KR102569975B1 - Binder composition for non-aqueous secondary battery electrode, conductive material paste composition for non-aqueous secondary battery electrode, slurry composition for non-aqueous secondary battery electrode, non-aqueous secondary battery electrode and non-aqueous secondary battery - Google Patents

Abstract

An object of the present invention is to provide a binder composition for non-aqueous secondary battery electrodes capable of forming an electrode mixture layer having excellent viscosity stability and suppressed swelling in an electrolyte solution. The binder composition of the present invention contains a polymer having a functional group bondable to a cationic group, and an organic compound having two or more cationic groups and having a molecular weight of 8000 or less.

Description

Binder composition for non-aqueous secondary battery electrode, conductive material paste composition for non-aqueous secondary battery electrode, slurry composition for non-aqueous secondary battery electrode, non-aqueous secondary battery electrode and non-aqueous secondary battery

The present invention relates to a binder composition for nonaqueous secondary battery electrodes, a conductive material paste composition for nonaqueous secondary battery electrodes, a slurry composition for nonaqueous secondary battery electrodes, an electrode for nonaqueous secondary batteries, and a nonaqueous secondary battery.

Nonaqueous secondary batteries such as lithium ion secondary batteries (hereinafter sometimes simply abbreviated as "secondary batteries") have characteristics such as small size, light weight, high energy density, and enabling repeated charging and discharging. It is used for a wide range of purposes. Therefore, in recent years, improvement of battery members such as electrodes has been studied for the purpose of further enhancing the performance of non-aqueous secondary batteries.

Here, an electrode used in a secondary battery such as a lithium ion secondary battery usually includes a current collector and an electrode mixture layer (positive electrode mixture layer or negative electrode mixture layer) formed on the current collector. And this electrode mixture layer is formed by, for example, applying a slurry composition containing an electrode active material and a binder composition containing a binder on a current collector, and drying the applied slurry composition.

Accordingly, in recent years, in order to achieve further improvement in the performance of secondary batteries, improvement of the binder composition used for forming the electrode mixture layer has been attempted.

Specifically, for example, in Patent Literature 1, a binder composition containing a non-crosslinked polymer having a functional group capable of bonding to a polyvalent metal ion, a polyvalent metal compound containing a polyvalent metal and a ligand having a molecular weight of 30 or more, and an organic solvent , It is excellent in viscosity stability, and it has been reported that by using this binder composition, the adhesion between the electrode mixture layer and the current collector can be improved, and the cycle characteristics of the secondary battery can be improved.

Japanese Unexamined Patent Publication No. 2008-166058

However, it could not be said that the viscosity stability of the conventional binder composition was sufficiently satisfactory. In addition, the electrode mixture layer obtained by using the conventional binder composition is excessively swollen in the electrolyte solution. In the case of an electrode having an electrode mixture layer obtained from such a binder composition, it has been difficult to exhibit excellent cycle characteristics in a secondary battery. That is, the conventional binder composition has room for improvement in terms of sufficiently improving the cycle characteristics of a secondary battery by suppressing swelling of the electrode mixture layer in the electrolyte solution while ensuring viscosity stability.

Accordingly, an object of the present invention is to provide a binder composition for non-aqueous secondary battery electrodes capable of forming an electrode mixture layer having excellent viscosity stability and suppressed swelling in an electrolyte solution.

In addition, the present invention is capable of forming an electrode mixture layer in which swelling in the electrolyte solution is suppressed, and also capable of exhibiting excellent cycle characteristics in non-aqueous secondary batteries A conductive material paste composition for non-aqueous secondary battery electrodes and a non-aqueous secondary battery It aims at providing the slurry composition for battery electrodes.

Another object of the present invention is to provide an electrode for a non-aqueous secondary battery, which is provided with an electrode mixture layer in which swelling in an electrolyte solution is suppressed, and which is capable of exhibiting excellent cycle characteristics in the non-aqueous secondary battery.

And, an object of the present invention is to provide a non-aqueous secondary battery having excellent cycle characteristics.

The inventors of the present invention conducted intensive studies for the purpose of solving the above problems. Then, the present inventors found that a binder composition comprising a polymer having a functional group capable of bonding with a cationic group and an organic compound having two or more cationic groups and having a molecular weight of a predetermined value or less has excellent viscosity stability, and furthermore, The present invention was completed by finding that an electrode mixture layer suppressed from swelling in an electrolyte solution can be formed by using the binder composition.

That is, this invention aims at solving the said subject advantageously, and the binder composition for non-aqueous secondary battery electrodes of this invention has a polymer which has a functional group bondable to a cationic group, and two or more cationic groups, , It is characterized by including an organic compound having a molecular weight of 8000 or less. As described above, a binder composition containing a polymer having a functional group capable of bonding with a cationic group and an organic compound having two or more cationic groups and having a molecular weight of a predetermined value or less has excellent viscosity stability, and when the binder composition is used , it is possible to form an electrode mixture layer in which swelling in the electrolyte solution is suppressed.

On the other hand, in the present invention, a "cationic group" refers to a functional group capable of exhibiting cationic character by being present alone or together with a substance that supplies static charge in a solvent. In the present invention, "functional group capable of bonding with a cationic group" refers to a functional group capable of interacting with a cationic group through an ionic bond, a hydrogen bond, a covalent bond, or the like in a solvent.

Here, in the binder composition for a non-aqueous secondary battery electrode of the present invention, it is preferable that the functional group bondable to the cationic group is at least one selected from the group consisting of a carboxylic acid group, a sulfonic acid group, a phosphoric acid group, and a hydroxyl group. When the polymer having the predetermined functional group described above is used, swelling of the electrode mixture layer in the electrolyte solution can be further suppressed while sufficiently securing the viscosity stability of the binder composition.

Further, in the binder composition for a non-aqueous secondary battery electrode of the present invention, the polymer preferably contains a monomer unit containing a functional group bondable to a cationic group in an amount of 0.1% by mass or more and 20% by mass or less. When a polymer containing a monomer unit containing a functional group capable of bonding with a cationic group in an amount within the above range is used, swelling of the electrode mixture layer in the electrolyte solution can be further suppressed while sufficiently securing the viscosity stability of the binder composition. .

On the other hand, in the present invention, "a monomer unit is included" means "a repeating unit derived from a monomer is contained in a polymer obtained using the monomer." On the other hand, the ratio of each monomer unit and/or structural unit contained in the polymer can be measured using nuclear magnetic resonance (NMR) methods such as ¹ H-NMR and ¹³ C-NMR.

Moreover, it is preferable that the binder composition for nonaqueous secondary battery electrodes of this invention contains 0.1 mass part or more and 20 mass parts or less of the said organic compound per 100 mass parts of said polymers. When the blending amount of the organic compound is within the above range, swelling of the electrode mixture layer in the electrolyte solution can be further suppressed while sufficiently securing the viscosity stability of the binder composition.

Here, in the binder composition for non-aqueous secondary battery electrodes of the present invention, the polymer contains at least one of a nitrile group-containing monomer unit, a conjugated diene monomer unit, and an alkylene structural unit, and the nitrile group-containing monomer in the polymer It is preferable that the unit ratio is 5% by mass or more and 35% by mass or less, and the sum of the ratio of the conjugated diene monomer unit and the ratio of the alkylene structural unit in the polymer is 30% by mass or more and 90% by mass or less. The polymer described above dissolves satisfactorily in the solvent of the binder composition, and at the same time adsorbs satisfactorily to a conductive material or the like and can disperse them satisfactorily (that is, has excellent dispersibility to a conductive material or the like). And swelling of the electrode mixture layer in the electrolyte solution can be further suppressed while sufficiently securing the viscosity stability of the binder composition by using the polymer.

In addition, this invention aims at advantageously solving the above problems, and the conductive material paste composition for non-aqueous secondary battery electrodes of the present invention comprises a conductive material and any one of the above-mentioned binders for non-aqueous secondary battery electrodes. It is characterized by comprising a composition. When a conductive material paste composition containing a conductive material and any one of the above-mentioned binder compositions is prepared, and an electrode active material or the like is added to the conductive material paste composition to prepare a slurry composition, swelling in the electrolyte solution is suppressed Electrode composite material A layer can be formed, and excellent cycle characteristics can be exhibited in a secondary battery.

Moreover, this invention aims at solving the said subject advantageously, and the slurry composition for non-aqueous secondary battery electrodes of this invention comprises an electrode active material and any one of the above-mentioned binder compositions for non-aqueous secondary battery electrodes, or It is characterized in that it includes the above-described conductive material paste for non-aqueous secondary battery electrodes. In this way, when the slurry composition containing the electrode active material and any one of the binder compositions or conductive material pastes described above is used, it is possible to form an electrode mixture layer in which swelling in the electrolyte solution is suppressed, and excellent cycle characteristics are exhibited for secondary batteries can make it

In addition, this invention aims at advantageously solving the above problems, and the electrode for a non-aqueous secondary battery of the present invention is provided with an electrode mixture layer formed using the above-mentioned slurry composition for a non-aqueous secondary battery electrode characterized by In this way, the electrode mixture layer obtained by using the above-described slurry composition is suppressed from swelling in the electrolyte solution, and the electrode including this electrode mixture layer can exhibit excellent cycle characteristics in a secondary battery.

Moreover, this invention aims to advantageously solve the said subject, and the non-aqueous secondary battery of this invention is provided with a positive electrode, a negative electrode, an electrolyte solution, and a separator, and at least one of the said positive electrode and the negative electrode has the above-mentioned non-aqueous secondary battery It is characterized in that it is an electrode for an aqueous secondary battery. In this way, the non-aqueous secondary battery provided with the electrode described above has excellent cycle characteristics.

ADVANTAGE OF THE INVENTION According to this invention, the binder composition for non-aqueous secondary battery electrodes which is excellent in viscosity stability and can form the electrode mixture layer in which swelling in electrolyte solution was suppressed is obtained.

In addition, according to the present invention, it is possible to form an electrode mixture layer in which swelling in the electrolyte solution is suppressed, and also to exhibit excellent cycle characteristics in non-aqueous secondary batteries A conductive material paste composition for non-aqueous secondary battery electrodes and non-aqueous A slurry composition for secondary battery electrodes is obtained.

Furthermore, according to the present invention, an electrode for a non-aqueous secondary battery can be obtained which has an electrode mixture layer in which swelling in the electrolyte solution is suppressed and which can exhibit excellent cycle characteristics in the non-aqueous secondary battery.

And according to the present invention, a non-aqueous secondary battery having excellent cycle characteristics is obtained.

EMBODIMENT OF THE INVENTION Hereinafter, embodiment of this invention is described in detail.

Here, the binder composition for non-aqueous secondary battery electrodes of this invention can be used when preparing the slurry composition for non-aqueous secondary battery electrodes. In addition, the binder composition for non-aqueous secondary battery electrodes of the present invention is mixed with a conductive material to obtain a conductive material paste composition for non-aqueous secondary battery electrodes containing the binder composition for non-aqueous secondary battery electrodes and a conductive material, and then non-aqueous It can be used for preparation of the slurry composition for secondary battery electrodes. And the slurry composition for nonaqueous secondary battery electrodes prepared using the binder composition for nonaqueous secondary battery electrodes of this invention can be used when forming the electrode of nonaqueous secondary batteries, such as a lithium ion secondary battery. In addition, the non-aqueous secondary battery of the present invention is characterized by using an electrode for non-aqueous secondary battery formed using the slurry composition for non-aqueous secondary battery electrode of the present invention.

On the other hand, the binder composition for non-aqueous secondary battery electrodes, the conductive material paste composition for non-aqueous secondary battery electrodes, and the slurry composition for non-aqueous secondary battery electrodes of the present invention can be used particularly suitably when forming a positive electrode of a non-aqueous secondary battery. there is.

(Binder composition for non-aqueous secondary battery electrode)

The binder composition for a non-aqueous secondary battery electrode of the present invention is a polymer having a functional group bondable to a cationic group (hereinafter sometimes referred to as “polymer (A)”), and an organic compound having two or more cationic groups ( Hereinafter, it may be referred to as “polyvalent cationic organic compound (B)”), and optionally further contains other components that can be incorporated into the electrode of a secondary battery. Here, in the binder composition for non-aqueous secondary battery electrodes of the present invention, the molecular weight of the polycationic organic compound (B) described above is 8000 or less. Moreover, the binder composition for non-aqueous secondary battery electrodes of this invention normally further contains solvents, such as an organic solvent.

In addition, since the binder composition of the present invention contains a polymer having a functional group capable of bonding with a cationic group and a polycationic organic compound (B) having a molecular weight of 8000 or less, the change in viscosity is small even when stored for a long period of time, and the electrode Swelling of the mixture layer in the electrolyte solution can be suppressed.

On the other hand, the reason why the binder composition of the present invention is excellent in viscosity stability and can suppress swelling of the electrode mixture layer in the electrolyte solution is not clear, but it is inferred as follows.

That is, in the binder composition of the present invention, the functional group in the polymer (A) and the cationic group in the polycationic organic compound (B) can interact favorably in a solvent, for example, the polymer (A) and the above Patent Document 1 Compared to the case where a polyvalent metal compound containing a predetermined ligand described above is used in combination, the change in viscosity over time is suppressed. In addition, since the binder composition of the present invention contains the polymer (A) and the polycationic organic compound (B), when the slurry composition containing the binder composition is dried or the like to form an electrode mixture layer, the polymer (A ) and the cationic group in the polycationic organic compound (B) interact more firmly by crosslinking or the like. Due to this strong interaction, a rigid network is formed, and the electrode mixture layer is not excessively swollen in the electrolyte solution. Furthermore, since the molecular weight of the above-mentioned polycationic organic compound (B) is 8000 or less, the polycationic organic compound (B) does not excessively thicken the binder composition, and the change in viscosity of the binder composition over time is further reduced. are suppressed

Therefore, according to the present invention, while securing the viscosity stability of the binder composition, swelling of the electrode mixture layer in the electrolyte solution can be suppressed, and excellent cycle characteristics can be exhibited in the secondary battery.

<Polymer (A)>

Polymer (A) is an electrode manufactured by forming an electrode mixture layer on a current collector using a slurry composition for non-aqueous secondary battery electrodes prepared using a binder composition, wherein the component contained in the electrode mixture layer is an electrode mixture layer (i.e., it is an adhesive polymer that functions as a binder).

<<Functional groups that can be combined with cationic groups>>

The functional group capable of bonding with the cationic group of the polymer (A) (hereinafter sometimes referred to as "bonding functional group") is not particularly limited, but is a carboxylic acid group or a sulfonic acid group that can interact favorably with the cationic group. , a phosphoric acid group, and a hydroxyl group. Among these, a carboxylic acid group, a sulfonic acid group, and a phosphoric acid group are more preferable, and a carboxylic acid group is particularly preferable. When the polymer (A) having these functional groups is used, the swelling of the electrode mixture layer in the electrolyte solution can be further suppressed while the viscosity stability of the binder composition is sufficiently secured, and the cycle characteristics of the secondary battery can be further improved. On the other hand, the polymer (A) may have only one type of bonding functional group, or may have two or more types.

<<Composition of Polymer (A)>>

Here, the method of introducing the binding functional group into the polymer (A) is not particularly limited, and a polymer is prepared using the above-mentioned monomer containing the binding functional group (binding functional group-containing monomer) to obtain a binding functional group-containing monomer unit. The containing polymer (A) may be obtained, or the polymer (A) having the above-mentioned bondable functional group at the terminal may be obtained by subjecting an arbitrary polymer to terminal modification, but the former is preferable. And the polymer (A) containing the binding functional group containing monomeric unit may contain repeating units other than the binding functional group containing monomeric unit.

[Combining Functional Group-Containing Monomer Unit]

Here, as the binding functional group-containing monomer capable of forming the binding functional group-containing monomer unit, preferably, a monomer having a carboxylic acid group, a monomer having a sulfonic acid group, a monomer having a phosphoric acid group, and a monomer having a hydroxyl group are selected. can be heard

Examples of the monomer having a carboxylic acid group include monocarboxylic acids and derivatives thereof, dicarboxylic acids and acid anhydrides thereof, and derivatives thereof.

As a monocarboxylic acid, acrylic acid, methacrylic acid, crotonic acid, etc. are mentioned.

Examples of monocarboxylic acid derivatives include 2-ethylacrylic acid, isocrotonic acid, α-acetoxyacrylic acid, β-trans-aryloxyacrylic acid, α-chloro-β-E-methoxyacrylic acid, and β-diaminoacrylic acid. can be heard

Maleic acid, fumaric acid, itaconic acid etc. are mentioned as a dicarboxylic acid.

Examples of dicarboxylic acid derivatives include methylmaleic acid, dimethylmaleic acid, phenylmaleic acid, chloromaleic acid, dichloromaleic acid, fluoromaleic acid, monobutyl maleate, monononyl maleate, monodecyl maleate, and maleic acid. and maleic acid monoesters such as monododecyl acid, monooctadecyl maleate, and monofluoroalkyl maleate.

Maleic anhydride, acrylic anhydride, methyl maleic anhydride, dimethyl maleic anhydride etc. are mentioned as an acid anhydride of dicarboxylic acid.

Moreover, as a monomer which has a carboxylic acid group, an acid anhydride which produces a carboxyl group by hydrolysis can also be used.

In addition, as a monomer having a sulfonic acid group, for example, vinylsulfonic acid, methylvinylsulfonic acid, (meth)allylsulfonic acid, 3-allyloxy-2-hydroxypropanesulfonic acid, 2-acrylamido-2-methylpropanesulfonic acid, etc. can be heard

In the present invention, "(meth)allyl" means allyl and/or methallyl.

Moreover, as a monomer which has a phosphoric acid group, phosphoric acid-2-(meth)acryloyloxyethyl, phosphoric acid methyl-2-(meth)acryloyloxyethyl, phosphoric acid ethyl-(meth)acryloyloxy, for example Ethyl etc. are mentioned.

In the present invention, "(meth)acryloyl" means acryloyl and/or methacryloyl.

And as a monomer which has a hydroxyl group, Ethylenically unsaturated alcohol, such as (meth) allyl alcohol, 3-buten-1-ol, and 5-hexen-1-ol; Acrylic acid-2-hydroxyethyl, acrylic acid-2-hydroxypropyl, methacrylic acid-2-hydroxyethyl, methacrylic acid-2-hydroxypropyl, maleic acid di-2-hydroxyethyl, maleic acid di-4- alkanol esters of ethylenically unsaturated carboxylic acids such as hydroxybutyl and di-2-hydroxypropyl itaconate; General formula: CH ₂ =CR ^Z -COO-(C _n H _2n O) _m -H (in the formula, m is an integer of 2 to 9, n is an integer of 2 to 4, R ^Z represents hydrogen or a methyl group) esters of polyalkylene glycol and (meth)acrylic acid represented by; Mono (of dihydroxy esters of dicarboxylic acids such as 2-hydroxyethyl-2'-(meth)acryloyloxyphthalate and 2-hydroxyethyl-2'-(meth)acryloyloxysuccinate) meth)acrylic acid esters; vinyl ethers such as 2-hydroxyethyl vinyl ether and 2-hydroxypropyl vinyl ether; (meth)allyl-2-hydroxyethyl ether, (meth)allyl-2-hydroxypropyl ether, (meth)allyl-3-hydroxypropyl ether, (meth)allyl-2-hydroxybutyl ether, (meth)allyl-2-hydroxybutyl ether, ) mono(meth)allyl ethers of alkylene glycols such as allyl-3-hydroxybutyl ether, (meth)allyl-4-hydroxybutyl ether, and (meth)allyl-6-hydroxyhexyl ether; polyoxyalkylene glycol mono(meth)allyl ethers such as diethylene glycol mono(meth)allyl ether and dipropylene glycol mono(meth)allyl ether; Halogens of (poly)alkylene glycols such as glycerin mono(meth)allyl ether, (meth)allyl-2-chloro-3-hydroxypropyl ether, and (meth)allyl-2-hydroxy-3-chloropropyl ether and mono(meth)allyl ether of hydroxy substituents; mono(meth)allyl ethers of polyhydric phenols such as eugenol and isoeugenol and halogen-substituted products thereof; (meth)allylthioethers of alkylene glycols such as (meth)allyl-2-hydroxyethylthioether and (meth)allyl-2-hydroxypropylthioether; etc. can be mentioned.

In addition, in this invention, "(meth)acryl" means an acryl and/or methacryl.

Among these, the polymer (A) interacts well with the polycationic organic compound (B) to further suppress the swelling of the electrode mixture layer in the electrolyte solution while sufficiently securing the viscosity stability of the binder composition, thereby improving the cycle of the secondary battery. From the viewpoint of further improving the properties, the monomer having a binding functional group is preferably a monomer having a carboxylic acid group, a monomer having a sulfonic acid group, and a monomer having a phosphoric acid group, and a monomer having a carboxylic acid group is more preferable. That is, the monomer unit containing a binding functional group is preferably at least one selected from the group consisting of a monomer unit having a carboxylic acid group, a monomer unit having a sulfonic acid group, and a monomer unit having a phosphoric acid group, and a monomer unit having a carboxylic acid group. is more preferable.

In addition, the binding functional group-containing monomer may be used alone or in combination of two or more at an arbitrary ratio.

The ratio of the bonding functional group-containing monomer units contained in the polymer (A) is preferably 0.1% by mass or more, more preferably 0.5% by mass or more, still more preferably 1% by mass or more, and 20% by mass or less. It is preferably 10% by mass or less, more preferably 6% by mass or less, and still more preferably 6% by mass or less. The polymer (A) does not interact excessively with the polycationic organic compound (B) as long as the proportion of the monomer units containing the binding functional group in the polymer (A) is equal to or less than the above upper limit. Accordingly, the viscosity stability of the binder composition is sufficiently secured by suppressing the aggregation of these components, and the cycle characteristics of the secondary battery can be further improved. In addition, when the ratio of the bonding functional group-containing monomer units contained in the polymer (A) is equal to or greater than the lower limit, the swelling of the electrode mixture layer in the electrolyte solution can be further suppressed while sufficiently securing the viscosity stability of the binder composition, resulting in a secondary battery The cycle characteristics of can be further improved.

[Repeating units other than monomeric units containing bondable functional groups]

In addition, the repeating unit other than the binding functional group-containing monomer unit that the polymer (A) may contain is not particularly limited, and a conjugated diene monomer unit, an alkylene structural unit, a nitrile group-containing monomer unit, (meth)acrylic acid An ester monomeric unit, and an aromatic vinyl monomeric unit etc. are mentioned.

-Conjugated Diene Monomer Unit-

Here, as a conjugated diene monomer which can form a conjugated diene monomeric unit, for example, 1,3-butadiene, isoprene, 2,3-dimethyl-1,3-butadiene, 1,3-pentadiene, etc. carbon number Four or more conjugated diene compounds are mentioned. Especially, 1,3-butadiene is preferable.

These can be used individually or in combination of 2 or more types.

-Alkylene Structural Unit-

In addition, the alkylene structural unit is a repeating unit composed only of an alkylene structure represented by the general formula: -C _n H _2n - [provided that n is an integer greater than or equal to 2].

Here, the alkylene structural unit may be linear or branched, but from the viewpoint of improving the dispersion stability of the slurry composition for non-aqueous secondary battery electrodes, the alkylene structural unit is linear, that is, a linear alkylene structural unit desirable. Moreover, from a viewpoint of further improving the dispersion stability of the slurry composition for nonaqueous secondary battery electrodes, it is preferable that the number of carbon atoms of an alkylene structural unit is 4 or more (ie, n in the said general formula is an integer of 4 or more).

And, the introduction method of the alkylene structural unit into the polymer (A) is not particularly limited, but is, for example, the method of the following (1) or (2):

(1) A method of converting a conjugated diene monomer unit into an alkylene structural unit by preparing a copolymer from a monomer composition containing a conjugated diene monomer and adding hydrogen to the copolymer.

(2) Method for preparing a copolymer from a monomer composition containing a 1-olefin monomer

can be heard Among these, the method (1) is preferable because it is easy to manufacture the polymer (A).

On the other hand, as the conjugated diene monomer used in the method (1) above, conjugated dienes having 4 or more carbon atoms such as 1,3-butadiene, isoprene, 2,3-dimethyl-1,3-butadiene, and 1,3-pentadiene compounds are exemplified, and among them, 1,3-butadiene is preferable. That is, the alkylene structural unit is preferably a structural unit (conjugated diene hydride unit) obtained by hydrogenating a conjugated diene monomer unit, and a structural unit obtained by hydrogenating a 1,3-butadiene unit (1,3-butadiene hydride unit). unit) is more preferable. And selective hydrogenation of the conjugated diene monomer unit can be performed using a well-known method, such as an oil-bed hydrogenation method and a water-bed hydrogenation method.

Moreover, as a 1-olefin monomer used by the method of said (2), ethylene, propylene, 1-butene, 1-hexene etc. are mentioned, for example.

These conjugated diene monomers and 1-olefin monomers can be used individually or in combination of 2 or more types.

-Nitrile group-containing monomer unit-

Further, as the nitrile group-containing monomer capable of forming the nitrile group-containing monomer unit, an α,β-ethylenically unsaturated nitrile monomer is exemplified. Specifically, the α,β-ethylenically unsaturated nitrile monomer is not particularly limited as long as it is an α,β-ethylenically unsaturated compound having a nitrile group, and examples thereof include acrylonitrile; α-halogenoacrylonitriles such as α-chloroacrylonitrile and α-bromoacrylonitrile; α-alkylacrylonitriles such as methacrylonitrile and α-ethylacrylonitrile; etc. can be mentioned. Among these, as a nitrile-group containing monomer, acrylonitrile and methacrylonitrile are preferable, and acrylonitrile is more preferable.

These can be used individually or in combination of 2 or more types.

-(meth)acrylic acid ester monomer unit-

In addition, as a (meth)acrylic acid ester monomer capable of forming a (meth)acrylic acid ester monomer unit, methyl acrylate, ethyl acrylate, n-propyl acrylate, isopropyl acrylate, n-butyl acrylate, t- Butyl acrylate, isobutyl acrylate, n-pentyl acrylate, isopentyl acrylate, hexyl acrylate, heptyl acrylate, octyl acrylate, 2-ethylhexyl acrylate, nonyl acrylate, decyl acrylate, lauryl acrylate acrylic acid alkyl esters such as late, n-tetradecyl acrylate, and stearyl acrylate; Methyl methacrylate, ethyl methacrylate, n-propyl methacrylate, isopropyl methacrylate, n-butyl methacrylate, t-butyl methacrylate, isobutyl methacrylate, n-pentyl methacrylate, Isopentyl methacrylate, hexyl methacrylate, heptyl methacrylate, octyl methacrylate, 2-ethylhexyl methacrylate, nonyl methacrylate, decyl methacrylate, lauryl methacrylate, n-tetradecyl methacrylate methacrylic acid alkyl esters such as acrylate and stearyl methacrylate; etc. can be mentioned. Among them, methyl acrylate, ethyl acrylate, n-butyl acrylate, 2-ethylhexyl acrylate, methyl methacrylate, ethyl methacrylate, n-butyl methacrylate, and 2-ethylhexyl methacrylate are preferred. And, n-butyl acrylate, ethyl methacrylate, and 2-ethylhexyl acrylate are more preferable.

These can be used individually or in combination of 2 or more types.

-Aromatic vinyl monomer unit-

Moreover, as an aromatic vinyl monomer which can form an aromatic vinyl monomer unit, styrene, (alpha)-methylstyrene, butoxy styrene, vinyl naphthalene, etc. are mentioned. Especially, styrene is preferable.

These can be used individually or in combination of 2 or more types.

Among repeating units other than the above-mentioned binding functional group-containing monomeric units, the solubility of the binder composition of the polymer (A) in a solvent and the dispersibility in a conductive material, etc. are improved, and as a result, the electrode composite material while sufficiently securing the viscosity stability of the binder composition From the viewpoint of further improving the cycle characteristics of the secondary battery by further suppressing the swelling of the layer in the electrolyte solution, the polymer (A) contains at least one of a nitrile group-containing monomer unit, a conjugated diene monomer unit, and an alkylene structural unit. It is preferable to do so, and it is more preferable to include a nitrile group-containing monomeric unit and an alkylene structural unit.

The ratio of the nitrile group-containing monomeric unit contained in the polymer (A) is preferably 5% by mass or more, more preferably 7% by mass or more, still more preferably 9% by mass or more, and particularly 10% by mass or more. It is preferably 35% by mass or less, more preferably 29% by mass or less, and still more preferably 23% by mass or less. When the ratio of the nitrile group-containing monomer units contained in the polymer (A) is equal to or less than the above upper limit, swelling of the electrode mixture layer in the electrolyte solution can be further suppressed, and the cycle characteristics of the secondary battery can be further improved. In addition, when the ratio of the nitrile group-containing monomer units contained in the polymer (A) is equal to or greater than the lower limit, the solubility of the polymer (A) in the binder composition in the solvent increases, and the viscosity stability of the binder composition can be sufficiently secured.

Further, the total ratio of the conjugated diene monomer unit and the alkylene structural unit contained in the polymer (A) is preferably 30% by mass or more, more preferably 40% by mass or more, preferably 90% by mass or less, and 75% by mass or less. It is more preferable that it is mass % or less. When the sum of the ratios of the conjugated diene monomer units and the alkylene structural units contained in the polymer (A) is equal to or less than the above upper limit, the solubility of the binder composition of the polymer (A) in a solvent is not impaired, and the viscosity stability of the binder composition is improved. enough can be secured. In addition, when the sum of the ratios of the conjugated diene monomer units and the alkylene structural units contained in the polymer (A) is equal to or greater than the above lower limit, the dispersibility of the polymer (A) to a conductive material or the like increases. In addition, the viscosity stability of the binder composition can be sufficiently secured, and the cycle characteristics of the secondary battery can be further improved.

On the other hand, the ratio of repeating units other than the binding functional group-containing monomer unit, the conjugated diene monomer unit, the alkylene structural unit, and the nitrile group-containing monomer unit contained in the polymer (A) is 0% by mass or more and 60% by mass or less. can

[Preparation method of polymer (A)]

The preparation method of the above-mentioned polymer (A) is not particularly limited, but the polymer (A) is obtained by, for example, polymerizing a monomer composition containing the above-mentioned monomers to obtain a copolymer, and then, if necessary, hydrogenating the obtained copolymer It can be prepared by (hydrogenation).

Here, the content ratio of each monomer in the monomer composition used for preparation of the polymer (A) can be determined according to the content ratio of each repeating unit in the polymer (A).

The polymerization mode is not particularly limited, and any method such as a solution polymerization method, a suspension polymerization method, a bulk polymerization method, or an emulsion polymerization method can be used. In addition, as a polymerization reaction, any reaction, such as ionic polymerization, radical polymerization, and living radical polymerization, can be used.

In addition, the hydrogenation method of the copolymer is, without particular limitation, a general method using a catalyst (see, for example, International Publication No. 2012/165120, International Publication No. 2013/080989 and Japanese Patent Application Publication No. 2013-8485) can be used.

<Polyvalent cationic organic compound (B)>

The polycationic organic compound (B) is not particularly limited as long as it is an organic compound having a plurality of cationic groups in one molecule. As the cationic group, for example, a substituted or unsubstituted amino group (-NH ₂ , -NHR ¹ , -NR ¹ R ² , -N ⁺ R ¹ R ² R ³ . Here, R ¹ to R ³ are arbitrary substituents ), a substituted or unsubstituted imino group (=NH, =NR ⁴ . Here, R ⁴ represents an arbitrary substituent), and a nitrogen-containing functional group (excluding an amide group) such as an oxazoline group. . Among these, the polycationic organic compound (B) interacts favorably with the polymer (A) to further suppress the swelling of the electrode mixture layer in the electrolyte solution while sufficiently securing the viscosity stability of the binder composition, thereby improving the cycle of the secondary battery. From the viewpoint of further improving the properties, a primary amino group (unsubstituted amino group, -NH ₂ ), a secondary amino group (-NHR ¹ ), and a substituted or unsubstituted imino group are preferable. On the other hand, the polycationic organic compound (B) may have only one type of cationic group and may have two or more types of cationic groups.

On the other hand, in the present invention, when the polymer, which is an organic compound having two or more cationic groups, has a functional group bondable to the cationic group, the polymer corresponds to the polycationic organic compound (B) instead of the polymer (A). do it by doing

<Molecular weight of polycationic organic compound (B)>

Here, the molecular weight of the polycationic organic compound (B) (when the polycationic organic compound (B) is a polymer, it refers to "number average molecular weight") is required to be 8000 or less, preferably 2000 or less, 1800 It is more preferably less than or equal to, more preferably less than or equal to 1600, and particularly preferably less than or equal to 1500. When the molecular weight of the polycationic organic compound (B) exceeds 8000, the binder composition is excessively thickened so that viscosity stability cannot be sufficiently secured, and the cycle characteristics of the secondary battery also deteriorate. On the other hand, the molecular weight of the polycationic organic compound (B) is preferably 60 or more, and more preferably 100 or more, from the viewpoint of sufficiently suppressing the swelling of the electrode mixture layer in the electrolyte solution and further improving the cycle characteristics of the secondary battery. do.

On the other hand, in the present invention, when the polycationic organic compound (B) is a polymer, its number average molecular weight can be obtained as a molecular weight in terms of polystyrene measured by gel permeation chromatography (developing solvent: tetrahydrofuran) .

<Example of polycationic organic compound (B)>

As the polycationic organic compound (B), as long as the molecular weight is within the above-mentioned range, a non-polymeric polycationic organic compound (B) may be used, or a polymeric polycationic organic compound (B) may be used.

Here, as the polyvalent cationic organic compound (B) which is a non-polymer, ethylenediamine, diethylenetriamine, triethylenetetramine, phenyldiamine, 4,4'-diaminodiphenyl ether, N,N'-bis(3 -Phenyl-2-propenylidene)-1,6-hexanediamine, bisaniline, etc. are mentioned.

Moreover, as a polycationic organic compound (B) which is a polymer, it is polyethyleneimine; polyethyleneimine derivatives such as poly N-hydroxylethyleneimine and carboxymethylated polyethyleneimine/sodium salt; polypropylene imine; polypropyleneimine derivatives such as poly N-2-dihydroxypropyleneimine; polyallylamine; polyallylamine derivatives such as polydimethyldiallylammonium halide; aminoethylated acrylic polymer obtained by aminoethylating an acrylic acid polymer; and cationized cellulose obtained by modifying a cellulose derivative (hydroxyethyl cellulose, carboxymethyl cellulose, etc.) with a cationizing agent having a substituted or unsubstituted amino group.

These can be used individually or in combination of 2 or more types. Among these, polyethyleneimine, polyethyleneimine derivatives, N,N' from the viewpoint of further suppressing swelling of the electrode mixture layer in the electrolyte solution while sufficiently securing the viscosity stability of the binder composition and further improving the cycle characteristics of the secondary battery -Bis(3-phenyl-2-propenylidene)-1,6-hexanediamine, polyallylamine, and diethylenetriamine are more preferable.

<Blending amount of polycationic organic compound (B)>

The compounding amount of the polycationic organic compound (B) having a molecular weight within the above range is preferably 0.1 part by mass or more, more preferably 0.2 part by mass or more, and still more preferably 0.5 part by mass or more per 100 parts by mass of the polymer (A). It is preferably 2 parts by mass or more, particularly preferably 20 parts by mass or less, more preferably 10 parts by mass or less, and still more preferably 6 parts by mass or less. When the amount of the polycationic organic compound (B) is excessive, the viscosity stability of the binder composition is rather deteriorated. However, if the blending amount of the polycationic organic compound (B) is 20 parts by mass or less, the viscosity stability of the binder composition can be sufficiently secured. In addition, when the compounding amount of the polycationic organic compound (B) is 0.1 parts by mass or more, a more rigid network can be formed between the polymer (A) and the polycationic organic compound (B) in the electrode mixture layer. Therefore, the swelling of the electrode mixture layer in the electrolyte solution can be further suppressed, and the cycle characteristics of the secondary battery can be further improved.

<Solvent>

As a solvent of the binder composition for non-aqueous secondary battery electrodes, an organic solvent is preferable. The organic solvent is not particularly limited, and examples thereof include methanol, ethanol, n-propanol, isopropanol, n-butanol, isobutanol, t-butanol, pentanol, hexanol, heptanol, octanol, nonanol, alcohols such as decanol and amyl alcohol; Ketones, such as acetone, methyl ethyl ketone, and cyclohexanone; esters such as ethyl acetate and butyl acetate; ethers such as diethyl ether, dioxane, and tetrahydrofuran; amide-based polar organic solvents such as N,N-dimethylformamide and N-methylpyrrolidone (NMP); aromatic hydrocarbons such as toluene, xylene, chlorobenzene, orthodichlorobenzene, and paradichlorobenzene; etc. can be mentioned. These may be used individually by 1 type, and may mix and use two or more types.

Especially, as a solvent, a polar organic solvent is preferable and NMP is more preferable.

<Other ingredients>

On the other hand, in the binder composition for nonaqueous secondary battery electrodes of the present invention, in addition to the above components, binders other than the polymer (A) (polyvinylidene fluoride, polyacrylonitrile, polyacrylate, etc.), reinforcing materials, leveling agents, viscosity Components such as a regulator and an electrolyte solution additive may be contained in the binder composition. These are not particularly limited as long as they do not affect the battery reaction, and known ones such as those described in International Publication No. 2012/115096 can be used. In addition, these components may be used individually by 1 type, and may be used combining two or more types by arbitrary ratios.

<Swelling degree of the electrolyte solution of the film made of the binder composition>

And, the electrolyte solution swelling degree of the film obtained by drying the binder composition of the present invention containing the above components is preferably less than 2000 mass%, more preferably less than 1000 mass%, still more preferably less than 800 mass%, and 600 Less than mass % is particularly preferred. If the degree of swelling of the electrolyte solution of the film made of the binder composition is less than 2000% by mass, the cycle characteristics of the secondary battery can be sufficiently improved. Moreover, the electrolyte solution swelling degree of the film which consists of a binder composition is 100 mass % or more normally.

On the other hand, the electrolyte solution swelling degree of the film made of the binder composition can be measured using the method described in Examples of the present specification.

(Slurry composition for non-aqueous secondary battery electrode)

The slurry composition for nonaqueous secondary battery electrodes of this invention contains an electrode active material and the above-mentioned binder composition, and optionally contains a conductive material and other components further. That is, the slurry composition of the present invention contains an electrode active material, the above-mentioned polymer (A), the above-mentioned polycationic organic compound (B), and a solvent, optionally a conductive material and other components. do. And, since the slurry composition of the present invention contains the above-mentioned binder composition, the electrode mixture layer formed using the slurry composition of the present invention suppresses swelling in the electrolyte solution, and also has excellent cycle characteristics for secondary batteries. can exert

<Electrode active material>

Here, the electrode active material is a material that exchanges electrons in the electrode of the non-aqueous secondary battery. And, for example, when the non-aqueous secondary battery is a lithium ion secondary battery, a material capable of intercalating and deintercalating lithium is usually used as the electrode active material.

On the other hand, in the following, as an example, a case where the slurry composition for non-aqueous secondary battery electrodes is a slurry composition for lithium ion secondary battery electrodes will be described, but the present invention is not limited to the following examples.

In addition, the positive electrode active material for lithium ion secondary batteries is not particularly limited, and lithium-containing cobalt oxide (LiCoO ₂ ), lithium manganate (LiMn ₂ O ₄ ), lithium-containing nickel oxide (LiNiO ₂ ), Co-Ni-Mn of lithium-containing composite oxide (Li(Co Mn Ni)O ₂ ), lithium-containing composite oxide of Ni-Mn-Al, lithium-containing composite oxide of Ni-Co-Al, olivine type lithium iron phosphate (LiFePO ₄ ), olivine type Lithium manganese phosphate (LiMnPO ₄ ), Li ₂ MnO ₃ -LiNiO ₂ based solid solution, lithium-excessive spinel compound represented by Li _1+x Mn _2-x O ₄ (0 < X < 2), Li[Ni _0.17 Li _0.2 and known positive electrode active materials such as Co _0.07 Mn _0.56 ]O ₂ and LiNi _0.5 Mn _1.5 O ₄ .

On the other hand, the blending amount and particle diameter of the positive electrode active material are not particularly limited, and can be the same as those of conventionally used positive electrode active materials.

Moreover, as a negative electrode active material for lithium ion secondary batteries, the carbon-type negative electrode active material, the metal-type negative electrode active material, the negative electrode active material which combined these, etc. are mentioned, for example.

Here, the carbon-based negative electrode active material refers to an active material having carbon as a main skeleton and capable of intercalating (also referred to as “dope”) lithium, and examples of the carbon-based negative electrode active material include carbonaceous materials and graphite materials. can

And as a carbonaceous material, easily graphitic carbon, difficult-graphitic carbon which has a structure close to the amorphous structure represented by glassy carbon, etc. are mentioned, for example.

Here, as easily graphitic carbon, the carbon material which used tar pitch obtained from petroleum or coal as a raw material is mentioned, for example. Specific examples thereof include coke, mesocarbon microbeads (MCMB), mesophase pitch-based carbon fibers, thermal decomposition vapor grown carbon fibers, and the like.

Moreover, as non-graphitic carbon, a phenol resin sintered body, polyacrylonitrile-type carbon fiber, quasi-isotropic carbon, furfuryl alcohol resin sintered body (PFA), hard carbon etc. are mentioned, for example.

Moreover, as a graphite material, natural graphite, artificial graphite, etc. are mentioned, for example.

Here, as artificial graphite, for example, artificial graphite obtained by heat-treating carbon containing easily graphitic carbon mainly at 2800 ° C. or higher, graphitized MCMB obtained by heat-treating MCMB at 2000 ° C. or higher, and mesophase pitch-based carbon fiber at 2000 ° C. or higher and graphitized mesophase pitch-based carbon fibers subjected to heat treatment.

In addition, a metal-based negative electrode active material is an active material containing a metal, which usually contains an element capable of intercalating lithium in its structure, and has a theoretical electric capacity per unit mass of 500 mAh/g or more when lithium is intercalated. . Examples of the metal-based active material include, for example, lithium metal and a simple metal capable of forming a lithium alloy (eg, Ag, Al, Ba, Bi, Cu, Ga, Ge, In, Ni, P, Pb, Sb, Si, Sn, Sr, Zn, Ti, etc.) and their alloys, and their oxides, sulfides, nitrides, silicides, carbides, phosphides, etc. are used. Among these, as the metal negative electrode active material, an active material containing silicon (silicon negative electrode active material) is preferable. It is because the capacity of a lithium ion secondary battery can be increased by using a silicon type negative electrode active material.

Examples of the silicon-based negative electrode active material include silicon (Si), a silicon-containing alloy, SiO, _SiOx , and a composite of a Si-containing material obtained by coating or combining a Si-containing material with conductive carbon and conductive carbon, and the like. can On the other hand, these silicon-type negative electrode active materials may be used individually by 1 type, and may be used in combination of 2 or more types.

On the other hand, the blending amount and particle size of the negative electrode active material are not particularly limited, and can be the same as those of conventionally used negative electrode active materials.

<Binder composition for non-aqueous secondary battery electrode>

As the binder composition for non-aqueous secondary battery electrodes, a binder composition for non-aqueous secondary battery electrodes containing the above-described polymer (A) and polycationic organic compound (B) is used.

Here, the content of the binder composition in the slurry composition for non-aqueous secondary battery electrodes is preferably an amount of 0.1 part by mass or more, and preferably 0.3 part by mass or more of the polymer (A) per 100 parts by mass of the electrode active material. More preferably, it is preferable that it is an amount used as 3 parts by mass or less, and it is more preferable that it is an amount used as 1.5 parts by mass or less. When the slurry composition contains the binder composition in an amount such that the amount of the polymer (A) is within the above range, swelling of the electrode mixture layer in the electrolyte solution can be further suppressed and the cycle characteristics of the secondary battery can be further improved.

<Challenging material>

The conductive material is for ensuring electrical contact between electrode active materials. And, as the conductive material, carbon black (for example, acetylene black, Ketjen Black (registered trademark), furnace black, etc.), single- or multi-layer carbon nanotubes (multi-layer carbon nanotubes include cup stack type), conductive carbon materials such as carbon nanohorns, vapor-grown carbon fibers, milled carbon fibers obtained by crushing polymer fibers after firing, single-layer or multi-layer graphene, and carbon non-woven fabric sheets obtained by firing non-woven fabrics composed of polymer fibers; Fibers or foils of various metals can be used.

These can be used individually by 1 type or in combination of 2 or more types.

On the other hand, the content ratio of the conductive material in the slurry composition for non-aqueous secondary battery electrodes is preferably 0.1 parts by mass or more, more preferably 0.5 parts by mass or more, preferably 5 parts by mass or less, and 3 parts by mass per 100 parts by mass of the electrode active material. It is more preferable that it is less than a part. When the amount of the conductive material is within the above range, sufficient electrical contact between the electrode active materials can be ensured, and excellent battery characteristics (such as cycle characteristics) can be exhibited in the secondary battery.

<Other ingredients>

The other components that can be incorporated into the slurry composition are not particularly limited, and include the same components as the other components that can be incorporated into the binder composition described above. In addition, other components may be used individually by 1 type, and may be used combining two or more types by arbitrary ratios.

<Preparation of slurry composition>

The slurry composition described above can be prepared by dissolving or dispersing the above components in a solvent such as an organic solvent. Specifically, by mixing the above components and a solvent using a mixer such as a ball mill, sand mill, bead mill, pigment disperser, brain grinder, ultrasonic disperser, homogenizer, planetary mixer, fill mix, slurry composition can be prepared. On the other hand, you may use the solvent contained in the binder composition as a solvent used for preparation of a slurry composition.

Here, the order in which each component is mixed in a solvent is not particularly limited, and can be any order. Specifically, when preparing a slurry composition, said each component can be mixed in any one of following (1)-(3) order, for example.

(1) All of the above components are mixed together.

(2) After mixing a binder composition containing a polymer (A) and a polycationic organic compound (B) and a conductive material to obtain a conductive material paste composition for a non-aqueous secondary battery electrode, a conductive material for a non-aqueous secondary battery electrode An electrode active material is added and mixed with respect to the paste composition.

(3) After mixing the conductive material and the electrode active material, a binder composition containing the polymer (A) and the polycationic organic compound (B) is added to the obtained mixture and mixed.

Among the above, it is preferable to mix each of the above components in the order of the above (1) or (2). On the other hand, when the procedure of (2) is adopted, that is, the binder composition and the conductive material are mixed in advance, and the conductive material and the above-described binder composition are mixed (ie, the conductive material, the polymer (A), and the polycationic When the conductive material paste composition for a non-aqueous secondary battery electrode (containing an organic compound (B) and a solvent) is used, the polymer (A) can be adsorbed on the surface of the conductive material to disperse the conductive material well. As a result, excellent battery characteristics (such as cycle characteristics) can be exhibited in the secondary battery.

Meanwhile, in the present invention, the conductive material paste composition for non-aqueous secondary battery electrodes is an intermediate product for preparing the slurry composition for non-aqueous secondary battery electrodes of the present invention, and as described above, the conductive material and the polymer (A ), a polycationic organic compound (B), and a solvent, while containing no electrode active material.

(Electrode for non-aqueous secondary battery)

The electrode for secondary batteries of the present invention includes a current collector and an electrode mixture layer formed on the current collector, and the electrode mixture layer is formed using the slurry composition for non-aqueous secondary battery electrodes. That is, the electrode mixture layer contains at least an electrode active material, a polymer (A), and a polycationic organic compound (B) having a molecular weight of a predetermined value or less. Here, the polymer (A) and the polycationic organic compound (B) may form a cross-linked structure. That is, the electrode mixture layer may contain a cross-linked product of the polymer (A) and the polycationic organic compound (B). On the other hand, each component contained in the electrode mixture layer was contained in the slurry composition for non-aqueous secondary battery electrodes, and the suitable abundance ratio of each component is the same as the suitable abundance ratio of each component in the slurry composition.

And since the slurry composition containing the binder composition for non-aqueous secondary battery electrodes of this invention is used in the electrode for non-aqueous secondary batteries of this invention, the polymer (A) and the polycationic organic compound (B) mutually firmly mutually A rigid electrode composite material layer can be favorably formed on the current collector. Therefore, when the electrode is used, swelling of the electrode mixture layer in the electrolyte solution is suppressed, and a secondary battery excellent in battery characteristics such as cycle characteristics is obtained.

<Method of manufacturing electrode>

On the other hand, the electrode for a non-aqueous secondary battery of the present invention, for example, a step of applying the above-described slurry composition on a current collector (application step), and drying the slurry composition applied on the current collector to form an electrode on the current collector It is manufactured through the process of forming a mixture layer (drying process).

<<Applying process>>

The method of applying the slurry composition on the current collector is not particularly limited, and a known method can be used. Specifically, as a coating method, a doctor blade method, a dip method, a reverse roll method, a direct roll method, a gravure method, an extrusion method, a brush coating method, or the like can be used. At this time, the slurry composition may be applied only to one side of the current collector, or may be applied to both sides. The thickness of the slurry film on the current collector after application and before drying can be appropriately set according to the thickness of the electrode mixture layer obtained by drying.

Here, as the current collector to which the slurry composition is applied, a material having electrical conductivity and electrochemical durability is used. Specifically, as the current collector, a current collector made of iron, copper, aluminum, nickel, stainless steel, titanium, tantalum, gold, platinum, or the like can be used, for example. In addition, said material may be used individually by 1 type, and may be used combining two or more types by arbitrary ratios.

<<Drying Process>>

The method for drying the slurry composition on the current collector is not particularly limited, and a known method can be used. For example, a drying method using warm air, hot air, or low humidity air, a vacuum drying method, or a drying method by irradiation with infrared rays or electron beams. can be heard By drying the slurry composition on the current collector in this way, an electrode mixture layer can be formed on the current collector to obtain a secondary battery electrode including the current collector and the electrode mixture layer. The drying temperature is preferably 60°C or higher and 200°C or lower, more preferably 90°C or higher and 150°C or lower.

On the other hand, for example, when a polymer having at least one of a carboxylic acid group, a sulfonic acid group, and a phosphoric acid group is used as the polymer (A) and a compound containing an amino group is used as the polycationic organic compound (B), the polymer (A) and the polycationic organic compound (B) are crosslinked by an amide bond, further suppressing swelling of the electrode mixture layer in the electrolyte solution, and further improving the cycle characteristics of the secondary battery.

On the other hand, after the drying step, a pressure treatment may be applied to the electrode mixture layer using a mold press, roll press, or the like. The pressure treatment can improve the adhesion between the electrode mixture layer and the current collector. In addition, when the electrode mixture layer contains a curable polymer, it is preferable to cure the polymer after formation of the electrode mixture layer.

(Non-aqueous secondary battery)

The non-aqueous secondary battery of the present invention includes a positive electrode, a negative electrode, an electrolyte solution, and a separator, and uses the electrode for secondary batteries of the present invention as at least one of the positive electrode and the negative electrode. And since the non-aqueous secondary battery of this invention is equipped with the electrode for non-aqueous secondary batteries of this invention, it is excellent in battery characteristics, such as cycle characteristics.

Meanwhile, in the following, as an example, a case where the non-aqueous secondary battery is a lithium ion secondary battery will be described, but the present invention is not limited to the following example.

<electrode>

Here, it is not specifically limited as an electrode other than the above-mentioned electrode for non-aqueous secondary batteries which can be used for the non-aqueous secondary battery of this invention, A known electrode used for manufacture of a secondary battery can be used. Specifically, as electrodes other than the electrodes for non-aqueous secondary batteries described above, electrodes formed by forming an electrode mixture layer on a current collector using a known manufacturing method can be used.

<Electrolyte>

As the electrolytic solution, an organic electrolytic solution obtained by dissolving a supporting electrolyte in an organic solvent is usually used. As a support electrolyte for a lithium ion secondary battery, a lithium salt is used, for example. Examples of the lithium salt include LiPF ₆ , LiAsF ₆ , LiBF ₄ , LiSbF ₆ , LiAlCl ₄ , LiClO ₄ , CF ₃ SO ₃ Li, C ₄ F ₉ SO ₃ Li, CF ₃ COOLi, (CF ₃ CO) ₂ NLi, (CF ₃ SO ₂ ) ₂ NLi, (C ₂ F ₅ SO ₂ ) NLi, and the like. Among them, LiPF ₆ , LiClO ₄ , CF ₃ SO ₃ Li are preferred, and LiPF ₆ is particularly preferred, since they are easily soluble in solvents and exhibit a high degree of dissociation. On the other hand, one type of electrolyte may be used alone, or two or more types may be used in combination at an arbitrary ratio. Usually, since lithium ion conductivity tends to increase as a supporting electrolyte having a high degree of dissociation is used, the lithium ion conductivity can be controlled by the type of supporting electrolyte.

The organic solvent used for the electrolyte solution is not particularly limited as long as it can dissolve the supporting electrolyte, and examples thereof include dimethyl carbonate (DMC), ethylene carbonate (EC), diethyl carbonate (DEC), and propylene carbonate (PC). carbonates such as butylene carbonate (BC) and ethyl methyl carbonate (EMC); esters such as γ-butyrolactone and methyl formate; ethers such as 1,2-dimethoxyethane and tetrahydrofuran; sulfur-containing compounds such as sulfolane and dimethyl sulfoxide; etc. are used appropriately. Moreover, you may use the liquid mixture of these solvents. Among them, it is preferable to use carbonates because they have a high dielectric constant and a wide range of stable potentials.

On the other hand, the concentration of the electrolyte in the electrolyte solution can be appropriately adjusted. In addition, known additives can be added to the electrolyte solution.

<Separator>

It does not specifically limit as a separator, For example, what was described in Unexamined-Japanese-Patent No. 2012-204303 can be used. Among these, polyolefin-based (polyethylene, polypropylene, polybutene, poly A microporous film made of a resin of vinyl chloride) is preferable.

<Method for Manufacturing Secondary Battery>

The secondary battery of the present invention, for example, overlapping a positive electrode and a negative electrode with a separator interposed therebetween, winding or folding this according to the shape of the battery, putting it in a battery container, injecting electrolyte into the battery container and sealing it can be manufactured In order to prevent an increase in pressure inside the secondary battery, an overcharge/discharge, or the like, a fuse, an overcurrent prevention element such as a PTC element, an expanded metal, a lead plate, or the like may be provided as necessary. The shape of the secondary battery may be, for example, a coin shape, a button shape, a sheet shape, a cylindrical shape, a prismatic shape, or a flat shape.

[Example]

Hereinafter, the present invention will be specifically described based on examples, but the present invention is not limited to these examples. Incidentally, in the following description, "%", "ppm", and "part" representing quantities are based on mass unless otherwise specified.

In addition, in a polymer produced by copolymerizing a plurality of types of monomers, the ratio of monomer units formed by polymerization of a certain monomer in the polymer is usually the total amount used for polymerization of the polymer, unless otherwise specified. It coincides with the ratio (input ratio) of any of the monomers occupied in the monomer.

In Examples and Comparative Examples, the viscosity stability of the binder composition, the swelling degree of the electrolyte solution of the film made of the binder composition, and the cycle characteristics of the secondary battery were evaluated by the following methods.

<Viscosity stability>

The viscosity M0 immediately after preparation of the binder composition and the viscosity M1 after storage at 60°C for 7 days were measured. On the other hand, the viscosity was measured using a B-type viscometer under conditions of temperature: 25°C, rotor: No. 4, and rotor rotation speed: 60 rpm.

Then, the viscosity change rate ΔM (= M1/M0 × 100 (%)) was calculated and evaluated according to the following criteria. The smaller the value of the viscosity change rate ΔM, the higher the viscosity stability of the binder composition.

A: Viscosity change rate ΔM is less than 110%

B: Viscosity change rate ΔM is 110% or more and less than 120%

C: Viscosity change rate ΔM is 120% or more and less than 130%

D: Viscosity change rate ΔM is 130% or more and less than 150%

E: Viscosity change rate ΔM is 150% or more

<Electrolyte swelling degree>

The binder composition in the Teflon (registered trademark) petri dish was dried at 120°C for 12 hours to obtain a film having a thickness of 1 mm. This film was blanked into a circular shape with a diameter of 1.6 mm to obtain a measurement sample (pseudo-electrode mixture layer), and the weight W0 of this measurement sample was measured.

After storing the obtained sample for measurement in an electrolyte solution at 60°C for 72 hours, the electrolyte solution adhering to the sample for measurement was wiped off, and the weight W1 of the sample for measurement was measured.

On the other hand, as the electrolyte solution, ethylene carbonate (EC), propylene carbonate (PC), ethylmethyl carbonate (EMC), and propylpropionate (PP) are EC:PC:EMC:PP = 2:1:1: 6 (mass ratio) was used in which LiPF ₆ was dissolved at a concentration of 1 mol/liter in a mixed solvent and 1.5 vol% of vinylene carbonate was added as an additive.

Then, the electrolyte solution swelling degree ΔW (= W1/W0 × 100 (%)) was calculated and evaluated according to the following criteria. It shows that the swelling of the electrode mixture layer obtained using the binder composition in the electrolyte solution can be suppressed, so that the value of electrolyte solution swelling degree (DELTA)W is small.

A: electrolyte swelling degree ΔW is less than 600%

B: electrolyte swelling degree ΔW is 600% or more and less than 800%

C: electrolyte swelling degree ΔW of 800% or more and less than 1000%

D: Electrolyte swelling degree ΔW is 1000% or more and less than 2000%

E: electrolyte swelling degree ΔW is 2000% or more

<Cycle characteristics>

With respect to the produced secondary battery, the operation of charging to 4.35 V at 0.2 C and discharging to 3.0 V in a 25°C environment was repeated three times. Thereafter, in a 45°C environment, charging was performed at 1 CmA until the battery voltage reached 4.35 V and discharged at 1 CmA until the battery voltage reached 3.0 V, and the operation was repeated 100 times. Then, the capacity retention rate ΔC = (C1/C0) x 100 (%) was calculated from the first discharge capacity (C0) and the 100th discharge capacity (C1), and evaluated according to the following criteria. The higher the value of this capacity retention rate, the smaller the decrease in discharge capacity, indicating excellent cycle characteristics.

A: The capacity retention rate ΔC is 85% or more

B: Capacity retention rate ΔC is 80% or more and less than 85%

C: Capacity retention rate ΔC is 75% or more and less than 80%

D: Capacity retention rate ΔC is 70% or more and less than 75%

E: capacity retention rate ΔC is less than 70%

(Example 1)

<Preparation of Polymer (A)>

In a metal bottle, 180 parts of ion-exchanged water, 25 parts of aqueous solution of sodium dodecylbenzenesulfonate having a concentration of 10% by mass, 5 parts of methacrylic acid as a binding functional group-containing monomer, 10 parts of acrylonitrile as a nitrile group-containing monomer, (meth) 25 parts of 2-ethylhexyl acrylate as an acrylic acid ester monomer and 0.5 part of t-dodecylmercaptan as a molecular weight modifier were sequentially introduced, and after replacing the internal gas with nitrogen three times, 1,3- as a conjugated diene monomer 60 parts of butadiene are added. The metal bottle was maintained at 5°C, 0.1 part of cumene hydroperoxide as a polymerization initiator was added, and polymerization was carried out for 16 hours while rotating the metal bottle. Subsequently, after stopping the polymerization reaction by adding 0.1 part of an aqueous solution of hydroquinone having a concentration of 10% by mass as a polymerization terminator, residual monomers are removed using a rotary evaporator at a water temperature of 60 ° C., and an aqueous dispersion of the polymer (solid content concentration of about 30% by mass) was obtained.

Then, in an autoclave, the aqueous dispersion prepared above and the palladium catalyst (1% by mass palladium acetic acid solution and ion-exchanged water were mixed so that the palladium content based on the dry weight of the polymer contained in the aqueous dispersion obtained above was 750 ppm). solution mixed in a 1:1 (mass ratio)) was added. Then, a hydrogenation reaction was performed at a hydrogen pressure of 3 MPa and a temperature of 50°C for 6 hours to obtain a hydrogenated polymer.

Subsequently, NMP as a solvent was added to the obtained aqueous dispersion of the hydrogenated polymer so that the solid content concentration of the hydrogenated polymer was 7%. Then, distillation under reduced pressure was performed at 90°C to remove water and excess NMP to obtain an NMP solution (solid content concentration: 8%) of polymer (A) (hydrogenated polymer).

<Preparation of polycationic organic compound (B)>

As a polycationic organic compound (B), polyethyleneimine (number average molecular weight: 600, "Eformin SP-006", manufactured by Nippon Catalyst Co., Ltd.) was prepared. Then, an NMP solution (solid content concentration: 8%) of this polyethyleneimine was prepared.

<Preparation of binder composition for positive electrode>

The NMP solution of the above-mentioned polymer (A) and the NMP solution of polyethyleneimine were mixed so that the mixing ratio might be set to 100:5 in terms of solid content, and the binder composition for positive electrodes was obtained. Viscosity stability and electrolyte solution swelling degree were evaluated using this binder composition for positive electrodes. The results are shown in Table 1.

<Preparation of slurry composition for positive electrode>

100 parts of lithium cobaltate (LiCoO ₂ , volume average particle diameter: 12 µm) as a positive electrode active material, and Ketjen black (manufactured by Lion Co., special oil furnace carbon powder product: number particle diameter 40 nm, specific surface area 800 m ² /g as a conductive material) ) 1.5 part, the positive electrode binder composition in an amount such that the polymer (A) is 0.6 part (in terms of solid content), 0.6 part (in terms of solid content) of an NMP solution of polyvinylidene fluoride (PVDF) as a binder, and an additional solvent A slurry composition for a positive electrode was prepared by mixing NMP as a planetary mixer. On the other hand, the amount of additional NMP is such that the viscosity of the resulting positive electrode slurry composition (using a B-type viscometer. Temperature: 25 ° C., rotor: No. 4, rotor rotation speed: 60 rpm) is within the range of 5000 ± 200 mPa s Adjusted.

<Production of positive electrode>

The obtained slurry composition for a positive electrode was applied to one side of a current collector made of an aluminum foil having a thickness of 15 μm so that the coating amount after drying was 20 mg/cm ² . Then, the applied slurry composition was dried at 90°C for 20 minutes and at 120°C for 20 minutes, and then heat treated at 150°C for 2 hours to obtain a positive electrode fabric. Then, the obtained positive electrode fabric was rolled by a roll press to obtain a positive electrode having a positive electrode composite material layer having a density of 3.7 g/cm ³ on an aluminum foil (current collector).

<Production of negative electrode>

100 parts of spherical artificial graphite (volume average particle diameter: 12 μm) as a negative electrode active material, 1 part of styrene-butadiene copolymer as a binder, 1 part of carboxymethylcellulose as a thickener, and an appropriate amount of water as a dispersion medium were mixed with a planetary mixer By mixing, the slurry composition for negative electrodes was prepared.

The obtained slurry composition for negative electrodes was applied to one side of a current collector made of copper foil with a thickness of 15 μm so that the coating amount after drying was 10 mg/cm ² . Then, the applied slurry composition was dried at 60°C for 20 minutes and at 120°C for 20 minutes to obtain a negative electrode fabric. Then, the obtained negative electrode fabric was rolled by a roll press to obtain a negative electrode having a negative electrode mixture layer having a density of 1.5 g/cm ³ on a copper foil (current collector).

<Preparation of separator>

A single-layer polypropylene separator (width 65 mm, length 500 mm, thickness 25 µm, dry method, porosity 55%) was cut out into a 4.4 cm x 4.4 cm square.

<Manufacture of secondary battery>

As an exterior of the battery, an aluminum packaging material exterior was prepared. Then, the positive electrode obtained above was cut out into a square of 4 cm × 4 cm, and the surface on the current collector side was placed in contact with the aluminum packaging material exterior. On the positive electrode mixture layer of the positive electrode, the square separator obtained above was disposed. Further, the negative electrode obtained above was cut out into a square of 4.2 cm x 4.2 cm, and this was placed on the separator so that the surface on the negative electrode mixture layer side faced the separator. Further, after filling the electrolyte solution, heat sealing was performed at 150°C to seal the opening of the aluminum packaging material exterior, and then the aluminum packaging material exterior was closed to obtain a lithium ion secondary battery. On the other hand, as the electrolyte solution, ethylene carbonate (EC), propylene carbonate (PC), ethylmethyl carbonate (EMC), and propylpropionate (PP) are EC:PC:EMC:PP = 2:1:1: 6 (mass ratio) was used in which LiPF ₆ was dissolved at a concentration of 1 mol/liter in a mixed solvent and 1.5 vol% of vinylene carbonate was added as an additive.

And evaluation of cycling characteristics was performed using the obtained lithium ion secondary battery. The results are shown in Table 1.

(Example 2, 4-15)

Polymer (A), binder composition for positive electrode, slurry composition for positive electrode, positive electrode, negative electrode, and secondary battery were produced in the same manner as in Example 1 except that the monomer composition of Table 1 was employed at the time of preparation of polymer (A). did Then, evaluation was conducted in the same manner as in Example 1. The results are shown in Table 1.

(Example 3)

When preparing the polymer (A), the monomer composition of Table 1 is employed, and when preparing the binder composition for the positive electrode, instead of the NMP solution of polyethyleneimine, N,N'-bis(3-phenyl-2-pro Phenylidene) -1,6-hexanediamine (molecular weight: 344) NMP solution (solid content concentration: 8%) was carried out in the same manner as in Example 1, except that polymer (A), positive electrode binder composition, positive electrode slurry A composition, a positive electrode, a negative electrode, and a secondary battery were prepared. Then, evaluation was conducted in the same manner as in Example 1. The results are shown in Table 1.

(Example 16, 17)

Polymer (A), binder composition for positive electrode, slurry for positive electrode in the same manner as in Example 1, except that the amount of polycationic organic compound (B) was changed as shown in Table 1 at the time of preparing the binder composition for positive electrode. A composition, a positive electrode, a negative electrode, and a secondary battery were prepared. Then, evaluation was conducted in the same manner as in Example 1. The results are shown in Table 1.

(Examples 18 and 19)

At the time of preparation of the binder composition for a positive electrode, polyethyleneimine (number average molecular weight: 1200, "Eformin SP-012", manufactured by Nippon Catalyst Co., Ltd.) or polyethyleneimine ( Number average molecular weight: 1800, polymer (A), positive electrode binder composition in the same manner as in Example 1 except that NMP solution (solid content concentration: 8%) of "Epomin SP-018", manufactured by Nippon Catalyst Co., Ltd. was used , a slurry composition for a positive electrode, a positive electrode, a negative electrode, and a secondary battery were produced. Then, evaluation was conducted in the same manner as in Example 1. The results are shown in Table 1.

(Examples 20 to 23)

When preparing the binder composition for the positive electrode, N,N'-bis(3-phenyl-2-propenylidene)-1,6-hexanediamine (molecular weight : 344), polyallylamine (number average molecular weight: 1600, "PAA-01", manufactured by Nittobo Medical), diethylenetriamine (molecular weight: 103), or NMP solution of ethylenediamine (molecular weight: 60) (solid content) Concentration 8%) was carried out similarly to Example 1, and the polymer (A), the binder composition for positive electrodes, the slurry composition for positive electrodes, the positive electrode, the negative electrode, and the secondary battery were produced. Then, evaluation was conducted in the same manner as in Example 1. The results are shown in Table 1.

(Comparative Example 1)

Polymer (A), binder composition for positive electrode, slurry composition for positive electrode, positive electrode, negative electrode in the same manner as in Example 1 except that the polycationic organic compound (B) was not used at the time of preparation of the binder composition for positive electrode. , and secondary batteries were fabricated. Then, evaluation was conducted in the same manner as in Example 1. The results are shown in Table 1.

(Comparative Example 2)

When preparing the binder composition for a positive electrode, NMP solution of polyethyleneimine (number average molecular weight: 10000, "Eformin SP-200", manufactured by Nippon Catalyst Co., Ltd.) instead of NMP solution of polyethyleneimine (number average molecular weight: 600) ( A polymer (A), a binder composition for a positive electrode, a slurry composition for a positive electrode, a positive electrode, a negative electrode, and a secondary battery were produced in the same manner as in Example 1 except that solid content concentration of 8%) was used. Then, evaluation was conducted in the same manner as in Example 1. The results are shown in Table 1.

(Comparative Example 3)

Polymer (A), binder composition for positive electrode, slurry composition for positive electrode, positive electrode, negative electrode, and secondary battery were produced in the same manner as in Example 1 except that the monomer composition of Table 1 was employed at the time of preparation of polymer (A). did Then, evaluation was conducted in the same manner as in Example 1. The results are shown in Table 1.

(Comparative Example 4)

Except for using aluminum chelate (manufactured by Kawaken Fine Chemical Co., Ltd., product name "aluminum chelate A (W)", aluminum tris (acetylacetonate)) in place of the polycationic organic compound (B) in preparation of the binder composition for the positive electrode , In the same manner as in Example 1, a polymer (A), a binder composition for a positive electrode, a slurry composition for a positive electrode, a positive electrode, a negative electrode, and a secondary battery were produced. Then, evaluation was conducted in the same manner as in Example 1. The results are shown in Table 1.

On the other hand, in Table 1 shown below,

"COOH" represents a carboxylic acid group,

"AA" represents an acrylic acid unit,

"IA" represents an itaconic acid unit,

"MAA" represents a methacrylic acid unit,

"MBM" represents a monobutyl maleate unit,

"MMA" represents a methyl methacrylate unit,

"EA" represents an ethyl acrylate unit,

"BA" represents an n-butyl acrylate unit,

"2-EHA" represents a 2-ethylhexyl acrylate unit,

"AN" represents an acrylonitrile unit,

"BD" represents a 1,3-butadiene unit or a 1,3-butadiene hydride unit;

"PEI" represents polyethyleneimine,

"NBH" represents N,N'-bis(3-phenyl-2-propenylidene)-1,6-hexanediamine,

"PAA" represents polyallylamine,

"DETA" represents diethylenetriamine,

"ED" represents ethylenediamine,

"AL" represents an aluminum chelate.

From Table 1, in Examples 1 to 23 using a binder composition containing a polymer having a binding functional group (A) and a polycationic organic compound (B) having a molecular weight of a predetermined value or less, the binder composition had excellent viscosity stability. In addition, it can be seen that a secondary battery having excellent cycle characteristics can be manufactured by obtaining a slurry composition capable of forming an electrode mixture layer in which swelling in the electrolyte solution is suppressed.

On the other hand, from Table 1, in Comparative Example 1 using a binder composition containing a polymer (A) having a binding functional group and not containing a polycationic organic compound (B) having a molecular weight of a predetermined value or less, in Comparative Example 1, the electrode mixture layer It can be seen that the swelling in the electrolyte solution cannot be sufficiently suppressed, and thus the cycle characteristics of the secondary battery deteriorate.

In addition, from Table 1, a binder composition containing a polymer (A) having a binding functional group and a polycationic organic compound (B), wherein the molecular weight of the polycationic organic compound (B) exceeds a predetermined value. In the comparative example 2 used, it turns out that the viscosity stability of the binder composition is inferior and the cycling characteristics of a secondary battery fall.

And, from Table 1, in Comparative Example 3 using a binder composition containing a polymer having no bonding functional group and a polycationic organic compound (B) having a molecular weight of a predetermined value or less, swelling of the electrode mixture layer in the electrolyte solution was It can be seen that the cycle characteristics of the secondary battery are lowered because it cannot be suppressed sufficiently.

In addition, from Table 1, in Comparative Example 4 using a binder composition containing a polymer (A) having a binding functional group and an aluminum chelate, it was found that the viscosity stability of the binder composition was poor and the cycle characteristics of the secondary battery were deteriorated. can The decrease in these performances is presumed to be due to aluminum ions derived from aluminum chelate. Specifically, it is presumed that the decrease in viscosity stability is due to the high mobility of aluminum ions in a solvent, causing a crosslinking reaction with the polymer (A) to thicken the polymer (A). In addition, the decrease in cycle characteristics is due to the temperature rise due to shear during preparation of the slurry composition, so that aluminum ions cause a crosslinking reaction with the polymer (A), and as a result, it is difficult for the polymer (A) to cover the conductive material, thereby reducing the amount of the conductive material. It is speculated that this is because acidity is damaged.

ADVANTAGE OF THE INVENTION According to this invention, the binder composition for non-aqueous secondary battery electrodes which is excellent in viscosity stability and can form the electrode mixture layer in which swelling in electrolyte solution was suppressed is obtained.

In addition, according to the present invention, it is possible to form an electrode mixture layer in which swelling in the electrolyte solution is suppressed, and also to exhibit excellent cycle characteristics in non-aqueous secondary batteries A conductive material paste composition for non-aqueous secondary battery electrodes and non-aqueous A slurry composition for secondary battery electrodes is obtained.

Further, according to the present invention, an electrode for a non-aqueous secondary battery can be obtained, which has an electrode mixture layer in which swelling in the electrolyte solution is suppressed, and which enables the non-aqueous secondary battery to exhibit excellent cycle characteristics.

And according to the present invention, a non-aqueous secondary battery having excellent cycle characteristics is obtained.

Claims (12)

A polymer having a functional group bondable to a cationic group and an organic compound having two or more cationic groups and a molecular weight of 100 or more and 1500 or less,
The polymer contains a monomer unit containing a functional group bondable to a cationic group and a nitrile group-containing monomer unit, and contains at least one of a conjugated diene monomer unit and an alkylene structural unit,
The proportion of monomer units containing functional groups capable of bonding with the cationic group in the polymer is 0.1% by mass or more and 6% by mass or less, and the proportion of monomer units containing a nitrile group in the polymer is 5% by mass or more and 29% by mass or less, The sum of the ratio of the conjugated diene monomeric unit and the ratio of the alkylene structural unit in the polymer is 30% by mass or more and 90% by mass or less, and
The binder composition for non-aqueous secondary battery electrodes containing 2 parts by mass or more and 6 parts by mass or less of the organic compound per 100 parts by mass of the polymer. According to claim 1,
The binder composition for non-aqueous secondary battery electrodes, wherein the functional group bondable to the cationic group is at least one selected from the group consisting of a carboxylic acid group, a sulfonic acid group, a phosphoric acid group, and a hydroxyl group. A conductive material paste composition for nonaqueous secondary battery electrodes comprising a conductive material and the binder composition for nonaqueous secondary battery electrodes according to claim 1 or 2. The slurry composition for nonaqueous secondary battery electrodes containing an electrode active material and the binder composition for nonaqueous secondary battery electrodes of Claim 1 or 2. An electrode for nonaqueous secondary batteries provided with an electrode mixture layer formed using the slurry composition for nonaqueous secondary battery electrodes according to claim 4. A positive electrode, a negative electrode, an electrolyte solution and a separator are provided,
A nonaqueous secondary battery, wherein at least one of the positive electrode and the negative electrode is the electrode for a nonaqueous secondary battery according to claim 5. The slurry composition for nonaqueous secondary battery electrodes containing an electrode active material and the electrically conductive material paste composition for nonaqueous secondary battery electrodes of Claim 3. An electrode for non-aqueous secondary batteries provided with an electrode mixture layer formed using the slurry composition for non-aqueous secondary battery electrodes according to claim 7. A positive electrode, a negative electrode, an electrolyte solution and a separator are provided,
A nonaqueous secondary battery, wherein at least one of the positive electrode and the negative electrode is the electrode for a nonaqueous secondary battery according to claim 8. delete delete delete