclohexanol, and allyl alcohol.

  Some of the functional groups of the monomers classified into the monomers (c4) to (c6) may react during particle polymerization and be used for intraparticle crosslinking. In the present invention, the monomers classified into the monomers (c4) to (c6) are 0.1 to 20% by weight in the whole ethylenically unsaturated monomers (100% by weight in total) used for emulsion polymerization. %, Preferably 1 to 15% by weight, particularly preferably 2 to 10% by weight. When the amount of the monomers (c4) to (c6) is less than 0.1% by weight, the amount of functional groups remaining in the interior of the particles or on the surface after polymerization is reduced, and the adhesion to the current collector is improved. Cannot contribute enough. On the other hand, if it exceeds 20% by weight, there will be a problem in the polymerization stability at the time of emulsion polymerization, or even if it can be polymerized, there will be a problem in the storage stability.

  The monomer (c7) is not particularly limited as long as it is a monomer having an ethylenically unsaturated group other than the monomers (c1), (c2), and (c4) to (c6). Examples thereof include an ethylenically unsaturated monomer (c8) having an alkyl group having 8 to 18 carbon atoms and an ethylenically unsaturated monomer (c9) having a cyclic structure. When the monomer (c8) and / or the monomer (c9) is used for the emulsion polymerization as the monomer (c7) (including other monomers as the monomer (c7)) The monomers (c8) and (c9) are all monomers having an ethylenically unsaturated group ((c1), (c2), (c4) to (c6) and (c7)). It is preferable that 30 to 95 weight% is contained in total. It is preferable to use the monomer (c8) or the monomer (c9) because the particle stability during particle synthesis and the resistance to electrolytic solution are excellent. If it is less than 30% by weight, the electrolyte solution resistance may be adversely affected. If it exceeds 95% by weight, the stability during particle synthesis will be adversely affected, or even if synthesis is possible, the temporal stability of the particles will be impaired. There is a case.

  Examples of the ethylenically unsaturated monomer (c8) having an alkyl group having 8 to 18 carbon atoms include 2-ethylhexyl (meth) acrylate, lauryl (meth) acrylate, myristyl (meth) acrylate, and cetyl (meth) acrylate. And stearyl (meth) acrylate.

  Examples of the ethylenically unsaturated monomer (c9) having a cyclic structure include alicyclic ethylenically unsaturated monomers and aromatic ethylenically unsaturated monomers. Examples of the alicyclic ethylenically unsaturated monomer include cyclohexyl (meth) acrylate and isobornyl (meth) acrylate, and examples of the aromatic ethylenically unsaturated monomer include benzyl (meth) acrylate. Phenoxyethyl (meth) acrylate, styrene, α-methylstyrene, 2-methylstyrene, chlorostyrene, allylbenzene, ethynylbenzene and the like.

  Examples of monomers other than the monomer (c8) and monomer (c9) classified as monomer (c7) include methyl (meth) acrylate, ethyl (meth) acrylate, and propyl (meta). ) Acrylate, n-butyl (meth) acrylate, pentyl (meth) acrylate, heptyl (meth) acrylate and other alkyl group-containing ethylenically unsaturated monomers; (meth) acrylonitrile and other nitrile group-containing ethylenically unsaturated monomers Body: perfluoromethylmethyl (meth) acrylate, perfluoroethylmethyl (meth) acrylate, 2-perfluorobutylethyl (meth) acrylate, 2-perfluorohexylethyl (meth) acrylate, 2-perfluorooctylethyl (meta ) Acrylate, 2-perfluoroisononylethyl (meth) Acrylate, 2-perfluorononylethyl (meth) acrylate, 2-perfluorodecylethyl (meth) acrylate, perfluoropropylpropyl (meth) acrylate, perfluorooctylpropyl (meth) acrylate, perfluorooctyl amyl (meth) acrylate Perfluoroalkyl group-containing ethylenically unsaturated monomers having 1 to 20 carbon atoms such as perfluorooctyl undecyl (meth) acrylate; perfluorobutylethylene, perfluorohexylethylene, perfluorooctyl Perfluoroalkyl such as ethylene and perfluorodecylethylene, and perfluoroalkyl group-containing ethylenically unsaturated compounds such as alkylenes; polyethylene glycol (meth) acrylate Methoxy polyethylene glycol (meth) acrylate, ethoxy polyethylene glycol (meth) acrylate, propoxy polyethylene glycol (meth) acrylate, n-butoxy polyethylene glycol (meth) acrylate, n-pentoxy polyethylene glycol (meth) acrylate, phenoxy polyethylene glycol (meta ) Acrylate, polypropylene glycol (meth) acrylate, methoxy polypropylene glycol (meth) acrylate, ethoxy polypropylene glycol (meth) acrylate, propoxy polypropylene glycol (meth) acrylate, n-butoxy polypropylene glycol (meth) acrylate, n-pentoxy polypropylene glycol (Meth) acrylate, phenoxypo Ripropylene glycol (meth) acrylate, polytetramethylene glycol (meth) acrylate, methoxypolytetramethylene glycol (meth) acrylate, phenoxytetraethylene glycol (meth) acrylate, hexaethylene glycol (meth) acrylate, methoxyhexaethylene glycol (meta ) Ethylenically unsaturated compounds having a polyether chain such as acrylate; ethylenically unsaturated compounds having a polyester chain such as lactone-modified (meth) acrylate; (meth) acrylic acid dimethylaminoethylmethyl chloride salt, trimethyl-3- ( 1- (meth) acrylamide-1,1-dimethylpropyl) ammonium chloride, trimethyl-3- (1- (meth) acrylamidopropyl) ammonium chloride And ethylenically unsaturated compounds containing quaternary ammonium bases such as trimethyl-3- (1- (meth) acrylamide-1,1-dimethylethyl) ammonium chloride; vinyl acetate, vinyl butyrate, vinyl propionate, vinyl hexanoate Fatty acid vinyl compounds such as vinyl caprylate, vinyl laurate, vinyl palmitate and vinyl stearate; vinyl ether ethylenically unsaturated monomers such as butyl vinyl ether and ethyl vinyl ether; 1-hexene, 1-octene, 1- Α-olefinic ethylenically unsaturated monomers such as decene, 1-dodecene, 1-tetradecene and 1-hexadecene; allyl monomers such as allyl acetate and allyl cyanide; vinyl cyanide, vinylcyclohexane and vinylmethylketone Vinyl monomers such as; And ethynyl monomers such as acetylene and ethynyltoluene.

  Examples of monomers other than the monomer (c8) and monomer (c9) classified as monomer (c7) include maleic acid, fumaric acid, itaconic acid, citraconic acid, or , These alkyl or alkenyl monoesters, phthalic acid β- (meth) acryloxyethyl monoester, isophthalic acid β- (meth) acryloxyethyl monoester, terephthalic acid β- (meth) acryloxyethyl monoester, succinic acid Carboxyl group-containing ethylenically unsaturated monomers such as β- (meth) acryloxyethyl monoester, acrylic acid, methacrylic acid, crotonic acid, and cinnamic acid; tertiary butyl groups such as tertiary butyl (meth) acrylate Ethylenically unsaturated monomers; Ethylene containing sulfonic acid groups such as vinyl sulfonic acid and styrene sulfonic acid Unsaturated monomers; phosphoric acid group-containing ethylenically unsaturated monomers such as (2-hydroxyethyl) methacrylate acid phosphate; diacetone (meth) acrylamide, acrolein, N-vinylformamide, vinyl methyl ketone, vinyl Keto group-containing ethylenically unsaturated monomers such as ethyl ketone, acetoacetoxyethyl (meth) acrylate, acetoacetoxypropyl (meth) acrylate, acetoacetoxybutyl (meth) acrylate (one ethylenically unsaturated group per molecule) And a monomer having a keto group).

  When a keto group-containing ethylenically unsaturated monomer is used as the monomer (c7), a polyfunctional hydrazide compound having two or more hydrazide groups capable of reacting with a keto group as a crosslinking agent is mixed with the binder composition. A tough coating film can be obtained by crosslinking between a keto group and a hydrazide group. This coating film has excellent electrolytic solution resistance and binding properties. Furthermore, since it is possible to achieve both durability and flexibility in a high temperature environment due to repeated charge / discharge and heat generation, a long-life non-aqueous secondary battery with reduced discharge capacity reduction in the charge / discharge cycle is obtained. Can do.

  Among the monomers (c7), an ethylenically unsaturated monomer having a carboxyl group, a tertiary butyl group (tertiary butanol is removed by heat to form a carboxyl group), a sulfonic acid group, and a phosphoric acid group. The resin fine particles obtained by copolymerization of the body have the effect of improving the physical properties such as adhesion to the current collector, and the functional groups remain in the particles and on the surface even after the polymerization. Since aggregation may be prevented or particle stability after synthesis may be maintained, it can be preferably used.

  A part of the carboxyl group, tertiary butyl group, sulfonic acid group, and phosphoric acid group may react during polymerization and be used for intraparticle crosslinking. In the case of using a monomer containing a carboxyl group, a tertiary butyl group, a sulfonic acid group, and a phosphoric acid group, the total amount of ethylenically unsaturated monomers used in the emulsion polymerization (100% by weight in total) is 0. The content is preferably 1 to 10% by weight, more preferably 1 to 5% by weight. When the monomer containing these functional groups is less than 0.1% by weight, the stability of the particles may be deteriorated. On the other hand, when the content exceeds 10% by weight, the hydrophilicity of the binder composition becomes too strong, and the electrolytic solution resistance may deteriorate. Furthermore, these functional groups may react during drying and be used for cross-linking within or between particles.

  For example, a carboxyl group can react with an epoxy group during polymerization and drying to introduce a crosslinked structure into the resin fine particles. Similarly, a tertiary butyl group can also react with an epoxy group in the same manner as described above because tertiary butyl alcohol is generated and a carboxyl group is formed when heat of a certain temperature or higher is applied.

  These monomers (c7) are used in combination of two or more of the above-mentioned monomers in order to adjust the polymerization stability and glass transition temperature of the particles, as well as the film formability and film properties. Can be used. Further, for example, by using (meth) acrylonitrile in combination, there is an effect that rubber elasticity is exhibited.

<Method for producing crosslinked resin fine particles>
The crosslinked resin fine particles can be synthesized by a conventionally known emulsion polymerization method.

<Emulsifier used in emulsion polymerization>
As the emulsifier used in the emulsion polymerization, conventionally known emulsifiers such as a reactive emulsifier having an ethylenically unsaturated group and a non-reactive emulsifier having no ethylenically unsaturated group can be arbitrarily used.

  Reactive emulsifiers having an ethylenically unsaturated group can be further roughly classified into anionic and nonionic nonionic ones. Especially when anionic reactive emulsifier or nonionic reactive emulsifier having an ethylenically unsaturated group is used, the dispersion particle size of the copolymer becomes finer and the particle size distribution becomes narrower, so it is used as a binder for secondary battery electrodes. In this case, the resistance to electrolytic solution can be improved. These anionic reactive emulsifiers or nonionic reactive emulsifiers having an ethylenically unsaturated group may be used singly or in combination.

  Specific examples of the anionic reactive emulsifier having an ethylenically unsaturated group are shown below, but usable emulsifiers are not limited thereto.

  As an emulsifier, an alkyl ether type (as commercial products, for example, Aqualon KH-05, KH-10, KH-20, manufactured by Daiichi Kogyo Seiyaku Co., Ltd., Adeka Soap SR-10N, SR-20N manufactured by ADEKA Co., Ltd., Laterum PD-104 manufactured by Kao Corporation); sulfosuccinic acid ester system (for example, LATEMUL S-120, S-120A, S-180P, S-180A manufactured by Kao Corporation, Elemiol manufactured by Sanyo Chemical Co., Ltd.) JS-2 etc.); alkylphenyl ether type or alkylphenyl ester type (commercially available products include, for example, Aqualon H-2855A, H-3855B, H-3855C, H-3856, HS-05 manufactured by Daiichi Kogyo Seiyaku Co., Ltd.) , HS-10, HS-20, HS-30, ADEKA Corporation ADEKA rear SDX-222, SDX-223, SDX-232, SDX-233, SDX-259, SE-10N, SE-20N, etc.) (meth) acrylate sulfate ester (commercially available products include, for example, Japanese emulsifiers) Antox MS-60, MS-2N, Sanyo Kasei Kogyo Co., Ltd., Eleminol RS-30, etc.); Phosphate ester (for example, H-3330PL, Daiichi Kogyo Seiyaku Co., Ltd., stock) Adeka Soap PP-70 manufactured by the company ADEKA).

  Nonionic reactive emulsifiers include, for example, alkyl ethers (for example, commercially available products such as Adeka Soap ER-10, ER-20, ER-30, ER-40 manufactured by ADEKA Corporation, LATEMUL PD- manufactured by Kao Corporation 420, PD-430, PD-450, etc.); alkylphenyl ethers or alkylphenyl esters (commercially available products include, for example, Aqualon RN-10, RN-20, RN-30, RN manufactured by Dai-ichi Kogyo Seiyaku Co., Ltd.) -50, Adeka Soap NE-10, NE-20, NE-30, NE-40, etc., manufactured by ADEKA Corporation; (meth) acrylate sulfate ester system (commercially available products include, for example, RMA- manufactured by Nippon Emulsifier Co., Ltd.) 564, RMA-568, RMA-1114, etc.).

  In obtaining the functional group-containing crosslinked resin fine particles by emulsion polymerization, a non-reactive emulsifier having no ethylenically unsaturated group can be used in combination with the above-described reactive emulsifier having an ethylenically unsaturated group, if necessary. . Non-reactive emulsifiers can be broadly classified into non-reactive anionic emulsifiers and non-reactive nonionic emulsifiers.

  Examples of non-reactive nonionic emulsifiers include polyoxyethylene alkyl ethers such as polyoxyethylene lauryl ether and polyoxyethylene stearyl ether; polyoxyethylene alkyl such as polyoxyethylene octyl phenyl ether and polyoxyethylene nonyl phenyl ether Sorbitan monolaurate, sorbitan monostearate, sorbitan higher fatty acid esters such as sorbitan trioleate; polyoxyethylene sorbitan higher fatty acid esters such as polyoxyethylene sorbitan monolaurate; polyoxyethylene monolaurate, Polyoxyethylene higher fatty acid esters such as polyoxyethylene monostearate; oleic acid monoglyceride, stearic acid monoglyceride Glycerine higher fatty acid esters such as chloride, polyoxyethylene-polyoxypropylene block copolymers, and the like can be exemplified polyoxyethylene distyrenated phenyl ether.

  Examples of non-reactive anionic emulsifiers include higher fatty acid salts such as sodium oleate; alkyl aryl sulfonates such as sodium dodecylbenzene sulfonate; alkyl sulfate esters such as sodium lauryl sulfate; polyoxyethylene lauryl ether Polyoxyethylene alkyl ether sulfates such as sodium sulfate; polyoxyethylene alkylaryl ether sulfates such as polyoxyethylene nonylphenyl ether sodium sulfate; sodium monooctyl sulfosuccinate, sodium dioctyl sulfosuccinate, polyoxyethylene lauryl sulfosuccinic acid Alkylsulfosuccinic acid ester salts such as sodium and derivatives thereof; polyoxyethylene distyrenated phenyl ether And the like can be exemplified sulfuric ester salts.

  The amount of the emulsifier used is not necessarily limited, and can be appropriately selected according to physical properties required when the crosslinked resin fine particles are finally used as a binder for a secondary battery electrode. For example, the amount of the emulsifier is usually preferably 0.1 to 30 parts by weight, more preferably 0.3 to 20 parts by weight, based on 100 parts by weight of the total of ethylenically unsaturated monomers. More preferably, it is in the range of 5 to 10 parts by weight.

  In emulsion polymerization, a water-soluble protective colloid can be used in combination. Examples of water-soluble protective colloids include polyvinyl alcohols such as partially saponified polyvinyl alcohol, fully saponified polyvinyl alcohol, and modified polyvinyl alcohol; cellulose derivatives such as hydroxyethyl cellulose, hydroxypropyl cellulose, and carboxymethyl cellulose salt; Examples thereof include saccharides, and these can be used alone or in a combination of plural kinds. The amount of the water-soluble protective colloid used is 0.1 to 5 parts by weight, more preferably 0.5 to 2 parts by weight, per 100 parts by weight of the total of ethylenically unsaturated monomers.

<Aqueous medium used in emulsion polymerization>
Examples of the aqueous medium used in the emulsion polymerization include water, and hydrophilic organic solvents can be used as long as the object of the present invention is not impaired.

<Polymerization initiator used in emulsion polymerization>
The polymerization initiator is not particularly limited as long as it has the ability to initiate radical polymerization, and known oil-soluble polymerization initiators and water-soluble polymerization initiators can be used.

  The oil-soluble polymerization initiator is not particularly limited, and examples thereof include benzoyl peroxide, tert-butyl peroxybenzoate, tert-butyl hydroperoxide, tert-butyl peroxy (2-ethylhexanoate), and tert-butyl peroxide. Organic peroxides such as oxy-3,5,5-trimethylhexanoate, di-tert-butyl peroxide; 2,2′-azobisisobutyronitrile, 2,2′-azobis-2,4- Examples thereof include azobis compounds such as dimethylvaleronitrile, 2,2′-azobis (4-methoxy-2,4-dimethylvaleronitrile), 1,1′-azobiscyclohexane-1-carbonitrile. These can be used alone or in combination of two or more. These polymerization initiators are preferably used in an amount of 0.1 to 10.0 parts by weight with respect to 100 parts by weight of the ethylenically unsaturated monomer.

  In particular, a water-soluble polymerization initiator is preferable. For example, a conventionally known one such as ammonium persulfate, potassium persulfate, hydrogen peroxide, 2,2′-azobis (2-methylpropionamidine) dihydrochloride is preferably used. Can do.

  Moreover, when performing emulsion polymerization, a reducing agent can be used together with a polymerization initiator if desired. Thereby, it becomes easy to accelerate the emulsion polymerization rate or to perform the emulsion polymerization at a low temperature. Examples of such a reducing agent include reducing organic compounds such as metal salts such as ascorbic acid, ersorbic acid, tartaric acid, citric acid, glucose, and formaldehyde sulfoxylate, sodium thiosulfate, sodium sulfite, sodium bisulfite, Examples include reducing inorganic compounds such as sodium bisulfite, ferrous chloride, Rongalite, thiourea dioxide, and the like. These reducing agents are preferably used in an amount of 0.05 to 5.0 parts by weight with respect to 100 parts by weight of the total ethylenically unsaturated monomer.

<Conditions for emulsion polymerization>
In addition, it can superpose | polymerize by a photochemical reaction, radiation irradiation, etc. irrespective of a polymerization initiator. The polymerization temperature is not less than the polymerization start temperature of each polymerization initiator. For example, in the case of a peroxide-based polymerization initiator, it may be usually about 70 ° C. The polymerization time is not particularly limited, but is usually 2 to 24 hours.

<Other materials used for reaction>
Further, if necessary, sodium acetate, sodium citrate, sodium bicarbonate, etc. as a buffering agent, and octyl mercaptan, 2-ethylhexyl thioglycolate, octyl thioglycolate, stearyl mercaptan, lauryl mercaptan as a chain transfer agent A suitable amount of mercaptans such as t-dodecyl mercaptan can be used.

  When a monomer having an acidic functional group such as a carboxyl group-containing ethylenically unsaturated monomer is used for the polymerization of the crosslinked resin fine particles, it may be neutralized with a basic compound before or after the polymerization. When neutralizing, it can be neutralized with ammonia or alkylamines such as trimethylamine, triethylamine and butylamine; alcohol amines such as 2-dimethylaminoethanol, diethanolamine, triethanolamine and aminomethylpropanol; and a base such as morpholine. . However, it is a highly volatile base that is highly effective in drying, and preferred bases are aminomethylpropanol and ammonia.

<Glass transition temperature of crosslinked resin fine particles>
Further, the glass transition temperature (hereinafter also referred to as Tg) of the crosslinked resin fine particles is preferably -30 to 70 ° C, more preferably -20 to 30 ° C. When Tg is less than −30 ° C., the binder excessively covers the electrode active material, and the impedance tends to increase. Moreover, when Tg exceeds 70 degreeC, the softness | flexibility and adhesiveness of a binder will become scarce, and the adhesiveness to the electrical power collector of an electrode active material and the moldability of an electrode may be inferior. The glass transition temperature is a value obtained using a DSC (differential scanning calorimeter).

  The measurement of the glass transition temperature by DSC (differential scanning calorimeter) can be performed as follows. About 2 mg of resin obtained by drying the cross-linked resin fine particles is weighed on an aluminum pan, the test container is set on a DSC measurement holder, and the endothermic peak of the chart obtained under a temperature rising condition of 10 ° C./min is read. The peak temperature at this time is defined as the glass transition temperature.

<Particle structure of cross-linked resin fine particles>
Further, the particle structure of the crosslinked resin fine particles may be a multi-layer structure, so-called core-shell particles. For example, it is possible to localize a resin in which a monomer having a functional group is mainly polymerized in the core part or the shell part, or to provide a difference in Tg or composition between the core and the shell, thereby improving the curability and drying. Property, film formability, and mechanical strength of the binder can be improved.

<Particle size of cross-linked resin fine particles>
The average particle diameter of the crosslinked resin fine particles is preferably 10 to 500 nm, more preferably 30 to 250 nm, from the viewpoint of the binding property of the electrode active material and the stability of the particles. Further, when a large amount of coarse particles exceeding 1 μm are contained, the stability of the particles is impaired, so that the coarse particles exceeding 1 μm are preferably at most 5% by weight. In addition, an average particle diameter represents a volume average particle diameter, and can be measured by the dynamic light scattering method.

  The average particle diameter can be measured by the dynamic light scattering method as follows. The cross-linked resin fine particle dispersion is diluted with water 200 to 1000 times depending on the solid content. About 5 ml of the diluted solution is injected into a cell of a measuring apparatus [Microtrack manufactured by Nikkiso Co., Ltd.] and measurement is performed after inputting the solvent (for example, water) and the refractive index condition of the resin according to the sample. The peak of the volume particle size distribution data (histogram) obtained at this time is defined as the average particle size.

<Uncrosslinked compound (D) added to polymerized fine resin particles>
In addition to the crosslinked resin fine particles, the binder composition further includes a non-crosslinked epoxy group-containing compound, an uncrosslinked amide group-containing compound, an uncrosslinked hydroxyl group-containing compound, and an uncrosslinked oxazoline group-containing compound. It is preferable to include at least one uncrosslinked compound (D) [hereinafter sometimes referred to as compound (D)].

  The “uncrosslinked functional group-containing compound” which is the compound (D) is an internal cross-linked structure (three-dimensional cross-linked structure) of cross-linked resin fine particles as in the monomer group (C1). Unlike the compound to be formed, it refers to a compound which is added after the resin fine particles are subjected to emulsion polymerization (polymer formation) (does not participate in the internal cross-linking of the resin fine particles). That is, “uncrosslinked” means not involved in the formation of an internal crosslinked structure (three-dimensional crosslinked structure) of the crosslinked resin fine particles.

  The cross-linked resin fine particles have a cross-linked structure, so that the electrolytic solution resistance is secured, and by using the compound (D), it is selected from an epoxy group, an amide group, a hydroxyl group, and an oxazoline group in the compound (D). The at least one functional group may contribute to adhesion with the current collector or the electrode. Furthermore, the binder composition for secondary battery electrodes excellent in flexibility can be obtained by adjusting the amount of the crosslinked structure and functional group.

  The crosslinked resin fine particles need to be crosslinked inside the particles. Electrolytic solution resistance can be ensured by appropriately adjusting the crosslinking inside the particles. Furthermore, by adding the uncrosslinked compound (D) to the functional group-containing crosslinked resin fine particles, an epoxy group, an amide group, a hydroxyl group or an oxazoline group acts on the current collector, and adhesion to the current collector or the electrode. Can be improved effectively. Since the functional group contained in the compound (D) is stable by heat during long-term storage or electrode production, the effect of adhesion to the current collector is large even when used in a small amount. Furthermore, it is excellent in storage stability. The compound (D) may react with the functional group in the cross-linked resin fine particles for the purpose of adjusting the flexibility and the electrolytic solution resistance of the binder. If the functional group in the compound (D) is excessively used for the reaction, the functional group capable of interacting with the current collector or the electrode is decreased. For this reason, the reaction between the crosslinked resin fine particles and the compound (D) needs to be at a level that does not impair the adhesion to the current collector or the electrode. Further, when a part of the functional group contained in the compound (D) is used for the crosslinking reaction [when the compound (D) is a polyfunctional compound], by adjusting the degree of crosslinking of these functional groups, It is possible to balance the resistance to electrolytic solution and the adhesion.

<Uncrosslinked epoxy group-containing compound>
Examples of the uncrosslinked epoxy group-containing compound include epoxy group-containing ethylenically unsaturated monomers such as glycidyl (meth) acrylate and 3,4-epoxycyclohexyl (meth) acrylate; Radical polymerization resins obtained by polymerizing ethylenically unsaturated monomers containing monomers; ethylene glycol diglycidyl ether, polyethylene glycol diglycidyl ether, glycerin diglycidyl ether, glycerin triglycidyl ether, 1,6-hexanediol Diglycidyl ether, trimethylolpropane triglycidyl ether, diglycidyl aniline, N, N, N ′, N′-tetraglycidyl-m-xylylenediamine, 1,3-bis (N, N′-diglycidylaminomethyl) Cyclohexane Polyfunctional epoxy compounds; bisphenol A- epichlorohydrin epoxy resins, and epoxy resins such as bisphenol F- epichlorohydrin type epoxy resin.

  Among epoxy group-containing compounds, in particular, epoxy resins such as bisphenol A-epichlorohydrin type epoxy resins and bisphenol F-epichlorohydrin type epoxy resins, and ethylenically unsaturated monomers containing epoxy group-containing ethylenically unsaturated monomers. A radical polymerization resin obtained by polymerizing a saturated monomer is preferred. The epoxy resin can be expected to have a synergistic effect of improving the electrolytic solution resistance by having a bisphenol skeleton and improving the adhesion of the current collector by a hydroxyl group contained in the skeleton. In addition, the radical polymerization resin obtained by polymerizing an ethylenically unsaturated monomer containing an epoxy group-containing ethylenically unsaturated monomer has a higher adhesion to the current collector by having more epoxy groups in the resin skeleton. In addition, since it is a resin, an effect of improving the resistance to electrolytic solution can be expected as compared with the monomer.

<Uncrosslinked amide group-containing compound>
As an uncrosslinked amide group-containing compound, for example, a primary amide group-containing compound such as (meth) acrylamide; N-methylolacrylamide, N, N-di (methylol) acrylamide, N-methylol-N-methoxymethyl (meta) ) Alkylol (meth) acrylamide compounds such as acrylamide; N-methoxymethyl- (meth) acrylamide, N-ethoxymethyl- (meth) acrylamide, N-propoxymethyl- (meth) acrylamide, N-butoxymethyl- (meta ) Monoalkoxy (meth) acrylamide compounds such as acrylamide and N-pentoxymethyl- (meth) acrylamide; N, N-di (methoxymethyl) acrylamide, N-ethoxymethyl-N-methoxymethylmethacrylamide, N, N -Di (Etoki Methyl) acrylamide, N-ethoxymethyl-N-propoxymethylmethacrylamide, N, N-di (propoxymethyl) acrylamide, N-butoxymethyl-N- (propoxymethyl) methacrylamide, N, N-di (butoxymethyl) Dialkoxy (meth) acrylamides such as acrylamide, N-butoxymethyl-N- (methoxymethyl) methacrylamide, N, N-di (pentoxymethyl) acrylamide, N-methoxymethyl-N- (pentoxymethyl) methacrylamide Compounds; dialkylamino (meth) acrylamide compounds such as N, N-dimethylaminopropylacrylamide and N, N-diethylaminopropylacrylamide; N, N-dimethylacrylamide and N, N-diethylacrylamide Any dialkyl (meth) acrylamide compound; keto group-containing (meth) acrylamide compound such as diacetone (meth) acrylamide or the like, and the above amide group-containing ethylenically unsaturated monomers; Examples thereof include a radical polymerization resin obtained by polymerizing an ethylenically unsaturated monomer containing a monomer.

  Among the amide group-containing compounds, radical polymerization resins obtained by polymerizing ethylenically unsaturated monomers including amide group-containing ethylenically unsaturated monomers such as acrylamide are particularly preferable. By having more amide groups in the resin skeleton, it is possible to improve the current collector adhesion, and by using the resin, the effect of improving the resistance to electrolytic solution compared to the monomer can be expected.

<Uncrosslinked hydroxyl group-containing compound>
Examples of the uncrosslinked hydroxyl group-containing compound include 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate, glycerol mono (meth) acrylate 4-hydroxyvinylbenzene, Hydroxyl group-containing ethylenically unsaturated monomers such as 1-ethynyl-1-cyclohexanol and allyl alcohol; radical polymerization obtained by polymerizing ethylenically unsaturated monomers containing the hydroxyl group-containing ethylenically unsaturated monomers Resins: linear aliphatic diols such as ethylene glycol, diethylene glycol, 1,3-propanediol, 1,4-butanediol, 1,5-pentanediol, 1,6-hexanediol; propylene glycol, neopentyl glycol 3-methyl-1,5 Pentanediol, 2,2-branched aliphatic diols such as diethyl-1,3-propanediol; and 1,4-bis cyclic diol such as (hydroxymethyl) cyclohexane.

  Among the hydroxyl group-containing compounds, radical polymerization resins obtained by polymerizing ethylenically unsaturated monomers including a hydroxyl group-containing ethylenically unsaturated monomer or cyclic diols are particularly preferable. The radical polymerization resin obtained by polymerizing ethylenically unsaturated monomers including hydroxyl group-containing ethylenically unsaturated monomers improves current collector adhesion by having more hydroxyl groups in the resin skeleton. In addition, the resin can be expected to have an effect of improving the resistance to electrolytic solution compared to the monomer. Moreover, cyclic diols can be expected to have an effect of improving the resistance to electrolytic solution by having a cyclic structure in the skeleton.

<Uncrosslinked oxazoline group-containing compound>
Examples of the uncrosslinked oxazoline group-containing compound include 2′-methylenebis (2-oxazoline), 2,2′-ethylenebis (2-oxazoline), and 2,2′-ethylenebis (4-methyl-2-oxazoline). ), 2,2′-propylenebis (2-oxazoline), 2,2′-tetramethylenebis (2-oxazoline), 2,2′-hexamethylenebis (2-oxazoline), 2,2′-octamethylene Bis (2-oxazoline), 2,2′-p-phenylenebis (2-oxazoline), 2,2′-p-phenylenebis (4,4′-dimethyl-2-oxazoline), 2,2′-p -Phenylenebis (4-methyl-2-oxazoline), 2,2'-p-phenylenebis (4-phenyl-2-oxazoline), 2,2'-m-phenylenebis (2-oxazoline), 2 , 2′-m-phenylenebis (4-methyl-2-oxazoline), 2,2′-m-phenylenebis (4,4′-dimethyl-2-oxazoline), 2,2′-m-phenylenebis ( 4-phenylenebis-2-oxazoline), 2,2′-o-phenylenebis (2-oxazoline), 2,2′-o-phenylenebis (4-methyl-2-oxazoline), 2,2′-bis (2-oxazoline), 2,2′-bis (4-methyl-2-oxazoline), 2,2′-bis (4-ethyl-2-oxazoline), 2,2′-bis (4-phenyl-2) -Oxazoline), and further an oxazoline group-containing radical polymerization resin.

  Among oxazoline group-containing compounds, in particular, phenylene bis-type oxazoline compounds such as 2′-p-phenylenebis (2-oxazoline), or ethylenically unsaturated monomers containing an oxazoline group-containing ethylenically unsaturated monomer A radical polymerization resin obtained by polymerizing is preferred. The phenylenebis type oxazoline compound has an effect of improving the resistance to electrolytic solution by having a phenyl group in the skeleton. In addition, a radical polymerization resin obtained by polymerizing an ethylenically unsaturated monomer containing an oxazoline group-containing ethylenically unsaturated monomer has a current collector adhesion by having more oxazoline groups in the resin skeleton. In addition, by using a resin, the resistance to an electrolytic solution can be improved as compared with a monomer.

<Addition amount of compound (D), molecular weight>
Compound (D) is preferably added in an amount of 0.1 to 50 parts by weight, more preferably 5 to 40 parts by weight, based on 100 parts by weight of the solid content of the binder composition (eg, crosslinked resin fine particles). . When the addition amount of the compound (D) is less than 0.1 parts by weight, the amount of the functional group contributing to the adhesion to the current collector decreases, and may not sufficiently contribute to the improvement in the adhesion to the current collector. is there. On the other hand, when the amount exceeds 50 parts by weight, adverse effects on the binder performance such as leakage of the compound (D) into the electrolyte solution may occur. Furthermore, two or more types of compounds (D) can be used in combination.

  Although the molecular weight of a compound (D) is not specifically limited, It is preferable that a weight average molecular weight is 1,000-1,000,000, Furthermore, 5,000-500,000 are more preferable. If the molecular weight is less than 1,000, the adhesion effect to the current collector may not be sufficient, and if the molecular weight exceeds 1,000,000, the viscosity of the compound may increase, The handling property may be deteriorated. In addition, the said weight average molecular weight is the value of polystyrene conversion measured by the gel permeation chromatography (GPC) method. Further, the compound (D) may be a compound that dissolves in a solvent or a compound that disperses.

<Composite ink>
The aqueous composition for forming a secondary battery electrode of the present invention can be used as a composite ink or a composition for forming a base layer. First, a description will be given of a composite ink that essentially includes an active material, which is one of the preferred embodiments of the electrode forming composition. The mixed ink includes positive electrode mixed ink or negative electrode mixed ink, and the mixed ink is composed of an electrode active material, a binder composition (C), a dispersant (A), and an aqueous liquid medium (E). Further, a carbon material which is a thickener and a conductive aid can be contained.

<Electrode active material>
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, transition metal sulfide powders such as TiS ₂ and FeS, and the like. 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, etc., 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.

  The size of these electrode active materials 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 dispersion | distribution particle diameter of the electrode active material 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.).

<Carbon material as a conductive aid>
The composite ink preferably contains a carbon material in order to further increase the conductivity of the formed electrode. The carbon material 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, etc. alone Or two or more types can be used together. 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 carbon black 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 adsorption amount of nitrogen 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. When 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.

  The particle size of carbon black is preferably 0.005 to 1 μm, and 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. 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 diameter of the carbon material as the conductive auxiliary agent exceeding 2 μm is used, problems such as variations in the material distribution of the composite coating film and variations in the resistance distribution of the electrode may occur. .

  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.

<Aqueous liquid medium (E)>
As the aqueous liquid medium (E), it is preferable to use water. However, if necessary, for example, a liquid medium compatible with water may be used to improve the coating property to the current collector. good. 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.

<Other additives>
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.

<Physical properties of compound ink>
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. Further, it is preferable that the active material is contained as much as possible within the viscosity range that can be applied. For example, the ratio of the active material to the solid content of the composite ink is preferably 80% by weight or more and 99% by weight or less. Moreover, it is preferable that the ratio of the dispersing agent (A) to solid ink solid content is 0.1 to 15 weight%. When the carbon material is included, the proportion of the carbon material in the solid material ink solid content is preferably 0.1 to 15% by weight.

<Method for preparing compound ink>
The composite ink can be obtained by various methods. However, the use of a carbon material is optional. For example,
(4-1) After obtaining an aqueous dispersion of an active material containing an active material, a dispersant (A) and an aqueous liquid medium (E), a binder containing a carbon material and cross-linked resin fine particles in the aqueous dispersion A composition ink can be obtained by adding the composition (C). In this case, the binder composition (C) containing the carbon material and the crosslinked resin fine particles can be added simultaneously, or after adding the carbon material, the binder may be added, or vice versa.
(4-2) A binder containing a carbon material, a dispersant (A), an aqueous liquid medium (E), and a conductive additive containing the conductive aid, and then containing an active material and cross-linked resin fine particles in the aqueous dispersion. A composition ink can be obtained by adding the composition (C). In this case, the active material and the binder can be added simultaneously, or after adding the active material, the binder composition (C) containing the crosslinked resin fine particles may be added, or vice versa.
(4-3) After obtaining the aqueous dispersion of the active material containing the active material, the dispersant (A), the binder composition (C) containing the crosslinked resin fine particles and the aqueous liquid medium (E), the aqueous dispersion A carbon material can be added to the body to obtain a composite ink.
(4-4) After obtaining an aqueous dispersion of a conductive additive containing a carbonaceous material, a dispersant (A), a binder composition (C) containing crosslinked resin fine particles and an aqueous liquid medium (E), the aqueous An active material can be added to the dispersion to obtain a composite ink.
(4-5) A composite ink can be obtained by mixing the active material, the carbon material, the dispersant (A), the binder composition (C) containing the crosslinked resin fine particles and the aqueous liquid medium (E) almost simultaneously. .
In the above step, the cellulosic thickener (B) may be added simultaneously with the dispersant (A) or may be added separately.

<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. In the case of a positive electrode 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>
The composition for forming an underlayer contains at least a conductive additive, a binder composition (C), a dispersant (A), and an aqueous liquid medium (E). Furthermore, a thickener (B) can also be used. About each component, it is the same as that of the case of compound ink.

  The ratio of the carbon material as a conductive additive to 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, more preferably 10% by weight or more and 90% by weight or less. If the carbon material that is the conductive auxiliary agent is small, the conductivity of the underlayer may not be maintained. On the other hand, if the carbon material that is the conductive auxiliary agent is too large, the resistance of the coating film may be reduced. 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>
The composite ink can be applied and dried on the current collector to form a composite layer, whereby a secondary battery electrode can be produced. Alternatively, after forming the underlayer on the current collector using the underlayer-forming composition, a composite material layer may be provided on the underlayer to produce a secondary battery electrode. The composite material layer provided on the base layer may be formed using the above-described composite material inks (1) to (4), 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, foil on a flat plate is generally used, but the surface is roughened, porous foam, perforated foil, and mesh current collector. Can also be used.

  There is no restriction | limiting in particular as a method of apply | coating mixed-material ink 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 thickness of the underlayer is generally 0.1 μm or more and 100 μm or less, preferably 0.5 μm or more and 50 μm or less.

<Secondary battery>
A secondary battery can be manufactured 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 the electrolyte, 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 etc. but are not limited to.

  Although it does not specifically limit as a non-aqueous solvent, For example, carbonates, such as ethylene carbonate, propylene carbonate, butylene carbonate, dimethyl carbonate, ethylmethyl carbonate, and diethyl carbonate; γ-butyrolactone, γ-valerolactone, and γ- Lactones such as octanoic lactone; tetrahydrofuran, 2-methyltetrahydrofuran, 1,3-dioxolane, 4-methyl-1,3-dioxolane, 1,2-methoxyethane, 1,2-ethoxyethane, and 1,2 -Glymes such as dibutoxyethane; esters such as methyl formate, methyl acetate, and methyl propionate; sulfoxides such as dimethyl sulfoxide and sulfolane; and nitriles such as acetonitrile. It is below. 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 and configuration>
The structure of the lithium ion secondary battery using the electrode forming 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, Various shapes can be formed according to the purpose of use, such as a button 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, “parts” represents “parts by weight”.

<Synthesis Example of Cationic Dispersant>
(Synthesis Example 1)
Cationic dispersant (A1-1)
A reaction vessel equipped with a gas introduction tube, a thermometer, a condenser and a stirrer was charged with 93.4 parts of butanol and replaced with nitrogen gas. The reaction vessel was heated to 110 ° C., and 10.0 parts of 2-ethylhexyl acrylate, 20.0 parts of methyl methacrylate, 70.0 parts of dimethylaminoethyl methacrylate and 4.5 parts of V-601 (manufactured by Wako Pure Chemical Industries, Ltd.) 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, 0.5 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. A solution of 1) was obtained. The weight average molecular weight of the cationic dispersant (A1-1) was about 20,000.

  Furthermore, after cooling to room temperature, 48.9 parts of hydrochloric acid 0.01% aqueous solution was added for neutralization. This is the amount that neutralizes 100% of dimethylaminoethyl methacrylate. Furthermore, after adding 103 parts of water, it heated to 90 degreeC or more, butanol was azeotroped with water, and butanol was distilled off. When the internal temperature reaches 100 ° C., 1 g is sampled, and heated and dried at 180 ° C. for 20 minutes to measure the nonvolatile content. Based on this measurement value, the nonvolatile content of the aqueous resin solution becomes 20%. So water was added. As a result, an aqueous solution or an aqueous dispersion having a non-volatile content of 20% of the cationic dispersant (A1-1) was obtained.

(Synthesis Examples 2-9 and 15-17)
An aqueous solution or dispersion of cationic dispersants (A1-2) to (A1-9) and (A1-15) to (A1-17) having the composition shown in Table 1 and the same method as in Synthesis Example 1. Got.

The explanation of the ellipsis in Table 1 is as follows.
St: Styrene BzMA: Benzyl methacrylate DM: Dimethylaminoethyl methacrylate HEMA: Hydroxyethyl methacrylate MMA: Methyl methacrylate 2EHA: 2-ethylhexyl acrylate Aam: Acrylamide

<Preparation of binder composition>
[Synthesis Example 18]
Binder composition (C1-4)
In a reaction vessel equipped with a stirrer, thermometer, dropping funnel and refluxing vessel, 40 parts of ion exchange water and 0.2 part of Adeka Soap SR-10 (manufactured by ADEKA Co., Ltd.) as a surfactant are charged. On the other hand, 48.5 parts of methyl 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- 1% of the pre-emulsion in which 1.8 parts of 10 (manufactured by ADEKA Co., Ltd.) was mixed in advance was further 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 inside of the reaction system at 70 ° C. for 5 minutes, the remaining pre-emulsion and the remaining 5% aqueous solution of potassium persulfate were dropped 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 exchange water to obtain a resin fine particle water dispersion. In addition, solid content was calculated | required by 150 degreeC 20 minute baking residue.

[Synthesis Examples 19 to 37]
Binder compositions (C1-5) to (C1-17) and (C1-1) to (C1-3) which are resin fine particle aqueous dispersions by the same method as in Synthesis Example 18 with the blending composition shown in Table 2. , (C2-1), (C3-1) and (C4-1) were obtained. However, in the binder compositions (C1-16) and (C1-17), the resin aggregated during the emulsion polymerization, and the desired resin fine particles could not be obtained.

In addition, the description of the symbol in Table 2 is as follows.
* 1: 3-methacryloxypropyltrimethoxysilane * 2: allyl methacrylate * 3: glycidyl methacrylate * 4: diacetone acrylamide * 5: diethyl acrylamide * 6: acrylamide * 7: N-methylol acrylamide * 8: hydroxyethyl methacrylate * 9: 2-ethylhexyl acrylate * 10: Lauryl methacrylate * 11: Styrene * 12: Cyclohexyl methacrylate * 13: Itaconic acid * 14: Acrylic acid * 15: Styrenesulfonic acid * 16: Acid phosphooxyethyl methacrylate * 17: Methyl methacrylate * 18: Butyl acrylate * 19: Acrylonitrile * 20: 1,3-butadiene * 21: Adecalia soap SR-10
Alkyl ether anionic surfactant (made by ADEKA Corporation)
* 22: ADEKA rear soap ER-20
Alkyl ether nonionic surfactant (manufactured by ADEKA Corporation)
* 23: 5% potassium persulfate aqueous solution

<Production of Compound (D) [Production of Epoxy Group-Containing Compound]>
[Production Example 1]
Into a reaction vessel equipped with a stirrer, a thermometer, a dropping funnel and a refluxing vessel, 20 parts of isopropyl alcohol and 20 parts of water are charged, and 40 parts of methyl methacrylate, 40 parts of methyl acrylate and 20 parts of glycidyl methacrylate are separately added to the dropping tank 1, Moreover, 2 parts of potassium persulfate was dissolved in 30 parts of isopropyl alcohol and 30 parts of water, and charged into the dropping tank 2. After raising the internal temperature to 80 ° C. and sufficiently purging with nitrogen, the contents of the dropping tanks 1 and 2 were dropped over 2 hours to carry out polymerization. After completion of dropping, stirring was continued for 1 hour while maintaining the internal temperature at 80 ° C. After confirming that the conversion rate exceeded 98% by solid content measurement, the temperature was cooled to 30 ° C., and the solid content was 50%. An epoxy group-containing compound (methyl methacrylate / methyl acrylate / glycidyl methacrylate copolymer) solution was obtained. In addition, solid content was calculated | required by 150 degreeC 20 minute baking residue.

<Production of Compound (D) [Production of Amide Group-Containing Compound]>
[Production Example 2]
A reaction vessel equipped with a stirrer, thermometer, dropping funnel and refluxing vessel was charged with 90 parts of water, and 20 parts of acrylamide was separately dissolved in the dropping tank 1 and 2 parts of potassium persulfate was dissolved in 90 parts of water and dropped. Tank 2 was charged. After raising the internal temperature to 80 ° C. and sufficiently purging with nitrogen, the contents of the dropping tanks 1 and 2 were dropped over 2 hours to carry out polymerization. After completion of dropping, stirring was continued for 1 hour while maintaining the internal temperature at 80 ° C. After confirming that the conversion rate exceeded 98% by solid content measurement, the temperature was cooled to 30 ° C., and the solid content was 10%. An amide group-containing compound (polyacrylamide) solution was obtained. In addition, solid content was calculated | required by 150 degreeC 20 minute baking residue.

[Production Example 3]
A reaction vessel equipped with a stirrer, a thermometer, a dropping funnel and a refluxing vessel was charged with 40 parts of water. Separately, 40 parts of 2-ethylhexyl acrylate, 40 parts of styrene and 20 parts of dimethylacrylamide were added to the dropping tank 1, and persulfuric acid. 2 parts of potassium was dissolved in 60 parts of water and charged into the dropping tank 2. After raising the internal temperature to 80 ° C. and sufficiently purging with nitrogen, the contents of the dropping tanks 1 and 2 were dropped over 2 hours to carry out polymerization. After completion of dropping, stirring was continued for 1 hour while maintaining the internal temperature at 80 ° C. After confirming that the conversion rate exceeded 98% by solid content measurement, the temperature was cooled to 30 ° C., and the solid content was 50%. An amide group-containing compound (2-ethylhexyl acrylate / styrene / dimethylacrylamide copolymer) solution was obtained. In addition, solid content was calculated | required by 150 degreeC 20 minute baking residue.

<Production of Compound (D) [Production of Hydroxyl-Containing Compound]>
[Production Example 4]
A reaction vessel equipped with a stirrer, a thermometer, a dropping funnel and a refluxing vessel is charged with 20 parts of isopropyl alcohol and 20 parts of water, and 40 parts of methyl methacrylate, 40 parts of butyl acrylate and 20 parts of 2-hydroxyethyl methacrylate are separately added to the dropping tank. In addition, 2 parts of potassium persulfate was dissolved in 30 parts of isopropyl alcohol and 30 parts of water and charged into the dropping tank 2. After raising the internal temperature to 80 ° C. and sufficiently purging with nitrogen, the contents of the dropping tanks 1 and 2 were dropped over 2 hours to carry out polymerization. After completion of dropping, stirring was continued for 1 hour while maintaining the internal temperature at 80 ° C. After confirming that the conversion rate exceeded 98% by solid content measurement, the temperature was cooled to 30 ° C., and the solid content was 50%. A hydroxyl group-containing compound (methyl methacrylate / butyl acrylate / 2-hydroxyethyl methacrylate copolymer) solution was obtained. In addition, solid content was calculated | required by 150 degreeC 20 minute baking residue.

[Synthesis Examples 38 to 44]
A binder composition containing an uncrosslinked compound (D) with the composition shown in Table 3 was obtained.

In addition, the description of the product name in Table 3 is as follows.
Epoxy resin; product name Adeka Resin EM-1-60L, manufactured by ADEKA Corporation, epoxy equivalent 320, bisphenol A-epichlorohydrin type epoxy resin oxazoline-containing acrylic / styrene resin; product name Epocros K-2020E, manufactured by Nippon Shokubai Co., Ltd. , Oxazoline equivalent 550

<Cellulose-based thickener (B)>
CMC: carboxymethyl cellulose, hydroxyl value: 415-500 mg KOH / g
-HEC: hydroxyethyl cellulose, hydroxyl value: 600-720 mgKOH / g

<Carbon material dispersion for secondary battery electrode>
10 parts of acetylene black (DENKA BLACK HS-100) as a carbon material which is a conductive additive, and 10 parts (2 parts as a solid content) of an aqueous solution or an aqueous dispersion of the cationic dispersant (A1-2) described in Synthesis Example 2 ), 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 having a composition ratio shown in Table 4.

  With the blending composition shown in Table 4, carbon material dispersions (2) to (29) for secondary battery electrodes were obtained in the same manner as the carbon material dispersion (1) for secondary battery electrodes.

  The degree of dispersion of the carbon material dispersion for secondary battery electrodes was determined by determination with a grind gauge (in accordance with JIS K5600-2-5). The evaluation results are shown in Table 4. The numbers in the table indicate the size of coarse particles. The smaller the value, the better the dispersibility and the more uniform secondary battery electrode forming composition.

The explanation of the ellipsis in Table 4 is as follows.
A: Acetylene black, Denka black HS-100 (manufactured by Denki Kagaku Kogyo)
F: Furnace black, Super-PLi (manufactured by TIMCAL)
C: Carbon nanotube, VGCF-H (manufactured by Showa Denko KK)
Commercially available dispersant A: allylamine polymer, weight average molecular weight: 25000, amine value: 982 mgKOH / g
Commercially available dispersant B: allylamine hydrochloride polymer, weight average molecular weight: 150,000, amine value: 982 mgKOH / g
Commercially available dispersant C: diallylamine hydrochloride polymer, weight average molecular weight: 110000, amine value: 505 mgKOH / g
Commercially available dispersant D: diallyldimethylammonium chloride polymer, weight average molecular weight: 200000, amine value: 505 mg KOH / g
Commercially available dispersant E: allylamine hydrochloride / diallylamine hydrochloride copolymer, weight average molecular weight: 100,000, amine value: 743 mgKOH / g
Commercially available dispersant F: polyethyleneimine, weight average molecular weight: about 70,000, amine value: 1008 mgKOH / g
CMC: Carboxymethylcellulose, Hydroxyl value: 415-500 mgKOH / g
HEC: hydroxyethyl cellulose, hydroxyl value: 600-720 mgKOH / g

<Composition for forming secondary battery electrode>
[Example 1]
Secondary battery electrode by mixing 50 parts of carbon material dispersion for secondary battery electrode (1) (6 parts in solids) and binder composition (C1-4) in an amount of 4 parts by weight in solids A forming composition was obtained.

[Examples 2 to 24, Comparative Examples 1 to 9]
The composition for forming secondary battery electrodes of Examples 2 to 24 and Comparative Examples 1 to 9 was prepared by mixing the carbon material dispersion for secondary battery electrodes and the binder composition so that the composition ratio shown in Table 5 was obtained. Got.

When an electrode is produced using the composition for forming a secondary battery electrode, elution into the electrolyte solution causes degradation of the battery characteristics due to electrode collapse after the battery is produced, and peeling of the electrode layer from the current collector. Therefore, it is desirable that the elution is not observed. The evaluation of the electrolyte dissolution property was performed as follows. The composition for forming a secondary battery electrode shown in Table 5 was applied on a 20 μm thick aluminum foil using a doctor blade, and then dried by heating under reduced pressure to form a coating film for forming a secondary battery electrode having a thickness of 5 μm. Produced. The obtained coating film was immersed in a 1: 1 (volume ratio) non-aqueous electrolyte solvent of ethylene carbonate and diethyl carbonate, stored in a 60 ° C. environment for 3 days, and then the state of the coating film was observed. The evaluation criteria are shown below, and the evaluation results are shown in Table 5.
○: “No disintegration or peeling of coating film”
Δ: “Partial disintegration and peeling of coating film are observed”
×: “Most of the coating film is disintegrated and peeled”

<Composite ink for lithium ion secondary battery electrode, positive electrode, coin-type battery>
[Example 25]
90 parts of LiCoO ₂ as a positive electrode active material, 5 parts of an aqueous solution of a dispersing agent (A1-3) (1 part as a resin solid content), 8 parts (4 parts as a solid content) of a binder composition (C1-4) and water 43. Two parts were mixed to produce a positive electrode material ink for a secondary battery electrode having a solid content of 65% by weight. 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 6A. 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 ink mixture for secondary battery electrodes.

  Next, this positive electrode secondary battery electrode composite ink was applied onto a 20 μm thick aluminum foil serving as a current collector using a doctor blade, and then dried under reduced pressure and dried to a thickness of 100 μm. It adjusted so that it might become. Furthermore, the rolling process by a roll press was performed and the positive electrode whose thickness is set to 80 micrometers was produced. The charge / discharge storage characteristics were evaluated using an evaluation coin type battery having a positive electrode as a working electrode and a metal lithium foil as a counter electrode.

[Examples 26 to 40, Comparative Examples 10 to 25]
For the secondary battery electrode for the positive electrode by changing the combination of the active material shown in Tables 6A and 6B, the carbon material as the conductive auxiliary agent, the carbon material dispersion, the composition for forming the secondary battery electrode, the dispersant and the binder composition. Except that water was added so that the final solid content of the composite ink was 65% by weight, a composite ink for a positive electrode for a positive electrode and a positive electrode were obtained and evaluated in the same manner as in Example 25. .

<Preparation of negative electrode for lithium ion secondary battery>
[Example 41]
95 parts of natural graphite as a negative electrode active material, 2.5 parts of an aqueous solution of a dispersant (A1-4) (0.5 parts as a resin solid content), 4 parts of a binder composition (C1-4) (2 parts as a solid content) And 93.5 parts of water were mixed to prepare a composite ink for a secondary battery electrode for a negative electrode having a solid content of 50% by weight. The degree of dispersion of the composite ink was determined by judgment using a grind gauge. The evaluation results are shown in Table 6C.

  Next, the negative electrode secondary battery electrode composite ink was applied onto a copper foil having a thickness of 20 μm as a current collector using a doctor blade, and then dried by heating under reduced pressure to obtain an electrode thickness of 100 μm. It adjusted so that it might become. Furthermore, the rolling process by a roll press was performed, the negative electrode whose thickness was set to 80 micrometers was produced, and it evaluated similarly to the case of a positive electrode. The charge / discharge storage 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 42 to 44, Comparative Examples 26 to 32]
The active material shown in Table 6C, a carbon material as a conductive additive, a carbon material dispersion, a composition for forming a secondary battery electrode, a combination of a dispersant and a binder composition was changed, and a composite material for a secondary battery electrode for a negative electrode Except that water was added so that the final solid content of the ink was 50% by weight, a mixture ink for a secondary battery electrode for a negative electrode and a negative electrode were obtained and evaluated in the same manner as in Example 41.

[Example 45]
90 parts of LiCoO ₂ as a positive electrode active material, 2.5 parts of an aqueous solution of a dispersant (A1-9) (0.5 parts as a resin solid content), 33.3 parts of a 3% aqueous solution of CMC as a thickener (as a solid content) 1 part), 7 parts of binder composition (C1-6) (3.5 parts as a solid content) and 13.3 parts of water are mixed to obtain a composite material for a secondary battery electrode for a positive electrode having a solid content of 65% by weight. An ink was prepared. The composition is shown in Table 7A. Production and evaluation of the positive electrode were carried out in the same manner as in Example 25.

[Examples 46 to 52, Examples 60 to 70, and Comparative Examples 33 to 40]
The active material shown in Table 7A and Table 8A, the carbon material that is a conductive auxiliary agent, the carbon material dispersion, the composition for forming a secondary battery electrode, the dispersant, the thickener, and the binder composition are changed to be used for the positive electrode. In the same manner as in Example 45 except that water was added so that the final solid content of the secondary battery electrode mixture ink was 65% by weight, a positive electrode secondary battery electrode mixture ink and a positive electrode were obtained. , Evaluated in the same way.

[Example 53]
94 parts of natural graphite as a negative electrode active material, 2.5 parts of an aqueous solution of a dispersing agent (A1-3) (0.5 parts as resin solids), 5 parts of binder composition (C1-4) (2.5 as solids) Part), 25 parts of a 2% aqueous solution of CMC as a thickener (0.5 part as a solid content) and 68.5 parts of water are mixed, and a composite material for a secondary battery electrode for a negative electrode having a solid content of 50% by weight. An ink was prepared. The composition is shown in Table 7B. Production and evaluation of the negative electrode were carried out in the same manner as in Example 41.

[Examples 54 to 59, Examples 71 to 78, Comparative Examples 41 to 43]
The active material shown in Table 7B and Table 8B, the carbon material that is a conductive auxiliary agent, the carbon material dispersion, the composition for forming a secondary battery electrode, the dispersant, the thickener, and the binder composition are changed to be used for the negative electrode. In the same manner as in Example 53 except that water was added so that the final solid content of the secondary battery electrode composite ink was 50% by weight, a secondary battery electrode composite ink for a negative electrode and a negative electrode were obtained. Evaluation was performed in the same manner.

In addition, the description of the ellipsis in Tables 6A-6C is as follows.
LCO: LiCoO ₂
LFP: LiFePO ₄
LMO: LiMn ₂ O ₄
NMC: LiNi _1/3 Mn _1/3 Co _1/3 O ₂
Carbon material A: Acetylene black, Denka black HS-100 (manufactured by Denki Kagaku Kogyo Co., Ltd.)
Commercially available dispersant B: Allylamine hydrochloride polymer Commercially available dispersant F: Polyethyleneimine HEC: Hydroxyethyl cellulose

The explanation of the ellipsis in Tables 7A and 7B is as follows.
LCO: LiCoO ₂
LFP: LiFePO ₄
LMO: LiMn ₂ O ₄
NMC: LiNi _1/3 Mn _1/3 Co _1/3 O ₂
Carbon material A: Acetylene black, Denka black HS-100 (manufactured by Denki Kagaku Kogyo Co., Ltd.)
Carbon material C: carbon nanotube, VGCF-H (manufactured by Showa Denko)
Commercial dispersant C: diallylamine hydrochloride polymer commercial dispersant D: diallyldimethylammonium chloride polymer commercial dispersant E: allylamine hydrochloride / diallylamine hydrochloride copolymer CMC: carboxymethylcellulose HEC: hydroxyethylcellulose

The explanation of the ellipsis in Tables 8A and 8B is as follows.
LFP: LiFePO ₄
LMO: LiMn ₂ O ₄
Carbon material A: Acetylene black, Denka black HS-100 (manufactured by Denki Kagaku Kogyo Co., Ltd.)
Carbon material C: carbon nanotube, VGCF-H (manufactured by Showa Denko)
CMC: Carboxymethylcellulose HEC: Hydroxyethylcellulose PTFE: Polytetrafluoroethylene

<Method of evaluation of produced composite ink, characteristics of coating film, battery evaluation>
(Dispersion degree of compound ink)
Similar to the degree of dispersion of the composition for forming a secondary battery electrode, it was determined by determination with a grind gauge (according to JIS K5600-2-5).

(Viscosity of compound ink)
For measuring the viscosity of the slurry, a rheometer (“AR-G2” manufactured by TA Instruments) was used, and 0.01 (when the share rate was changed from 0.001 (1 / s) to 10 (1 / s). The viscosities of 1 / s) and 1 (1 / s) were determined.
Viscosity of 0.01 (1 / s) ○: greater than 10000 mPa · s and less than or equal to 50000 mPa · s Δ: greater than 50000 mPa · s and less than or equal to 100,000 mPa · s ×: greater than 100,000 mPa · s 1 (1 /: When the viscosity is greater than 1000 mPa · s and less than or equal to 5000 mPa · s Δ: When greater than 5000 mPa · s and less than or equal to 8000 mPa · s ×: When greater than 8000 mPa · s

(Sedimentability of compound ink)
One day after producing the composite ink, it was confirmed whether or not a sediment was formed at the bottom.
○: No sediment is observed in the composite ink after 1 day.
X: Sediment can be confirmed even slightly in the composite ink after 1 day.

(Peeling strength of coating film)
In the electrode produced above (see Example 25), using a knife, notches from the electrode surface to the depth reaching the current collector were 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”

(Flexibility of coating film)
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”

(Electrolytic solution elution)
It calculated | required by the method similar to evaluation of the electrolyte solution elution property in Example 1. FIG.

(Charge / discharge storage characteristics)
A working electrode produced by punching the electrode produced in the above to a diameter of 16 mm, a counter electrode of metallic lithium foil, a separator (porous polypropylene film) inserted between the working electrode and the counter electrode, and an electrolyte (ethylene carbonate and diethyl) 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 was mixed at a ratio of 1: 1 (volume ratio) was produced. The coin-type battery was produced in a glove box substituted with argon gas.

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 and constant voltage charging was continued to a charge end voltage of 4.5 V at a charging current of 1.0 C. After the voltage of the battery reached 4.5V, constant current discharge was performed at a discharge current of 1.0C until the discharge end voltage of 2.0V was reached. These charging / discharging cycles were taken as one cycle, and 100 cycles of charging / discharging were repeated. The discharge capacity at the third cycle was defined as the initial discharge capacity (the initial discharge capacity was set to 100% discharge capacity retention rate), and the discharge capacity retention rate after 100 cycles was calculated (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%.

When the active material used was LiCoO ₂ , LiMn ₂ O ₄ , or LiNiO ₂ , constant current / constant voltage charging was continued to a charge end voltage of 4.2 V at a charging current of 1.0 C. After the battery voltage reached 4.2 V, constant current discharge was performed at a discharge current of 1.0 C until the discharge end voltage of 3.0 V was reached. These charging / discharging cycles were taken as one cycle, and 100 cycles of charging / discharging were repeated.

When the active material used was LiNi _1/3 Mn _1/3 Co _1/3 O ₂ , constant current and constant voltage charging was continued up to a charge end voltage of 4.3 V at a charging current of 1.0 C. After the voltage of the battery reached 4.3 V, constant current discharge was performed at a discharge current of 1.0 C until the discharge end voltage of 2.8 V was reached. These charging / discharging cycles were taken as one cycle, and 100 cycles of charging / discharging were repeated.

(Appearance of paint film after charge / discharge cycle)
After the charge / discharge cycle characteristics evaluation, the cell was disassembled, and the appearance of the electrode coating film was visually confirmed. The better the evaluation result, the better the strength of the electrode.
○: “No peeling”
Δ: “Slightly peeled”
×: “Most peeled off”

  As shown in Tables 6A to C, Table 7A, Table 7B, Tables 8A and 8B, when the aqueous composition for forming a secondary battery electrode of the present invention is used, the active material or the carbon material which is a conductive additive is combined. Since it is uniformly dispersed in the material ink, it is considered that the flow characteristics of the composite ink, the flexibility of the electrode, and the adhesion are balanced, and the charge / discharge storage characteristics are also improved in the battery characteristics.

  If the carbon material that is the active material or conductive aid is insufficiently dispersed in the composite ink, a uniform conductive network is not formed when it is used as an electrode. It is considered that the resulting resistance distribution occurs and current concentration occurs when used as a battery, thereby causing deterioration. When the dispersion control of the carbon material or the active material, which is a conductive auxiliary agent, is insufficient, that is, when the cationic dispersant is not used or the cationic dispersant is not within the scope of the present invention, In the case where is used, there is a tendency that the coating film characteristics and battery characteristics of the electrode are insufficient. In particular, when the dispersion control of the carbon material that is a conductive additive is insufficient, the tendency is remarkable.

  Furthermore, it is considered that the resistance of the electrode coating film to the electrolytic solution is further improved by combining a dispersant and a binder composition (particularly, a binder composition containing a crosslinkable resin fine particle aqueous dispersion).

[Examples 79 and 80, Comparative Example 44]
The composition for forming a secondary battery electrode shown in Table 9 was applied onto a 20 μm-thick aluminum foil serving as a current collector using a doctor blade, and then dried by heating, so that the base layer was 5 μm in thickness. Formed. Subsequently, after applying the mixed ink for secondary battery positive electrode shown in Table 6A on the underlayer, it was dried by heating under reduced pressure to obtain a positive electrode in the same manner as in Example 25 and evaluated in the same manner.

  As shown in Table 9, it can be seen that when the composition for forming a secondary battery electrode of the present invention is used for the underlayer, it is as good as the evaluation results of Examples 27 and 32. 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 uniform and strong. However, the dispersion state of the composition for forming the secondary battery electrode for the underlayer of Comparative Example 6 and the elution resistance to the electrolytic solution are insufficient, and even when the electrode is used, it is compared with the evaluation result of Example 26. The result was inferior. 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 (12)

An aqueous composition for forming a secondary battery electrode, comprising at least one of a carbon material that is an electrode active material or a conductive additive, a cationic dispersant (A), and water,
The cationic dispersant (A)
It is a copolymer obtained by copolymerizing the following monomers,
Ethylenically unsaturated monomer having an aromatic ring (a1): 0 to 30% by weight
Ethylenically unsaturated monomer having an aliphatic amino group or an aromatic amino group (a2): 30 to 80% by weight
Ethylenically unsaturated monomers (a3) other than (a1) to (a2): 0 to 70% by weight
(However, the total of the above (a1) to (a3) is 100% by weight.)
Having at least one of an aliphatic amine or an aromatic amine as a cationic site, an amine value of 110 to 1000 mgKOH / g, a hydroxyl value of 0 to 400 mgKOH / g, and a weight average molecular weight of 5000 or more; An aqueous composition for forming a secondary battery electrode.   Furthermore, the composition of Claim 1 containing a cellulose thickener (B).   Furthermore, the composition of Claim 1 or 2 containing a binder composition (C).   The composition according to claim 3, wherein the binder composition (C) contains crosslinked resin fine particles. The composition according to claim 4, wherein the crosslinked resin fine particles are resin fine particles obtained by emulsion polymerization of the following monomers.
(C1) From the group consisting of an ethylenically unsaturated monomer (c1) having a monofunctional or polyfunctional alkoxysilyl group and a monomer (c2) having two or more ethylenically unsaturated groups in one molecule At least one monomer selected: 0.1 to 5% by weight
(C2) Ethylenically unsaturated monomers (c3) other than the monomers (c1) to (c2): 95 to 99.9% by weight
(However, the total of (c1) to (c3) is 100% by weight.) The composition according to claim 5, wherein the ethylenically unsaturated monomer (c3) has the following composition.
Ethylenically unsaturated monomer (c4) having a monofunctional or polyfunctional epoxy group, ethylenically unsaturated monomer (c5) having a monofunctional or polyfunctional amide group, and ethylene having a monofunctional or polyfunctional hydroxyl group At least one monomer selected from the group consisting of polymerizable unsaturated monomers (c6): 0.1 to 20% by weight
Ethylenically unsaturated monomers (c7) other than the monomers (c1), (c2), (c4) to (c6): 75 to 99.8% by weight
(However, the total of (c1) to (c3) is 100% by weight.) The composition according to claim 6, wherein the ethylenically unsaturated monomer (c7) has the following composition.
At least one monomer selected from the group consisting of an ethylenically unsaturated monomer (c8) having an alkyl group having 8 to 18 carbon atoms and an ethylenically unsaturated monomer (c9) having a cyclic structure: 30 ~ 95 wt%
Ethylenically unsaturated monomers other than the above (c1) to (c6), (c8) and (c9): 0 to 69.8% by weight
(However, the total of (c1) to (c3) is 100% by weight.)   The binder composition (C) is at least one uncrosslinked selected from the group consisting of an uncrosslinked epoxy group-containing compound, an uncrosslinked amide group-containing compound, an uncrosslinked hydroxyl group-containing compound, and an uncrosslinked oxazoline group-containing compound. The composition according to any one of claims 4 to 7, further comprising the compound (D). The composition according to any one of claims 2 to 8 , wherein the cellulosic thickener (B) is hydroxyalkyl cellulose.   An electrode for a secondary battery, comprising a current collector and at least one of a composite material layer or an electrode underlayer formed from the composition according to claim 1.   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 according to claim 10. A lithium secondary battery comprising a positive electrode, a negative electrode, and an electrolyte solution, wherein at least one of the positive electrode and the negative electrode is the secondary battery electrode according to claim 10 .