JP2017157481A - Binder composition for nonaqueous secondary battery electrode and manufacturing method thereof, slurry composition for nonaqueous secondary battery electrode, nonaqueous secondary battery electrode, and nonaqueous secondary battery - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a binder composition for a nonaqueous secondary battery electrode, which is superior in conductive material dispersibility, and which enables the formation of an electrode mixture material layer superior in peel strength.SOLUTION: A binder composition for a nonaqueous secondary battery electrode comprises a polymer, and an organic solvent. In the polymer, a tetrahydrofuran insoluble content is 3-50 mass%. The content of amide groups in the polymer is 0.01-1.0 mmol/g, and the content of acid groups in the polymer is 0-1.0 mmol/g.SELECTED DRAWING: None

Description

  The present invention relates to a binder composition for non-aqueous secondary battery electrodes, a method for producing a binder composition for non-aqueous secondary battery electrodes, a slurry composition for non-aqueous secondary battery electrodes, a non-aqueous secondary battery electrode, and a non-aqueous system. The present invention relates to a secondary battery.

  Non-aqueous secondary batteries such as lithium ion secondary batteries (hereinafter sometimes simply referred to as “secondary batteries”) have the characteristics of being small and lightweight, having high energy density, and capable of repeated charge and discharge. Yes, 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 improving the performance of non-aqueous secondary batteries.

  Here, an electrode used in a secondary battery such as a lithium ion secondary battery is usually a current collector and an electrode mixture layer (a positive electrode mixture layer or a negative electrode mixture layer) formed on the current collector. It has. And this electrode compound material layer apply | coats the slurry composition containing an electrode active material, the binder composition containing a binder, etc. on a collector, for example, and dries the apply | coated slurry composition. It is formed.

Thus, in recent years, attempts have been made to improve the binder composition used for forming the electrode mixture layer in order to achieve further improvement in the performance of the secondary battery.
Specifically, for example, in Patent Document 1, a block unit composed of polyvinylpyrrolidone, an α, β-unsaturated carboxylic acid and a derivative thereof, an α, β-unsaturated ketone, an unsaturated hydrocarbon compound, a cyano group-containing unsaturated compound. A block unit obtained by polymerizing one or more selected from hydrocarbon compounds, vinyl ether compounds, vinyl ester compounds, unsaturated alcohol compounds, aromatic alkenyl compounds, and N-vinylamine compounds having 7 or more carbon atoms; By using a copolymer having a binder as the binder, the binding property and the electrolytic solution resistance of the binder are improved, and the charge / discharge characteristics of the secondary battery are improved.

Japanese Patent Laying-Open No. 2015-149177

  Here, a conductive material may be blended in the electrode mixture layer of the secondary battery in order to satisfactorily form a conductive path in the electrode mixture layer. From the viewpoint of improving the performance of the secondary battery by favorably forming the electrode mixture layer on the current collector, the slurry composition used for forming the electrode mixture layer containing the conductive material includes a conductive material. Is favorably dispersed, and the adhesion strength (peel strength) between the electrode mixture layer to be formed and the current collector is required to be increased.

  However, in the slurry composition using the binder composed of the conventional copolymer, the conductive material cannot be dispersed well while ensuring the peel strength of the electrode mixture layer to be formed.

Therefore, the present invention provides a binder composition for a non-aqueous secondary battery electrode and a slurry composition for a non-aqueous secondary battery electrode that can form an electrode mixture layer that is excellent in dispersibility of a conductive material and excellent in peel strength. The purpose is to provide.
Another object of the present invention is to provide an electrode for a non-aqueous secondary battery that has excellent peel strength and can exhibit excellent rate characteristics and cycle characteristics for a non-aqueous secondary battery.
Furthermore, an object of the present invention is to provide a nonaqueous secondary battery having excellent rate characteristics and cycle characteristics.

  The present inventor has intensively studied for the purpose of solving the above problems. The present inventor has found that a binder composition containing a polymer having a predetermined property and an organic solvent such as N-methylpyrrolidone has excellent dispersibility of the conductive material and excellent peel strength. The present inventors have found that a material layer can be formed and completed the present invention.

That is, the present invention aims to advantageously solve the above problems, and the binder composition for a non-aqueous secondary battery electrode of the present invention comprises a non-aqueous secondary battery containing a polymer and an organic solvent. A binder composition for a battery electrode, wherein the polymer has a tetrahydrofuran insoluble content of 3% by mass or more and 50% by mass or less, and the amount of amide groups in the polymer is 0.01 mmol / g or more and 1.0 mmol. / G or less, and the amount of acid groups in the polymer is 0 mmol / g or more and 1.0 mmol / g or less. Thus, the binder composition containing the polymer in which the tetrahydrofuran (THF) insoluble amount, the amount of amide groups and the amount of acid groups are within the above ranges and the organic solvent is excellent in the dispersibility of the conductive material. At the same time, an electrode mixture layer having excellent peel strength can be formed.
In the present invention, “amount of tetrahydrofuran insoluble in polymer”, “amount of amide group in polymer” and “amount of acid group in polymer” are the same as those described in the examples of this specification. It can be obtained using.

  Moreover, this invention aims at solving the said subject advantageously, The manufacturing method of the binder composition for non-aqueous secondary battery electrodes of this invention is the binder for non-aqueous secondary battery electrodes mentioned above. A method for producing a composition comprising an acid group-containing polymer containing an acid group-containing monomer unit in a proportion of 0.5% by mass or more and 10% by mass or less, and a primary amine and a secondary amine. And mixing with an amine compound selected from the group to prepare the polymer. Thus, when an acid group-containing polymer containing a predetermined amount of an acid group-containing monomer unit and a predetermined amine compound are mixed, the amount of insoluble tetrahydrofuran, the amount of amide groups, and the amount of acid groups are within a predetermined range. The polymer inside can be easily prepared. Therefore, a binder composition for a nonaqueous secondary battery electrode capable of forming an electrode mixture layer having excellent dispersibility of the conductive material and excellent peel strength can be easily obtained.

  Here, in the method for producing a binder composition for a non-aqueous secondary battery electrode according to the present invention, the acid group-containing monomer unit is preferably a monomer unit having a carboxylic acid group. If the acid group-containing monomer unit is a monomer unit having a carboxylic acid group, the polymer is prepared well, and the dispersibility of the conductive material and the electrode mixture layer formed using the binder composition Peel strength can be further improved.

  Moreover, it is preferable that the said amine compound is a monoamine compound in the manufacturing method of the binder composition for non-aqueous secondary battery electrodes of this invention. If the amine compound is a monoamine compound, the polymer can be prepared satisfactorily to further improve the dispersibility of the conductive material and the peel strength of the electrode mixture layer formed using the binder composition.

  And in the manufacturing method of the binder composition for non-aqueous secondary battery electrodes of this invention, it is preferable that the said monoamine compound is a primary amine. If the monoamine compound is a primary amine, the polymer can be prepared more satisfactorily, and the dispersibility of the conductive material and the peel strength of the electrode mixture layer formed using the binder composition can be further improved. it can.

  Furthermore, in the method for producing a binder composition for a non-aqueous secondary battery electrode according to the present invention, the amine compound is added in an amount of 0.01 parts by mass or more and 5.0 parts by mass or less per 100 parts by mass of the acid group-containing polymer. It is preferable to mix. If the amount of the amine compound to be mixed with the acid group-containing polymer is within the above range, the polymer is well prepared, and the dispersibility of the conductive material and the peel of the electrode mixture layer formed using the binder composition The strength can be further improved.

  Moreover, this invention aims at solving the said subject advantageously, The slurry composition for non-aqueous secondary battery electrodes of this invention is an electrode active material, a conductive material, and the non-aqueous system mentioned above. And a binder composition for a secondary battery electrode. Thus, if the binder composition for non-aqueous secondary battery electrodes described above is used, the non-aqueous secondary battery in which the conductive material is well dispersed and an electrode mixture layer having excellent peel strength can be formed. A slurry composition for an electrode is obtained.

  Here, it is preferable that the slurry composition for non-aqueous secondary battery electrodes of the present invention further contains a fluorine-containing polymer. If a fluorine-containing polymer is further contained, the peel strength of the electrode mixture layer formed using the slurry composition for non-aqueous secondary battery electrodes can be further increased.

  And the slurry composition for non-aqueous secondary battery electrodes of the present invention is such that the ratio of the content of the polymer to the total content of the polymer and the fluorine-containing polymer is 5% by mass or more and 95% by mass or less. Preferably there is. When the ratio of the polymer is within the above range when the fluorine-containing polymer is used in combination with the binder composition for a non-aqueous secondary battery electrode containing a polymer, the dispersibility of the conductive material is improved, and the non-aqueous secondary battery An improvement in peel strength of the electrode mixture layer formed using the electrode slurry composition can be satisfactorily achieved.

  Moreover, this invention aims at solving the said subject advantageously, The electrode for non-aqueous secondary batteries of this invention is formed using the slurry composition for non-aqueous secondary battery electrodes mentioned above. It is characterized by including the electrode mixture layer which carried out. Thus, if the slurry composition for non-aqueous secondary battery electrodes described above is used, the electrode composite material layer has excellent peel strength and exhibits excellent rate characteristics and cycle characteristics for the non-aqueous secondary battery. Can be obtained.

  Furthermore, this invention aims to solve the above-mentioned problem advantageously, and the non-aqueous secondary battery of the present invention is a non-aqueous secondary battery comprising a positive electrode, a negative electrode, a separator and an electrolytic solution. In addition, at least one of the positive electrode and the negative electrode is the electrode for a non-aqueous secondary battery described above. Thus, if the electrode for non-aqueous secondary batteries described above is used as at least one of the positive electrode and the negative electrode, a non-aqueous secondary battery having excellent rate characteristics and cycle characteristics can be obtained.

According to the present invention, there are provided a binder composition for a non-aqueous secondary battery electrode and a slurry composition for a non-aqueous secondary battery electrode that can form an electrode mixture layer that is excellent in dispersibility of a conductive material and excellent in peel strength. can get.
In addition, according to the present invention, there can be obtained a non-aqueous secondary battery electrode that is excellent in peel strength and capable of exhibiting excellent rate characteristics and cycle characteristics in a non-aqueous secondary battery.
Furthermore, according to the present invention, a nonaqueous secondary battery having excellent rate characteristics and cycle characteristics can be obtained.

Hereinafter, embodiments of the present invention will be described in detail.
Here, the binder composition for non-aqueous secondary battery electrodes of the present invention can be used when preparing a slurry composition for non-aqueous secondary battery electrodes, and is not particularly limited. It can manufacture using the manufacturing method of the binder composition for water based secondary battery electrodes. And the slurry composition for non-aqueous secondary battery electrodes prepared using the binder composition for non-aqueous secondary battery electrodes of the present invention is used for producing electrodes for non-aqueous secondary batteries such as lithium ion secondary batteries. Can be used. Furthermore, the non-aqueous secondary battery of the present invention is characterized by using the non-aqueous secondary battery electrode of the present invention formed using the slurry composition for a non-aqueous secondary battery electrode of the present invention.

(Binder composition for non-aqueous secondary battery electrode)
The binder composition for a non-aqueous secondary battery electrode of the present invention has a tetrahydrofuran insoluble content (hereinafter sometimes referred to as “THF insoluble content”) of 3% by mass to 50% by mass, A polymer having an amount of 0.01 mmol / g to 1.0 mmol / g and an acid group content of 0 mmol / g to 1.0 mmol / g, and an organic solvent. .

The binder composition for a non-aqueous secondary battery electrode of the present invention contains a polymer in which the THF-insoluble content, the amount of amide groups, and the amount of acid groups are within a predetermined range. When used for the preparation of the slurry composition for battery electrodes, it is possible to disperse the conductive material satisfactorily and to form an electrode mixture layer having excellent peel strength.
The reason why a binder composition for a non-aqueous secondary battery electrode capable of forming an electrode mixture layer having excellent dispersibility of the conductive material and excellent peel strength is not clear, but is as follows. It is guessed. That is, in the binder composition of the present invention, a polymer having an acid group amount of not more than the above upper limit value and an amide group amount of not less than the above lower limit value is used. Adsorption can be promoted and the dispersibility of the conductive material can be improved. In the binder composition of the present invention, since the polymer having a THF-insoluble content equal to or higher than the lower limit is used, the strength of the polymer can be secured and the peel strength of the electrode mixture layer can be increased. . Furthermore, in the binder composition of the present invention, a polymer having a THF-insoluble content below the upper limit and an amide group amount below the upper limit is used. It is possible to suppress the decrease in solubility and to form a homogeneous electrode mixture layer, thereby increasing the peel strength of the electrode mixture layer.

<Polymer>
The polymer of the binder composition for non-aqueous secondary battery electrodes has a THF insoluble content of 3% by mass to 50% by mass and an amide group content of 0.01 mmol / g to 1.0 mmol / g. In addition, any polymer can be used as long as the amount of acid groups is 0 mmol / g or more and 1.0 mmol / g or less. And a polymer functions as a binder in the electrode compound-material layer formed using the slurry composition containing a binder composition.

[THF insoluble content]
Here, the THF-insoluble content of the polymer needs to be 3% by mass or more and 50% by mass or less, preferably 5% by mass or more, more preferably 8% by mass or more, It is preferable that it is mass% or less, and it is more preferable that it is 15 mass% or less. If THF insoluble content is more than the said lower limit, the intensity | strength of a polymer can be ensured and the peel strength of an electrode compound-material layer can be raised. Moreover, if the THF-insoluble amount is not more than the above upper limit value, it is possible to suppress the decrease in the solubility of the polymer in the organic solvent and to form a homogeneous electrode mixture layer, and to peel the electrode mixture layer. Can be increased. Therefore, if the THF-insoluble content is within the above range, an electrode having excellent strength can be formed, and a secondary battery having excellent cycle characteristics can be obtained. Further, if the THF-insoluble content is not more than the above upper limit value, the affinity of the polymer for the electrolytic solution can be improved, and a secondary battery excellent in rate characteristics can be obtained.
The THF-insoluble content of the polymer can be adjusted, for example, by changing the polymer composition and preparation conditions.

[Amido group]
Further, the amount of the amide group contained in the polymer needs to be 0.01 mmol / g or more and 1.0 mmol / g or less, preferably 0.05 mmol / g or more, preferably 0.1 mmol / g. More preferably, it is 0.7 mmol / g or less, and more preferably 0.3 mmol / g or less. When the amount of the amide group is not less than the above lower limit, the dispersibility of the conductive material can be improved in the slurry composition for a non-aqueous secondary battery electrode prepared using the binder composition. Therefore, it is possible to obtain a secondary battery having excellent rate characteristics and cycle characteristics by forming an electrode mixture layer in which conductive paths are well formed. Moreover, if the quantity of an amide group is below the said upper limit, the peel strength of an electrode compound-material layer can be raised. Therefore, an electrode having excellent strength can be formed, and a secondary battery having excellent cycle characteristics can be obtained.
The amount of amide group in the polymer can be adjusted, for example, by changing the composition and preparation conditions of the polymer.

[Acid group]
Furthermore, the amount of the acid group optionally contained in the polymer needs to be 0 mmol / g or more and 1.0 mmol / g or less, preferably 0.01 mmol / g or more, and 0.05 mmol / g. More preferably, it is 0.9 mmol / g or less, and more preferably 0.8 mol / g or less. If the amount of acid groups is not more than the above upper limit, the dispersibility of the conductive material can be improved in the slurry composition for non-aqueous secondary battery electrodes prepared using the binder composition. Therefore, it is possible to obtain a secondary battery having excellent rate characteristics and cycle characteristics by forming an electrode mixture layer in which conductive paths are well formed. Moreover, when a polymer contains an acid group, if the quantity of an acid group is more than the said lower limit, the peel strength of an electrode compound-material layer can be raised. Therefore, an electrode having excellent strength can be formed, and a secondary battery having excellent cycle characteristics can be obtained.
The amount of acid groups in the polymer can be adjusted, for example, by changing the polymer composition and preparation conditions.

[Preparation of polymer]
Here, the polymer having the above-described properties is not particularly limited, and can be prepared, for example, using the following preparation method (1) or (2).
(1) An acid group-containing polymer containing an acid group-containing monomer unit and an amine compound selected from the group consisting of a primary amine and a secondary amine are mixed, and the acid group-containing polymer is a molecule. A method for preparing a polymer containing a modified polymer having an amide group by modifying a part or all of the acid groups contained therein with an amine compound.
(2) A method for preparing a polymer by polymerizing a monomer composition containing a monomer having an amide group such as acrylamide and methacrylamide, and optionally further containing a monomer having an acid group.

  Among these, from the viewpoint of ease of adjustment of the THF-insoluble content, the amount of amide groups, and the amount of acid groups of the polymer to be prepared, the polymer is preferably prepared using the preparation method (1). Therefore, hereinafter, the polymer preparation method (1) will be described in detail.

[[Preparation method (1)]]
Preparation method (1) comprises mixing an acid group-containing polymer containing an acid group-containing monomer unit with an amine compound selected from the group consisting of primary amines and secondary amines, A step (modification step) of preparing a polymer containing the union. The modified polymer obtained by reacting the acid group of the acid group-containing polymer with the amine compound in the preparation method (1) is the kind of acid group that the acid group-containing polymer had (that is, the amine compound). Depending on the type of acid group modified in (1), it has an amide group such as a carboxylic acid amide group, a sulfonamide group, or a phosphoric acid amide group. Therefore, the polymer including the modified polymer contains at least an amide group, and optionally further contains an unmodified acid group that has not reacted with the amine compound.

  In addition, the amount of the amide group and the acid group in the polymer prepared by using the preparation method (1) is the acid group-containing monomer unit contained in the acid group-containing polymer mixed with the amine compound. It can be prepared by changing the amount, the amount of the amine compound mixed with the acid group-containing polymer, the mixing conditions of the acid group-containing polymer and the amine compound, and the like. Specifically, for example, if the amount of the amine compound mixed with the acid group-containing polymer is increased, the amount of amide groups in the polymer is increased and the amount of acid groups is decreased. For example, if the temperature at which the acid group-containing polymer and the amine compound are mixed is increased, the amount of amide groups in the polymer increases and the amount of acid groups decreases.

-Denaturation process-
Here, in the modification step, an acid group-containing polymer containing an acid group-containing monomer unit and an amine compound selected from the group consisting of a primary amine and a secondary amine are mixed to produce a modified polymer. A polymer containing the coalesced is prepared. Specifically, in the modification step, part or all of the acid groups contained in the molecule of the acid group-containing polymer are modified with an amine compound to prepare a polymer containing a modified polymer having an amide group.
The polymer obtained in the modification step may be composed only of a modified polymer or a mixture of a modified polymer and an unmodified acid group-containing polymer. That is, in the modification step, the total amount of the acid group-containing polymer mixed with the amine compound may be modified with the amine compound, or only a part of the acid group-containing polymer mixed with the amine compound may be modified with the amine compound. Also good.

-Acid group-containing polymer-
As the acid group-containing polymer, any polymer containing an acid group-containing monomer unit can be used. Specifically, as the acid group-containing polymer, a polymer containing an acid group-containing monomer unit and a repeating unit other than the acid group-containing monomer unit can be used.

Acid group-containing monomer unit Here, the acid group-containing monomer capable of forming an acid group-containing monomer unit is a monomer having an acid group, for example, a monomer having a carboxylic acid group, Examples thereof include a monomer having a sulfonic acid group and a monomer having a phosphoric acid group.

And as a monomer which has carboxylic acid group, monocarboxylic acid and its derivative (s), dicarboxylic acid, its acid anhydride, those derivatives, etc. are mentioned.
Examples of monocarboxylic acids include acrylic acid, methacrylic acid, and crotonic acid.
Examples of monocarboxylic acid derivatives include 2-ethylacrylic acid, isocrotonic acid, α-acetoxyacrylic acid, β-trans-aryloxyacrylic acid, α-chloro-β-E-methoxyacrylic acid, β-diaminoacrylic acid, and the like. Can be mentioned.
Examples of the dicarboxylic acid include maleic acid, fumaric acid, itaconic acid and the like.
Dicarboxylic acid derivatives include methylmaleic acid, dimethylmaleic acid, phenylmaleic acid, chloromaleic acid, dichloromaleic acid, fluoromaleic acid, nonyl maleate, decyl maleate, dodecyl maleate, octadecyl maleate, fluoro maleate And maleic acid monoesters such as alkyl.
Examples of the acid anhydride of dicarboxylic acid include maleic anhydride, acrylic anhydride, methyl maleic anhydride, and dimethyl maleic anhydride.
Moreover, as a monomer which has a carboxylic acid group, the acid anhydride which produces | generates a carboxyl group by hydrolysis can also be used.

Examples of the monomer having a sulfonic acid group include vinyl sulfonic acid, methyl vinyl sulfonic acid, (meth) allyl sulfonic acid, and 3-allyloxy-2-hydroxypropane sulfonic acid.
In the present invention, “(meth) allyl” means allyl and / or methallyl.

Furthermore, examples of the monomer having a phosphate group include phosphoric acid-2- (meth) acryloyloxyethyl phosphate, methyl-2- (meth) acryloyloxyethyl phosphate, and ethyl phosphate- (meth) acryloyloxyethyl phosphate. Etc.
In the present invention, “(meth) acryloyl” means acryloyl and / or methacryloyl.

Among these, from the viewpoint of forming the modified polymer well and further improving the dispersibility of the conductive material and the peel strength of the electrode mixture layer formed using the binder composition, an acid group-containing monomer Is preferably a monomer having a carboxylic acid group, more preferably a monocarboxylic acid, and still more preferably itaconic acid and (meth) acrylic acid. That is, the acid group-containing monomer unit is preferably a monomer unit having a carboxylic acid group, more preferably a monocarboxylic acid unit, and an itaconic acid unit or a (meth) acrylic acid unit. Is more preferable. In the present invention, “(meth) acryl” means acryl and / or methacryl.
Moreover, an acid group containing monomer may be used individually by 1 type, and may be used combining two or more types by arbitrary ratios.

  The ratio of the acid group-containing monomer unit contained in the acid group-containing polymer is preferably 0.5% by mass or more, more preferably 1.0% by mass or more, and 1.5% by mass. % Or more, more preferably 10% by mass or less, more preferably 9% by mass or less, and still more preferably 8% by mass or less. If the ratio of the acid group-containing monomer unit contained in the acid group-containing polymer is not more than the above upper limit, the dispersion of the conductive material in the slurry composition for non-aqueous secondary battery electrodes prepared using the binder composition Can be sufficiently improved. Therefore, it is possible to obtain a secondary battery having excellent rate characteristics and cycle characteristics by forming an electrode mixture layer in which conductive paths are well formed. Moreover, if the ratio of the acid group containing monomer unit which an acid group containing polymer contains is more than the said lower limit, the peel strength of an electrode compound-material layer can be raised. Therefore, an electrode having excellent strength can be formed, and a secondary battery having excellent cycle characteristics can be obtained.

Repeating units other than acid group-containing monomer units The repeating units other than acid group-containing monomer units that can be contained in the acid group-containing polymer are not particularly limited, and are conjugated diene monomer units. , Alkylene structural units, nitrile group-containing monomer units, (meth) acrylic acid ester monomer units, aromatic vinyl monomer units, and the like.
The acid group-containing polymer may contain an amide group-containing monomer unit derived from a monomer having an amide group such as (meth) acrylamide as a repeating unit other than the acid group-containing monomer unit. Suppresses an increase in the amount of insoluble THF in a polymer including an acid group-containing polymer and a modified polymer prepared by using an acid group-containing polymer due to crosslinking of an acid group and an amide group during polymerization. From the viewpoint, the acid group-containing polymer preferably does not contain an amide group-containing monomer unit.

  Here, examples of the conjugated diene monomer capable of forming a conjugated diene monomer unit include 1,3-butadiene, isoprene, 2,3-dimethyl-1,3-butadiene, and 1,3-pentadiene. Examples thereof include conjugated diene compounds having 4 or more carbon atoms. Of these, 1,3-butadiene is preferred.

The alkylene structural unit is a repeating unit composed only of an alkylene structure represented by the general formula: —C _n H _2n — [where n is an integer of 2 or more].
Here, although the alkylene structural unit may be linear or branched, the viewpoint of improving the dispersion stability of the slurry composition for non-aqueous secondary battery electrodes prepared using the binder composition Therefore, the alkylene structural unit is preferably a straight chain, that is, a linear alkylene structural unit. Further, from the viewpoint of further improving the dispersion stability of the slurry composition for a non-aqueous secondary battery electrode prepared using the binder composition, the alkylene structural unit has 4 or more carbon atoms (that is, the above general formula n is preferably an integer of 4 or more.

The method for introducing the alkylene structural unit into the acid group-containing polymer is not particularly limited. For example, the following method (A) or (B):
(A) 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 hydrogenating the copolymer (B) And a method of preparing a copolymer from a monomer composition containing a 1-olefin monomer. Among these, the method (A) is preferable because the production of the acid group-containing polymer is easy.

In addition, as the conjugated diene monomer used in the method (A), 1,3-butadiene, isoprene, 2,3-dimethyl-1,3-butadiene, 1,3-pentadiene and the like having 4 or more carbon atoms. Examples thereof include conjugated diene compounds, and among these, 1,3-butadiene is preferable. That is, the alkylene structural unit is preferably a structural unit obtained by hydrogenating a conjugated diene monomer unit (conjugated diene hydride unit), and a structural unit obtained by hydrogenating a 1,3-butadiene unit (1 , 3-butadiene hydride unit). The selective hydrogenation of the conjugated diene monomer unit can be performed using a known method such as an oil layer hydrogenation method or an aqueous layer hydrogenation method.
Examples of the 1-olefin monomer used in the method (B) include ethylene, propylene, 1-butene, 1-hexene and the like.
These conjugated diene monomers and 1-olefin monomers can be used alone or in combination of two or more.

Further, examples of the nitrile group-containing monomer that can form a nitrile group-containing monomer unit include α, β-ethylenically unsaturated nitrile monomers. 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. For example, acrylonitrile; α-chloroacrylonitrile, α-halogenoacrylonitrile such as α-bromoacrylonitrile; α-alkylacrylonitrile such as methacrylonitrile and α-ethylacrylonitrile; and the like. Among these, as the nitrile group-containing monomer, acrylonitrile and methacrylonitrile are preferable, and acrylonitrile is more preferable.
These can be used alone or in combination of two or more.

Examples of the (meth) acrylate monomer that can form a (meth) acrylate monomer unit include methyl acrylate, ethyl acrylate, n-propyl acrylate, isopropyl acrylate, n-butyl acrylate, and t-butyl. Alkyl acrylates such as acrylate, isobutyl acrylate, n-pentyl acrylate, isopentyl acrylate, hexyl acrylate, heptyl acrylate, octyl acrylate, 2-ethylhexyl acrylate, nonyl acrylate, decyl acrylate, lauryl acrylate, n-tetradecyl acrylate, stearyl acrylate Esters; methyl methacrylate, ethyl methacrylate, n-propyl methacrylate, isopropyl methacrylate, n-buty 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, stearyl methacrylate Methacrylic acid alkyl esters such as; Among these, methyl acrylate, ethyl acrylate, n-butyl acrylate, 2-ethylhexyl acrylate, methyl methacrylate, ethyl methacrylate, n-butyl methacrylate, and 2-ethylhexyl methacrylate are preferable, and 2-ethylhexyl acrylate is more preferable.
These can be used alone or in combination of two or more.

Furthermore, examples of the aromatic vinyl monomer that can form an aromatic vinyl monomer unit include styrene, α-methylstyrene, butoxystyrene, and vinylnaphthalene. Of these, styrene is preferred.
These can be used alone or in combination of two or more.

  Among the above, the repeating unit other than the acid group-containing monomer unit preferably includes a nitrile group-containing monomer unit, more preferably includes a nitrile group-containing monomer unit and an alkylene structural unit, and an acrylonitrile unit. And more preferably 1,3-butadiene hydride units. That is, the acid group-containing polymer is preferably a hydrogenated acrylonitrile butadiene copolymer obtained by hydrogenating an acrylonitrile butadiene copolymer having a predetermined amount of acid group-containing monomer units.

  When the repeating unit other than the acid group-containing monomer unit includes a nitrile group-containing monomer unit, the ratio of the nitrile group-containing monomer unit contained in the acid group-containing polymer is 5% by mass or more. It is preferably 10% by mass or more, more preferably 90% by mass or less, and even more preferably 85% by mass or less. If the ratio of the nitrile group-containing monomer unit contained in the acid group-containing polymer is not less than the above lower limit value, the strength of the acid group-containing polymer can be increased, so the electrode composition formed using the binder composition. The peel strength of the material layer can be increased. Therefore, an electrode having excellent strength can be formed, and a secondary battery having excellent cycle characteristics can be obtained. In addition, if the ratio of the nitrile group-containing monomer unit contained in the acid group-containing polymer is not more than the above upper limit value, the polymer containing the acid group-containing polymer and the polymer containing the modified polymer prepared using the acid group-containing polymer is contained. The increase in the amount of THF-insoluble matter in the coalescence can be suppressed, and the dispersibility of the conductive material can be sufficiently improved in the slurry composition for a non-aqueous secondary battery electrode prepared using the binder composition. Therefore, it is possible to obtain a secondary battery having excellent rate characteristics and cycle characteristics by forming an electrode mixture layer in which conductive paths are well formed.

-Preparation method of acid group-containing polymer The method for preparing the acid group-containing polymer described above is not particularly limited. For example, the acid group-containing polymer is obtained by polymerizing a monomer composition containing the above-described monomer. After obtaining the copolymer, it can be prepared by hydrogenating (hydrogenating) the obtained copolymer as required.

Here, the content ratio of each monomer in the monomer composition used for the preparation of the acid group-containing polymer can be determined according to the content ratio of each repeating unit in the acid group-containing polymer.
The polymerization mode is not particularly limited, and any method such as a solution polymerization method, a suspension polymerization method, a bulk polymerization method, and an emulsion polymerization method can be used. As the polymerization reaction, any reaction such as ionic polymerization, radical polymerization, and living radical polymerization can be used.
Furthermore, the hydrogenation method of the copolymer is not particularly limited, and is a general method using a catalyst (see, for example, International Publication No. 2012/165120, International Publication No. 2013/088099 and JP2013-8485A). Can be used.

~ Amine compound ~
As the amine compound mixed with the acid group-containing polymer, a primary amine and / or a secondary amine can be used.
Here, the primary amine is not particularly limited, and examples thereof include methylamine, ethylamine, n-propylamine, 1-ethylpropylamine, n-butylamine, sec-butylamine, tert-butylamine, hexylamine, Primary monoamines such as heptylamine, octylamine, 2-octylamine, cyclohexylamine, benzylamine and aniline; primary polyamines such as hexamethylenediamine, heptamethylenediamine, octamethylenediamine, nonamethylenediamine and decamethylenediamine And the like.
The secondary amine is not particularly limited, and examples thereof include dimethylamine, diethylamine, dipropylamine, N-ethylbutylamine, dipentylamine, dihexylamine, N-methylhexylamine, and N-ethylbenzylamine. N, N′-dimethylethylenediamine, N, N′-diethylethylenediamine, N, N′-dibutylethylenediamine, N, N′-dimethylpropylenediamine, N, N′-diethylpropylenediamine, N, Secondary polyamines such as N′-dibutylpropylenediamine; and the like.

Among the above-described compounds, the amine compound is preferably a monoamine compound selected from the group consisting of a primary monoamine and a secondary monoamine, and more preferably a primary monoamine.
If a monoamine compound is used as the amine compound, the acid group-containing polymer can be prevented from cross-linking with each other via the amine compound, so that the polymer obtained by mixing the acid group-containing polymer and the amine compound An increase in the amount of THF-insoluble matter can be suppressed. Accordingly, it is possible to further increase the peel strength of the electrode mixture layer by making it possible to form a homogeneous electrode mixture layer while enhancing the dispersibility of the conductive material. In addition, when a primary monoamine is used as the amine compound, the acid group-containing polymer is well modified with the amine compound to further improve the dispersibility of the conductive material, and an electrode formed using the binder composition The peel strength of the composite material layer can be further improved.
From the standpoint of further modifying the acid group-containing polymer with an amine compound to further improve the dispersibility of the conductive material and the peel strength of the electrode mixture layer formed using the binder composition, The primary monoamine is preferably a monoamine in which a saturated aliphatic hydrocarbon group having 3 to 20 carbon atoms is bonded to a nitrogen atom and a monoamine in which an aromatic hydrocarbon group is bonded to a nitrogen atom, N-hexylamine is more preferable.

  The amount of the amine compound mixed with the acid group-containing polymer is preferably 0.01 parts by mass or more and more preferably 0.1 parts by mass or more per 100 parts by mass of the acid group-containing polymer. 0.5 parts by mass or more, more preferably 5.0 parts by mass or less, more preferably 4.0 parts by mass or less, and further preferably 3.5 parts by mass or less. preferable. If the amount of the amine compound mixed with the acid group-containing polymer is set to the above lower limit or more, the acid group-containing polymer can be sufficiently modified to further improve the dispersibility of the conductive material. Further, if the amount of the amine compound mixed with the acid group-containing polymer is set to the above upper limit or less, the amount of THF-insoluble matter in the polymer obtained by mixing the acid group-containing polymer and the amine compound increases. It can suppress and can form a homogeneous electrode compound-material layer, and can further raise the peel strength of an electrode compound-material layer.

~mixture~
In the modification step, the above-described mixing of the acid group-containing polymer and the amine compound is not particularly limited and can be performed using a known stirring device such as a disper. In the modification step, the acid group-containing polymer and the amine compound are mixed to react the acid group of the acid group-containing polymer with the amine compound, so that the carboxylic acid amide group, the sulfonamide group, the phosphoric acid amide group A polymer containing a modified polymer having an amide group such as is obtained. Note that the mixing may be performed in an organic solvent or in water.

  Here, from the viewpoint of the reactivity between the acid group-containing polymer and the amine compound and the ease of production of the binder composition, the mixing of the acid group-containing polymer and the amine compound is preferably performed in an organic solvent. In addition, as an organic solvent, it is preferable to use the organic solvent mentioned later, ie, the organic solvent which will be contained in the binder composition prepared. When an acid group-containing polymer prepared in water using an emulsion polymerization method or the like is used, the water used for preparing the acid group-containing polymer may be removed before mixing with the organic solvent. Alternatively, the aqueous dispersion of the acid group-containing polymer and the organic solvent may be mixed and then removed by evaporating the water.

The temperature at which the acid group-containing polymer and the amine compound are mixed is not particularly limited as long as the acid group of the acid group-containing polymer can be reacted with the amine compound, but the acid group and the amine compound are good. From the viewpoint of reacting, for example, it is preferably 80 ° C. or higher, more preferably 100 ° C. or higher, preferably 200 ° C. or lower, and more preferably 150 ° C. or lower.
Furthermore, the time for mixing the acid group-containing polymer and the amine compound is not particularly limited as long as the acid group of the acid group-containing polymer and the amine compound can be sufficiently reacted. Is preferably 5 hours or longer, more preferably 12 hours or shorter, and even more preferably 10 hours or shorter.

<Organic solvent>
In addition, the organic solvent of the binder composition for non-aqueous secondary battery electrodes is not particularly limited. For example, methanol, ethanol, n-propanol, isopropanol, n-butanol, isobutanol, t-butanol, pentanol , Hexanol, heptanol, octanol, nonanol, decanol, amyl alcohol and other alcohols; acetone, methyl ethyl ketone, cyclohexanone and other ketones; ethyl acetate, butyl acetate and other esters; diethyl ether, dioxane, tetrahydrofuran and other ethers; N Amide polar organic solvents such as N, dimethylformamide and N-methyl-2-pyrrolidone (NMP); such as toluene, xylene, chlorobenzene, orthodichlorobenzene and paradichlorobenzene Aromatic hydrocarbons; and the like. These may be used alone or in combination of two or more.
Especially, as a solvent, a polar organic solvent is preferable and NMP is more preferable.

<Other ingredients>
The binder composition for a non-aqueous secondary battery electrode of the present invention may contain components such as a reinforcing material, a leveling agent, a viscosity modifier, and an electrolyte solution additive in addition to the polymer and the organic solvent. Good. 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. Moreover, these components may be used individually by 1 type, and may be used combining two or more types by arbitrary ratios.

<Method for producing binder composition for non-aqueous secondary battery electrode>
The binder composition for a non-aqueous secondary battery electrode of the present invention is obtained by preparing the polymer described above in the organic solvent described above, or after preparing the polymer described above in water, It can be prepared by adding an organic solvent to the mixture with water and then evaporating the water. In addition, the preparation method (1) or (2) mentioned above can be used for preparation of a polymer. Moreover, when mix | blending the said other component with the binder composition for non-aqueous secondary battery electrodes, the method and order of adding the said other component can be made into arbitrary methods and order.

  Among them, the binder composition for a non-aqueous secondary battery electrode of the present invention is a mixture of an acid group-containing polymer and an amine compound in the organic solvent described above, and the acid group-containing polymer has one acid group in the molecule. It is preferable to produce by modifying part or all with an amine compound.

(Slurry composition for non-aqueous secondary battery electrode)
The slurry composition for non-aqueous secondary battery electrodes of the present invention includes an electrode active material, a conductive material, and the binder composition for non-aqueous secondary battery electrodes described above, and optionally other polymers and other components. Is further contained.

  In addition, since the slurry composition for non-aqueous secondary battery electrodes of the present invention includes the binder composition described above, the conductive material is well dispersed, and an electrode mixture layer having excellent peel strength is formed. Is possible. Therefore, by using the slurry composition, it is possible to produce a non-aqueous secondary battery electrode that is excellent in peel strength and can exhibit excellent rate characteristics and cycle characteristics in a non-aqueous secondary battery. it can.

<Electrode active material>
Here, the electrode active material is a material that transfers electrons in the electrode of the non-aqueous secondary battery. For example, when the non-aqueous secondary battery is a lithium ion secondary battery, a material that can occlude and release lithium is usually used as the electrode active material.
In addition, although the case where the slurry composition for non-aqueous secondary battery electrodes is a slurry composition for lithium ion secondary battery electrodes is demonstrated as an example below, this invention is not limited to the following example.

The positive electrode active material for the lithium ion secondary battery 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 lithium-containing composite oxide (Li (Co Mn Ni) O ₂ ), Ni—Mn—Al lithium-containing composite oxide, Ni—Co—Al lithium-containing composite oxide, olivine type Lithium iron phosphate (LiFePO ₄ ), olivine-type lithium manganese phosphate (LiMnPO ₄ ), Li ₂ MnO ₃ —LiNiO ₂ solid solution, Li _{1 + x} Mn _2−x O ₄ (0 <X <2) Examples of known positive electrode active materials such as Li-rich spinel compounds, Li [Ni _0.17 Li _0.2 Co _0.07 Mn _0.56 ] O ₂ , LiNi _0.5 Mn _1.5 O ₄ .
In addition, the compounding quantity and particle diameter of a positive electrode active material are not specifically limited, It can be made to be the same as that of the positive electrode active material used conventionally.

  Moreover, examples of the negative electrode active material for the lithium ion secondary battery include a carbon-based negative electrode active material, a metal-based negative electrode active material, and a negative electrode active material obtained by combining these.

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

Examples of the carbonaceous material include graphitizable carbon and non-graphitizable carbon having a structure close to an amorphous structure typified by glassy carbon.
Here, as the graphitizable carbon, for example, a carbon material using tar pitch obtained from petroleum or coal as a raw material can be mentioned. Specific examples include coke, mesocarbon microbeads (MCMB), mesophase pitch carbon fibers, pyrolytic vapor grown carbon fibers, and the like.
In addition, examples of the non-graphitizable carbon include a phenol resin fired body, polyacrylonitrile-based carbon fiber, pseudo-isotropic carbon, furfuryl alcohol resin fired body (PFA), and hard carbon.

Furthermore, examples of the graphite material include natural graphite and artificial graphite.
Here, as the artificial graphite, for example, artificial graphite obtained by heat-treating carbon containing graphitizable carbon mainly at 2800 ° C. or higher, graphitized MCMB heat-treated at 2000 ° C. or higher, and mesophase pitch-based carbon fiber at 2000 ° C. Examples thereof include graphitized mesophase pitch-based carbon fibers that have been heat-treated.

  Further, the metal-based negative electrode active material is an active material containing a metal, and usually includes an element capable of inserting lithium in the structure, and the theoretical electric capacity per unit mass when lithium is inserted is 500 mAh / The active material which is more than g. Examples of the metal active material include lithium metal and a single metal capable of forming a lithium alloy (for example, Ag, Al, Ba, Bi, Cu, Ga, Ge, In, Ni, P, Pb, Sb, Si, Sn). , Sr, Zn, Ti, etc.) and alloys thereof, and oxides, sulfides, nitrides, silicides, carbides, phosphides, and the like thereof. Among these, as the metal-based negative electrode active material, an active material containing silicon (silicon-based negative electrode active material) is preferable. This is because the capacity of the lithium ion secondary battery can be increased by using the silicon-based negative electrode active material.

Examples of silicon-based negative electrode active materials include silicon (Si), alloys containing silicon, SiO, SiO _x , and a composite of a Si-containing material obtained by coating or combining a Si-containing material with conductive carbon and conductive carbon. Etc. In addition, these silicon type negative electrode active materials may be used individually by 1 type, and may be used in combination of 2 types.

<Conductive material>
The conductive material is used to ensure electrical contact between the electrode active materials and to favorably form a conductive path in the electrode mixture layer formed using the slurry composition. Examples of the conductive material include carbon black (for example, acetylene black, ketjen black (registered trademark), furnace black, etc.), single-walled or multi-walled carbon nanotubes (multi-walled carbon nanotubes include cup stack type), carbon Conductive carbon materials such as nanohorns, vapor-grown carbon fibers, milled carbon fibers obtained by crushing polymer fibers after firing, single-layer or multilayer graphene, and carbon nonwoven fabric sheets obtained by firing nonwoven fabrics made of polymer fibers; Metal fibers or foils can be used.
These can be used alone or in combination of two or more.

  In addition, it is preferable that the content rate of the electrically conductive material in the slurry composition for non-aqueous secondary battery electrodes is 0.5 mass part or more per 100 mass parts of electrode active materials, and it is more preferable that it is 1 mass part or more. Preferably, it is 10 parts by mass or less, and more preferably 5 parts by mass or less. If the amount of the conductive material is too small, there may be a case where sufficient electrical contact between the electrode active materials cannot be ensured. On the other hand, if the amount of the conductive material is too large, the dispersibility of the slurry composition may decrease, and the density of the electrode mixture layer may decrease, and the secondary battery may not have a sufficiently high capacity. There is.

<Binder composition for non-aqueous secondary battery electrode>
As the binder composition for non-aqueous secondary battery electrodes, the non-aqueous secondary battery containing the above-mentioned polymer in which the amount of insoluble THF, the amount of amide groups, and the amount of acid groups are within a predetermined range and an organic solvent is included. A binder composition for secondary battery electrodes is used.

  Here, the content ratio of the binder composition in the slurry composition for non-aqueous secondary battery electrodes is preferably such that the amount of the polymer is 0.1 parts by mass or more per 100 parts by mass of the electrode active material. The amount is more preferably 0.5 parts by mass or more, more preferably 5 parts by mass or less, and even more preferably 3 parts by mass or less. When the amount of the polymer is outside the above range, the dispersibility of the slurry composition and the peel strength of the electrode mixture layer formed using the slurry composition may be reduced.

<Other polymers>
The other polymer usually functions as a binder together with the polymer contained in the binder composition for nonaqueous secondary battery electrodes. The other polymer that can function as a binder together with the above-described polymer is not particularly limited, and examples thereof include fluorine-containing polymers such as polyvinylidene fluoride, polyacrylonitrile, and polymethyl methacrylate. Among these, as the other polymer, a fluorine-containing polymer is preferable, and polyvinylidene fluoride is more preferable.

  Then, when both the polymer contained in the binder composition and the other polymer such as a fluorine-containing polymer are contained in the slurry composition for a non-aqueous secondary battery electrode, it is contained in the binder composition. The proportion of the polymer contained in the binder composition in a total of 100% by mass of the polymer and other polymer such as a fluorine-containing polymer is preferably 5% by mass or more, It is more preferably 10% by mass or more, further preferably 20% by mass or more, preferably 95% by mass or less, more preferably 90% by mass or less, and 80% by mass or less. Is more preferable. If the ratio of the polymer contained in the binder composition is not less than the above lower limit value, the dispersibility of the conductive material can be sufficiently improved. Moreover, if the ratio of the polymer contained in the binder composition is not more than the above upper limit value, the peel strength of the electrode mixture layer can be further increased.

<Other ingredients>
Other components that can be blended in the slurry composition are not particularly limited, and examples thereof include those similar to the other components that can be blended in the binder composition described above. Moreover, the other component may be used individually by 1 type, and may be used combining two or more types by arbitrary ratios.

<Manufacture of slurry composition for non-aqueous secondary battery electrode>
And the slurry composition for non-aqueous secondary battery electrodes is a mixture of an electrode active material, a conductive material, the binder composition for non-aqueous secondary battery electrodes described above, and any other polymer and other components. Can be manufactured.
Here, mixing of the above-described components can be performed in a state where each of the above components is dissolved or dispersed in an organic solvent. Specifically, the above components and the organic solvent are mixed using a blender such as a ball mill, a sand mill, a bead mill, a pigment disperser, a crushed grinder, an ultrasonic disperser, a homogenizer, a planetary mixer, or a fill mix. Thus, a slurry composition can be prepared. As the organic solvent, only the organic solvent contained in the binder composition may be used, or the organic solvent contained in the binder composition and the organic solvent newly added at the time of mixing may be used. Good.

(Electrode for non-aqueous secondary battery)
The electrode for non-aqueous secondary batteries of this invention is equipped with the electrode compound-material layer formed using the slurry composition for non-aqueous secondary battery electrodes mentioned above. Therefore, the electrode mixture layer contains at least an electrode active material, a conductive material, the above-described polymer, and any other polymer and other components. In addition, each component contained in the electrode mixture layer is contained in the slurry composition for non-aqueous secondary battery electrodes, and a suitable abundance ratio of each of these components is the slurry composition. It is the same as the preferred abundance ratio of each component in
And in the electrode for non-aqueous secondary batteries of the present invention, since the electrode mixture layer is formed using the slurry composition for non-aqueous secondary battery electrodes described above, the conductive material is uniformly dispersed. It is possible to satisfactorily provide an electrode mixture layer having high properties on the current collector. Therefore, the electrode for non-aqueous secondary batteries of the present invention is excellent in the peel strength of the electrode mixture layer, and can exhibit excellent rate characteristics and cycle characteristics in the non-aqueous secondary battery.

<Manufacture of electrodes for non-aqueous secondary batteries>
Here, the electrode mixture layer of the electrode for a non-aqueous secondary battery of the present invention was applied on the current collector, for example, a step of applying the slurry composition described above onto the current collector (application step). The slurry composition can be dried and formed on the current collector through a step of forming an electrode mixture layer on the current collector (drying step).

[Coating process]
And it does not specifically limit as a method of apply | coating the said slurry composition on a collector, A well-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 to only 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, an electrically conductive and electrochemically durable material is used. Specifically, as the current collector, for example, a current collector made of iron, copper, aluminum, nickel, stainless steel, titanium, tantalum, gold, platinum, or the like can be used. In addition, the 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 hot air, hot air, low-humidity air, vacuum drying method, infrared ray, electron beam, etc. The drying method by irradiation is mentioned. Thus, by drying the slurry composition on the current collector, an electrode mixture layer is formed on the current collector, and an electrode for a non-aqueous secondary battery including the current collector and the electrode mixture layer is obtained. be able to.
In addition, when the polymer and amine compound which have an unreacted acid group remain in the slurry composition, the said acid group and amine compound can form an amide group at the time of drying of a slurry composition. As a result, the affinity between the conductive material and the polymer is further increased, and the peel strength is further improved.

  Note that after the drying step, the electrode mixture layer may be subjected to pressure treatment using a die press or a roll press. The adhesion between the electrode mixture layer and the current collector can be improved by the pressure treatment. Moreover, when an electrode compound-material layer contains a curable polymer, it is preferable to harden the said polymer after formation of an electrode compound-material layer.

(Method for producing non-aqueous secondary battery)
The non-aqueous secondary battery of the present invention includes a positive electrode, a negative electrode, an electrolytic solution, and a separator, and uses the above-described non-aqueous secondary battery electrode as at least one of the positive electrode and the negative electrode. And since the nonaqueous secondary battery of this invention uses the electrode for nonaqueous secondary batteries mentioned above as at least one of a positive electrode and a negative electrode, it can exhibit the outstanding rate characteristic and cycling characteristics.
In the following, a case where the secondary battery is a lithium ion secondary battery will be described as an example, but the present invention is not limited to the following example.

<Electrode>
Here, the electrode other than the electrode for the non-aqueous secondary battery described above that can be used in the non-aqueous secondary battery of the present invention is not particularly limited, and is a known electrode used for manufacturing a secondary battery. An electrode can be used. Specifically, as an electrode other than the electrode for a non-aqueous secondary battery described above, an electrode 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 in which a supporting electrolyte is dissolved in an organic solvent is usually used. As the supporting electrolyte for the lithium ion secondary battery, for example, a lithium salt is used. 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. Of these, LiPF ₆ , LiClO ₄ , and CF ₃ SO ₃ Li are preferable, and LiPF ₆ is particularly preferable because it is easily dissolved in a solvent and exhibits a high degree of dissociation. In addition, electrolyte may be used individually by 1 type and may be used combining two or more types by arbitrary ratios. Usually, the lithium ion conductivity tends to increase as the supporting electrolyte having a higher degree of dissociation is used, so that the lithium ion conductivity can be adjusted depending on the type of the supporting electrolyte.

The organic solvent used in the electrolytic solution is not particularly limited as long as it can dissolve the supporting electrolyte. For example, dimethyl carbonate (DMC), ethylene carbonate (EC), diethyl carbonate (DEC), 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 preferably used. Moreover, you may use the liquid mixture of these solvents. Among these, carbonates are preferably used because they have a high dielectric constant and a wide stable potential region.
The concentration of the electrolyte in the electrolytic solution can be adjusted as appropriate. Further, known additives can be added to the electrolytic solution.

<Separator>
As a separator, it is not specifically limited, For example, the thing of Unexamined-Japanese-Patent No. 2012-204303 can be used. Among these, the film thickness of the entire separator can be reduced, thereby increasing the ratio of the electrode active material in the secondary battery and increasing the capacity per volume. A microporous film made of a resin such as polyethylene, polypropylene, polybutene, or polyvinyl chloride is preferable.

  In the secondary battery, for example, a positive electrode and a negative electrode are overlapped via a separator, and this is wound in accordance with the shape of the battery, folded as necessary, and placed in the battery container. Can be manufactured by injecting and sealing. Here, in the non-aqueous secondary battery of this invention, the electrode for non-aqueous secondary batteries mentioned above is used as at least one of a positive electrode and a negative electrode. The non-aqueous secondary battery of the present invention includes an overcurrent prevention element such as a fuse or a PTC element, if necessary, in order to prevent the occurrence of pressure rise inside the secondary battery, overcharge / discharge, etc. An expanded metal, a lead plate, or the like may be provided. The shape of the secondary battery may be any of, for example, a coin shape, a button shape, a sheet shape, a cylindrical shape, a square shape, and a flat shape.

EXAMPLES Hereinafter, although this invention is demonstrated concretely based on an Example, this invention is not limited to these Examples. In the following description, “%”, “ppm”, and “parts” representing amounts are based on mass unless otherwise specified.
In addition, in a polymer produced by copolymerizing a plurality of types of monomers, the proportion of monomer units formed by polymerizing a certain monomer in the polymer is usually unless otherwise specified. This coincides with the ratio (charge ratio) of the certain monomer in the total monomers used for polymerization of the polymer.
In Examples and Comparative Examples, the amount of polymer insoluble in THF, the amount of amide groups and acid groups in the polymer, the dispersibility of the slurry composition, the peel strength of the positive electrode mixture layer, and the secondary battery Rate characteristics and cycle characteristics were measured and evaluated by the following methods.

<THF insoluble content>
The prepared binder composition was dried at 120 ° C. for 10 hours to produce a film having a thickness of 0.2 mm to 0.5 mm. And the obtained film was cut | judged to 1 mm square, and the obtained film piece was precisely weighed. The weight of the film piece is W0.
The obtained film piece was immersed in 100 g of tetrahydrofuran (THF) at 60 ° C. for 24 hours. Then, the film piece pulled up from THF was vacuum-dried at 105 degreeC for 3 hours, and the weight W1 of THF insoluble matter was measured. Then, the THF insoluble content (%) was calculated according to the following formula.
THF insoluble content = (W1 / W0) × 100%
<Amount of amide group>
The amount of amide group contained in the polymer was determined as follows using a fluorescent X-ray analyzer and an X-ray photoelectron spectrum (XPS) measuring device.
Specifically, first, the prepared binder composition was dried at 120 ° C. for 10 hours to prepare a measurement sample. Next, the weight ratio of oxygen atoms to all atoms contained in the polymer was measured using a fluorescent X-ray analyzer (PW2400, manufactured by Philips). Then, by dividing the obtained weight ratio by the atomic weight of oxygen, the number of moles O _x (unit: mol / g) of oxygen atoms contained in 1 g of the polymer was calculated. Moreover, the 1s orbital spectrum of the oxygen atom in the 100-nm depth part from the surface of the polymer was measured with the X-ray photoelectron spectroscopy (XPS) measuring device. Then, the total peak area A _all of the 1s orbital spectrum of the obtained oxygen atom is calculated, and the obtained spectrum is peak-separated to obtain the peak area A _amid derived from the amide bond observed in the vicinity of 531.2 eV. Calculated. And the value obtained by the following formula was made into the quantity (unit: mmol / g) of the amide group in a polymer.
Amount of amide group in polymer = O _x × (A _amid / A _all ) × 1000
<Amount of acid group>
5 g of the polymer obtained by drying (120 ° C., 10 hours) the prepared binder composition was dissolved in 200 g of a mixed solution of toluene and ethanol (toluene / ethanol (volume ratio) = 1/4). And the quantity of the acid group in a polymer was calculated | required by the potentiometric titration method using 0.1N potassium hydroxide (KOH) aqueous solution.
<Dispersibility>
The prepared slurry composition was stored at a temperature of 25 ° C. for 5 days while stirring with a mix rotor (stirring speed: 60 rpm). The viscosity change rate (= (η _5d / η _ini ) × 100%) is calculated using the viscosity η _ini of the slurry composition immediately after preparation and the viscosity η _5d of the slurry composition after storage for 5 days. did. A B-type viscometer was used for measuring the viscosity.
And the dispersibility of the slurry composition was evaluated according to the following criteria. It shows that the dispersibility of the electrically conductive material etc. which are contained in a slurry composition is excellent, so that a viscosity change rate is small.
A: Viscosity change rate is 90% or more and 110% or less B: Viscosity change rate is 80% or more and less than 90% or more than 110% and 120% or less C: Viscosity change rate is 70% or more and less than 80% or more than 120% and 130% or less D: Viscosity change rate is 60% or more and less than 70% or more than 130% and 140% or less E: Viscosity change rate is less than 60% or more than 140% <Peel Strength>
The produced positive electrode was cut into a rectangle having a width of 1.0 cm and a length of 10 cm to obtain a test piece. And the test piece was fixed to the test stand with the surface on the positive electrode mixture layer side facing up. Next, after attaching a cellophane tape (as defined in JIS Z1522) to the surface of the test piece on the positive electrode mixture layer side, the cellophane tape was applied to the test piece in the 180 ° direction (the other end side) at 50 mm / mm. The stress when peeled at a rate of minutes was measured. The measurement was performed 10 times, the average value was obtained, and this was taken as the peel strength (N / m) and evaluated according to the following criteria. It shows that it is excellent in the adhesive strength of a collector and a positive mix layer, so that peel strength is large.
A: Peel strength is 20 N / m or more B: Peel strength is 10 N / m or more and less than 20 N / m C: Peel strength is 5 N / m or more and less than 10 N / m D: Peel strength is less than 5 N / m <Rate characteristics>
The secondary battery whose initial capacity was measured was charged with a constant current at 0.2 CmA until the battery voltage reached 4.2 V, and then charged with a constant voltage at 4.2 V until the charging current reached 0.02 CmA. Subsequently, constant current discharge was performed until the battery voltage became 3.0 V at 2 CmA, and the 2 C capacity was obtained. The capacity change rate (= {(2C capacity) / (initial capacity)} × 100%) was calculated and evaluated according to the following criteria. The larger the capacity change rate, the better the rate characteristics.
A: Capacity change rate is 90% or more B: Capacity change rate is 87% or more and less than 90% C: Capacity change rate is 84% or more and less than 87% D: Capacity change rate is less than 84% <Cycle characteristics>
About the produced secondary battery, the charge / discharge cycle which charges to 4.3V with a 1C constant current and discharges to 3.0V with a 1C constant current was repeated 300 cycles in a 45 degreeC environment. The ratio of the discharge capacity at the 300th cycle to the initial discharge capacity was defined as the capacity retention ratio (= {(discharge capacity at the 300th cycle) / (initial discharge capacity)} × 100%), and the determination was made according to the following criteria. It shows that it is excellent in cycling characteristics, so that a capacity | capacitance maintenance factor is large.
A: Capacity maintenance ratio is 80% or more B: Capacity maintenance ratio is 75% or more and less than 80% C: Capacity maintenance ratio is 60% or more and less than 75% D: Capacity maintenance ratio is less than 60%

Example 1
<Preparation of acid group-containing polymer>
In a metal bottle, 180 parts of ion-exchanged water, 25 parts of an aqueous solution of sodium dodecylbenzenesulfonate having a concentration of 10% by mass, 35 parts of acrylonitrile as a nitrile group-containing monomer, a monomer having a carboxylic acid group (an acid group-containing monomer) Methacrylic acid as a polymer) and 0.5 part of t-dodecyl mercaptan as a molecular weight regulator were sequentially charged, and the internal gas was substituted with nitrogen three times. 60 parts of 3-butadiene was added. The metal bottle was kept at 5 ° C., 0.1 part of cumene hydroperoxide as a polymerization initiator was added, and polymerization was performed for 16 hours while rotating the metal bottle. Next, 0.1 parts of a hydroquinone aqueous solution having a concentration of 10% by mass as a polymerization terminator was added to terminate the polymerization reaction, and then the residual monomer was removed using a rotary evaporator at a water temperature of 60 ° C. to disperse the copolymer in water. A liquid (solid content concentration of about 30% by mass) was obtained.
Next, in the autoclave, the aqueous dispersion prepared above and the palladium catalyst (1 mass) so that the palladium content relative to the dry weight of the copolymer contained in the aqueous dispersion obtained above was 750 ppm. % Palladium acetate / acetone solution and ion-exchanged water mixed at 1: 1 (mass ratio). And hydrogenation reaction was performed at a hydrogen pressure of 3 MPa and a temperature of 50 ° C. for 6 hours to obtain a hydrogenated copolymer.
Subsequently, N-methyl-2-pyrrolidone (NMP) as an organic solvent was added to the aqueous dispersion of the obtained hydrogenated copolymer so that the solid content concentration of the hydrogenated copolymer was 7%. Then, distillation under reduced pressure was performed at a temperature of 90 ° C. to remove water and excess NMP, and an NMP solution (solid content concentration 8%) containing a hydrogenated copolymer as an acid group-containing polymer was obtained.
<Modification of acid group-containing polymer>
Ratio of n-hexylamine as amine compound to 3 parts of n-hexylamine per 100 parts of hydrogenated copolymer as acid group-containing polymer with respect to NMP solution containing hydrogenated copolymer Added at. And it mixed at the temperature of 110 degreeC for 10 hours, and obtained the binder composition for non-aqueous secondary battery positive electrodes containing the polymer containing a modified polymer and NMP as an organic solvent (modification process).
Then, the amount of the polymer insoluble in THF, and the amount of amide group and acid group in the polymer were measured. The results are shown in Table 1.
<Preparation of slurry composition for positive electrode>
Co-Ni-Mn lithium-containing composite oxide (cell seed (registered trademark) NMC111, LiNi _1/3 Co _1/3 Mn _1/3 O ₂ , manufactured by Nippon Chemical Industry Co., Ltd.) as a positive electrode active material, and a conductive material 2.0 parts of acetylene black (Denka Black (registered trademark) HS-100, manufactured by Denki Kagaku Kogyo Co., Ltd.), 1 part of the binder composition in terms of solid content, and polyvinylidene fluoride as other polymer ( 1 part of KF polymer # 7200 (manufactured by Kureha) and NMP as an additional organic solvent are added so that the solid content concentration becomes 75%, and mixed with a planetary mixer, for a non-aqueous secondary battery positive electrode A slurry composition was prepared.
And the dispersibility of the slurry composition was evaluated. The results are shown in Table 1.
<Preparation of positive electrode>
The obtained positive electrode slurry composition was defoamed and then applied onto a current collector made of an aluminum foil having a thickness of 20 μm using a comma coater so that the film thickness after drying was about 70 μm. And the apply | coated slurry composition was dried for 20 minutes at the temperature of 50 degreeC, and was then heat-processed at 110 degreeC for 2 hours, and the positive electrode original fabric was obtained. And the obtained positive electrode original fabric was rolled with the roll press, and the positive electrode (thickness: 60 micrometers) provided with the positive electrode compound-material layer whose density is 3.2 g / cm < ³ > on aluminum foil (current collector) was obtained.
And the peel strength of the positive mix layer was evaluated using the produced positive electrode. The results are shown in Table 1.
<Production of negative electrode>
Planetary graphite 100 parts spherical artificial graphite (volume average particle size: 12 μm) as negative electrode active material, 1 part styrene butadiene copolymer as binder, 1 part carboxymethyl cellulose as thickener, and appropriate amount of water as dispersion medium The mixture was stirred with a mixer to prepare a slurry composition for a non-aqueous secondary battery negative electrode.
Next, a copper foil having a thickness of 15 μm was prepared as a current collector. And the said slurry composition for non-aqueous secondary battery negative electrodes was apply | coated so that the application quantity after drying might be 10 mg / cm < ² > on the single side | surface of copper foil. And the apply | coated slurry composition was dried for 20 minutes at the temperature of 50 degreeC, and was then heat-processed for 20 minutes at 60 degreeC, and 20 minutes at 120 degreeC, and the negative electrode original fabric was obtained. The obtained negative electrode raw material was rolled with a roll press to prepare a sheet-like negative electrode comprising a negative electrode mixture layer having a density of 1.5 g / cm ³ and a copper foil.
<Production of secondary battery>
An aluminum packaging exterior was prepared as the battery exterior. The positive electrode obtained above was cut into a 4 cm × 4 cm square and arranged so that the current collector-side surface was in contact with the aluminum packaging exterior. A separator made of a polyethylene microporous film cut into a square of 4.4 cm × 4.4 cm was disposed on the positive electrode mixture layer of the positive electrode. Furthermore, the negative electrode obtained above was cut into a square of 4.2 cm × 4.2 cm, and this was arranged on the separator so that the surface on the negative electrode mixture layer side faces the separator. Furthermore, an electrolytic solution composed of a 1.0% LiPF ₆ solution containing 1.5% vinylene carbonate (VC) was filled. The solvent of this LiPF ₆ solution is a mixed solvent (EC / EMC = 3/7 (volume ratio)) of ethylene carbonate (EC) and ethyl methyl carbonate (EMC). Thereafter, in order to seal the opening of the aluminum packaging material exterior, heat sealing was performed at 150 ° C. to close the aluminum packaging material exterior, and a secondary battery was obtained.
And the rate characteristic and cycling characteristic of the produced secondary battery were evaluated. The results are shown in Table 1.

(Example 2)
In the preparation of the acid group-containing polymer, the acid group-containing content was the same as in Example 1 except that the amount of methacrylic acid was changed to 0.7 parts and the amount of 1,3-butadiene was changed to 64.3 parts. A polymer, a positive electrode binder composition, a positive electrode slurry composition, a positive electrode, a negative electrode, and a secondary battery were produced. Various evaluations were performed in the same manner as in Example 1. The results are shown in Table 1.

(Example 3)
In the preparation of the acid group-containing polymer, the acid group content was changed in the same manner as in Example 1 except that the amount of methacrylic acid was changed to 8.5 parts and the amount of 1,3-butadiene was changed to 56.5 parts. A polymer, a positive electrode binder composition, a positive electrode slurry composition, a positive electrode, a negative electrode, and a secondary battery were produced. Various evaluations were performed in the same manner as in Example 1. The results are shown in Table 1.

Example 4
The acid group-containing polymer, the positive electrode binder composition, and the positive electrode slurry composition were the same as in Example 1 except that 5 parts of itaconic acid was used instead of 5 parts of methacrylic acid when preparing the acid group-containing polymer. A positive electrode, a negative electrode, and a secondary battery were produced. Various evaluations were performed in the same manner as in Example 1. The results are shown in Table 1.

(Examples 5-6)
When the acid group-containing polymer was modified, the amount of n-hexylamine per 100 parts of the hydrogenated copolymer as the acid group-containing polymer was 4.5 parts (Example 5) and 0.2 parts (implemented), respectively. Example 6) An acid group-containing polymer, a positive electrode binder composition, a positive electrode slurry composition, a positive electrode, a negative electrode, and a secondary battery were prepared in the same manner as in Example 1 except that n-hexylamine was added. Produced. Various evaluations were performed in the same manner as in Example 1. The results are shown in Table 1.

(Example 7)
The acid group-containing polymer, the positive electrode binder composition, and the positive electrode slurry composition were the same as in Example 1 except that benzylamine was used in place of n-hexylamine as the amine compound when the acid group-containing polymer was modified. Product, positive electrode, negative electrode and secondary battery were prepared. Various evaluations were performed in the same manner as in Example 1. The results are shown in Table 1.

(Example 8)
When modifying the acid group-containing polymer, ethylamine is used instead of n-hexylamine as the amine compound so that the amount of ethylamine per 100 parts of the hydrogenated copolymer as the acid group-containing polymer is 2 parts. An acid group-containing polymer, a positive electrode binder composition, a positive electrode slurry composition, a positive electrode, a negative electrode, and a secondary battery were produced in the same manner as in Example 1 except that ethylamine was added. Various evaluations were performed in the same manner as in Example 1. The results are shown in Table 1.

Example 9
A positive electrode binder composition, a positive electrode slurry composition, a positive electrode, a negative electrode, and a secondary battery were produced in the same manner as in Example 1 except that the acid group-containing polymer prepared as follows was used. Various evaluations were performed in the same manner as in Example 1. The results are shown in Table 1.
<Preparation of acid group-containing polymer>
In a metal bottle, 180 parts of ion-exchanged water, 25 parts of an aqueous solution of sodium dodecylbenzenesulfonate having a concentration of 10% by mass, 95 parts of acrylonitrile as a nitrile group-containing monomer, a monomer having a carboxylic acid group (acid group-containing monomer) 5 parts of methacrylic acid as a polymer and 0.5 part of t-dodecyl mercaptan as a molecular weight modifier were sequentially charged, and the internal gas was substituted with nitrogen three times. The metal bottle was kept at 5 ° C., 0.1 part of cumene hydroperoxide as a polymerization initiator was added, and polymerization was performed for 16 hours while rotating the metal bottle. Next, 0.1 parts of a hydroquinone aqueous solution having a concentration of 10% by mass as a polymerization terminator was added to terminate the polymerization reaction, and then the residual monomer was removed using a rotary evaporator at a water temperature of 60 ° C. to disperse the copolymer in water. A liquid (solid content concentration of about 30% by mass) was obtained.
Subsequently, N-methyl-2-pyrrolidone (NMP) as an organic solvent was added to the aqueous dispersion of the copolymer so that the solid content concentration of the copolymer was 7%. Then, distillation under reduced pressure was performed at a temperature of 90 ° C. to remove water and excess NMP, and an NMP solution (solid content concentration 8%) containing a copolymer as an acid group-containing polymer was obtained.

(Example 10)
A positive electrode binder composition, a positive electrode slurry composition, a positive electrode, a negative electrode, and a secondary battery were produced in the same manner as in Example 1 except that the acid group-containing polymer prepared as follows was used. Various evaluations were performed in the same manner as in Example 1. The results are shown in Table 1.
<Preparation of acid group-containing polymer>
In a metal bottle, 180 parts of ion-exchanged water, 25 parts of an aqueous solution of sodium dodecylbenzenesulfonate having a concentration of 10% by mass, 5 parts of acrylonitrile as a nitrile group-containing monomer, a monomer having a carboxylic acid group (acid group-containing monomer) 5 parts of methacrylic acid as a monomer, 60 parts of 2-ethylhexyl acrylate as a (meth) acrylic acid ester monomer, 30 parts of styrene as an aromatic vinyl monomer, and t-dodecyl as a molecular weight modifier. Mercaptan (0.5 parts) was sequentially charged, and the internal gas was replaced with nitrogen three times. The metal bottle was kept at 5 ° C., 0.1 part of cumene hydroperoxide as a polymerization initiator was added, and polymerization was performed for 16 hours while rotating the metal bottle. Next, 0.1 parts of a hydroquinone aqueous solution having a concentration of 10% by mass as a polymerization terminator was added to terminate the polymerization reaction, and then the residual monomer was removed using a rotary evaporator at a water temperature of 60 ° C. to disperse the copolymer in water. A liquid (solid content concentration of about 30% by mass) was obtained.
Subsequently, N-methyl-2-pyrrolidone (NMP) as an organic solvent was added to the aqueous dispersion of the copolymer so that the solid content concentration of the copolymer was 7%. Then, distillation under reduced pressure was performed at a temperature of 90 ° C. to remove water and excess NMP, and an NMP solution (solid content concentration 8%) containing a copolymer as an acid group-containing polymer was obtained.

(Comparative Example 1)
In the preparation of the acid group-containing polymer, the acid group-containing content was the same as in Example 1 except that the amount of methacrylic acid was changed to 0.1 part and the amount of 1,3-butadiene was changed to 64.9 parts. A polymer, a positive electrode binder composition, a positive electrode slurry composition, a positive electrode, a negative electrode, and a secondary battery were produced. Various evaluations were performed in the same manner as in Example 1. The results are shown in Table 1.

(Comparative Example 2)
At the time of preparation of the acid group-containing polymer, the amount of methacrylic acid was changed to 11 parts, the amount of 1,3-butadiene was changed to 54 parts, and when the acid group-containing polymer was modified, In the same manner as in Example 1 except that n-hexylamine was added so that the amount of n-hexylamine per 100 parts of the hydrogenated copolymer was 0.1 part, an acid group-containing polymer and a positive electrode binder A composition, a slurry composition for positive electrode, a positive electrode, a negative electrode, and a secondary battery were produced. Various evaluations were performed in the same manner as in Example 1. The results are shown in Table 1.

(Comparative Example 3)
NMP solution containing a hydrogenated copolymer as an acid group-containing polymer without modification of the acid group-containing polymer (ie, without adding an amine compound to the NMP solution containing the hydrogenated copolymer) The acid group-containing polymer, the positive electrode binder composition, the positive electrode slurry composition, the positive electrode, the negative electrode, and the secondary battery were prepared in the same manner as in Example 1 except that was used as a positive electrode binder composition. Various evaluations were performed in the same manner as in Example 1. The results are shown in Table 1.

(Comparative Example 4)
During the preparation of the acid group-containing polymer, the amount of 1,3-butadiene was changed to 59 parts, and 1 part of acrylamide was added as the amide group-containing monomer without modifying the acid group-containing polymer (ie, The NMP solution containing the hydrogenated copolymer as the acid group-containing polymer was used as the positive electrode binder composition as it was without adding an amine compound to the NMP solution containing the hydrogenated copolymer. In the same manner as in Example 1, an acid group-containing polymer, a positive electrode binder composition, a positive electrode slurry composition, a positive electrode, a negative electrode, and a secondary battery were produced. Various evaluations were performed in the same manner as in Example 1. The results are shown in Table 1.

From Table 1, in Examples 1-10 using the binder composition containing the polymer in which the amount of THF insolubles, the amount of amide groups, and the amount of acid groups are within the predetermined ranges, the dispersibility of the conductive material is excellent. In addition, it is understood that a slurry composition capable of forming an electrode mixture layer having excellent peel strength can be obtained, and a secondary battery having excellent rate characteristics and cycle characteristics can be manufactured.
Further, from Table 1, in Comparative Example 1 using a binder composition containing a polymer with a small amount of THF-insoluble matter, the peel strength of the electrode mixture layer is lowered, and the cycle characteristics of the secondary battery are lowered. I understand. Furthermore, it can be seen from Table 1 that in Comparative Example 2 using a binder composition containing a polymer having a large amount of acid groups, the dispersibility of the conductive material is lowered and the rate characteristics of the secondary battery are lowered. . Further, from Table 1, in Comparative Example 3 using a binder composition containing a polymer containing no amide group and in Comparative Example 4 using a binder composition containing a polymer having a large amount of THF insoluble matter, the dispersion of the conductive material It can be seen that the peel strength of the electrode material layer and the electrode composite layer are lowered, and the rate characteristics and cycle characteristics of the secondary battery are degraded.

According to the present invention, there are provided a binder composition for a non-aqueous secondary battery electrode and a slurry composition for a non-aqueous secondary battery electrode that can form an electrode mixture layer that is excellent in dispersibility of a conductive material and excellent in peel strength. can get.
In addition, according to the present invention, there can be obtained a non-aqueous secondary battery electrode that is excellent in peel strength and capable of exhibiting excellent rate characteristics and cycle characteristics in a non-aqueous secondary battery.
Furthermore, according to the present invention, a nonaqueous secondary battery having excellent rate characteristics and cycle characteristics can be obtained.

Claims (11)

A binder composition for a non-aqueous secondary battery electrode comprising a polymer and an organic solvent,
The polymer has a tetrahydrofuran insoluble content of 3% by mass or more and 50% by mass or less,
The amount of amide groups in the polymer is 0.01 mmol / g or more and 1.0 mmol / g or less,
The binder composition for nonaqueous secondary battery electrodes whose amount of acid groups in the polymer is 0 mmol / g or more and 1.0 mmol / g or less. It is a manufacturing method of the binder composition for non-aqueous secondary battery electrodes according to claim 1,
An acid group-containing polymer containing an acid group-containing monomer unit in a proportion of 0.5% by mass or more and 10% by mass or less, and an amine compound selected from the group consisting of a primary amine and a secondary amine The manufacturing method of the binder composition for non-aqueous secondary battery electrodes including mixing and preparing the said polymer.   The manufacturing method of the binder composition for non-aqueous secondary battery electrodes of Claim 2 whose said acid group containing monomer unit is a monomer unit which has a carboxylic acid group.   The manufacturing method of the binder composition for non-aqueous secondary battery electrodes of Claim 2 or 3 whose said amine compound is a monoamine compound.   The manufacturing method of the binder composition for non-aqueous secondary battery electrodes of Claim 4 whose said monoamine compound is a primary amine.   The non-aqueous secondary battery electrode according to any one of claims 2 to 5, wherein the amine compound is mixed at a ratio of 0.01 parts by mass or more and 5.0 parts by mass or less per 100 parts by mass of the acid group-containing polymer. For producing a binder composition for use.   A slurry composition for a non-aqueous secondary battery electrode, comprising an electrode active material, a conductive material, and the binder composition for a non-aqueous secondary battery electrode according to claim 1.   Furthermore, the slurry composition for non-aqueous secondary battery electrodes of Claim 7 containing a fluorine-containing polymer.   The slurry composition for a non-aqueous secondary battery electrode according to claim 8, wherein a ratio of the content of the polymer to a total content of the polymer and the fluorine-containing polymer is 5% by mass or more and 95% by mass or less. object.   The electrode for non-aqueous secondary batteries containing the electrode compound-material layer formed using the slurry composition for non-aqueous secondary battery electrodes in any one of Claims 7-9. A non-aqueous secondary battery comprising a positive electrode, a negative electrode, a separator and an electrolyte solution,
The non-aqueous secondary battery whose at least one of the said positive electrode and the said negative electrode is the electrode for non-aqueous secondary batteries of Claim 10.