JPWO2018168502A1 - Binder composition for non-aqueous secondary battery electrode, conductive material paste composition for non-aqueous secondary battery electrode, slurry composition for non-aqueous secondary battery electrode, electrode for non-aqueous secondary battery, and non-aqueous secondary battery - Google Patents

Abstract

An object of the present invention is to provide a binder composition for a non-aqueous secondary battery electrode that has excellent viscosity stability and can form an electrode mixture layer in which swelling in an electrolytic solution is suppressed. The binder composition of the present invention includes a polymer having a functional group capable of binding to a cationic group, and an organic compound having two or more cationic groups and having a molecular weight of 8000 or less.

Description

  The present invention relates to a binder composition for a non-aqueous secondary battery electrode, a conductive paste composition for a non-aqueous secondary battery electrode, a slurry composition for a non-aqueous secondary battery electrode, a non-aqueous secondary battery electrode, and a non-aqueous secondary battery. It relates to the next 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, lightweight, high in energy density, and capable of being repeatedly charged and discharged. Yes, used for a wide range of applications. Therefore, in recent years, improvements in battery members such as electrodes have 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 generally includes 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. Then, this electrode mixture layer, for example, by applying a slurry composition containing an electrode active material and a binder composition including a binder on the current collector, and drying the applied slurry composition It is formed.

Therefore, in recent years, in order to further improve the performance of the secondary battery, attempts have been made to improve the binder composition used for forming the electrode mixture layer.
Specifically, for example, in Patent Document 1, a non-crosslinked polymer having a functional group capable of binding to a polyvalent metal ion, a polyvalent metal compound containing a polyvalent metal and a ligand having a molecular weight of 30 or more, The binder composition containing a solvent is excellent in viscosity stability, and by using this binder composition, the adhesion between the electrode mixture layer and the current collector is increased, and the cycle characteristics of the secondary battery are improved. It has been reported that it can be improved.

JP 2008-166058 A

  However, the viscosity stability of the above conventional binder composition has not been sufficiently satisfactory. Further, the electrode mixture layer obtained by using the above-mentioned conventional binder composition excessively swells in the electrolytic solution. And it was difficult for an electrode provided with an electrode mixture layer obtained from such a binder composition to exhibit excellent cycle characteristics in a secondary battery. That is, the conventional binder composition is improved in that the viscosity stability is secured, the swelling of the electrode mixture layer in the electrolytic solution is suppressed, and the cycle characteristics of the secondary battery are sufficiently improved. There was room for

Thus, an object of the present invention is to provide a binder composition for a non-aqueous secondary battery electrode that has excellent viscosity stability and can form an electrode mixture layer in which swelling in an electrolytic solution is suppressed. .
Further, the present invention provides a non-aqueous secondary battery capable of forming an electrode mixture layer in which swelling in an electrolytic solution is suppressed and capable of exhibiting excellent cycle characteristics to a non-aqueous secondary battery. An object is to provide a conductive material paste composition for an electrode and a slurry composition for a non-aqueous secondary battery electrode.
Furthermore, the present invention provides an electrode for a non-aqueous secondary battery which includes an electrode mixture layer in which swelling in an electrolytic solution is suppressed, and which can exhibit excellent cycle characteristics to a non-aqueous secondary battery. The purpose is to provide.
Then, an object of the present invention is to provide a non-aqueous secondary battery having excellent cycle characteristics.

  The inventor of the present invention has conducted intensive studies for the purpose of solving the above problems. Then, the present inventors provide a binder composition comprising a polymer having a functional group capable of binding to a cationic group, and an organic compound having two or more cationic groups and having a molecular weight of not more than a predetermined value. However, they have found that they are excellent in viscosity stability and can form an electrode mixture layer in which swelling in an electrolytic solution is suppressed by using the binder composition, thereby completing the present invention.

That is, an object of the present invention is to advantageously solve the above-mentioned problems, and a binder composition for a non-aqueous secondary battery electrode of the present invention is a polymer having a functional group capable of binding to a cationic group. And an organic compound having two or more cationic groups and a molecular weight of 8000 or less. As described above, a binder composition containing a polymer having a functional group capable of binding to a cationic group and an organic compound having two or more cationic groups and having a molecular weight of a predetermined value or less has a viscosity of The use of the binder composition, which is excellent in stability, makes it possible to form an electrode mixture layer in which swelling in an electrolytic solution is suppressed.
In the present invention, the term "cationic group" refers to a functional group that can have a cationic property when present alone or together with a substance that supplies a positive charge in a solvent. In the present invention, the term "functional group capable of binding to a cationic group" refers to a functional group capable of interacting with a cationic group by an ionic bond, a hydrogen bond, a covalent bond, or the like in a solvent.

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

Further, in the binder composition for a non-aqueous secondary battery electrode of the present invention, the polymer may have a monomer unit having a functional group capable of binding to a cationic group in an amount of 0.1% by mass or more and 20% by mass or less. It is preferable to include them in a ratio. If a polymer containing a monomer unit containing a functional group capable of binding to a cationic group in an amount within the above range is used, while sufficiently securing the viscosity stability of the binder composition, the electrode mixture layer Swelling in an electrolytic solution can be further suppressed.
In the present invention, "including a monomer unit" means that "a polymer obtained by using the monomer contains a repeating unit derived from the monomer". The proportion of each monomer unit and / or structural unit in the polymer can be measured using nuclear magnetic resonance (NMR) methods such as ¹ H-NMR and ¹³ C-NMR.

  Furthermore, the binder composition for a non-aqueous secondary battery electrode of the present invention preferably contains the organic compound in an amount of 0.1 to 20 parts by mass per 100 parts by mass of the polymer. When the compounding amount of the organic compound is within the above range, the swelling of the electrode mixture layer in the electrolytic solution can be further suppressed while sufficiently securing the viscosity stability of the binder composition.

  Here, the binder composition for a non-aqueous secondary battery electrode of the present invention, wherein the polymer comprises a nitrile group-containing monomer unit and at least one of a conjugated diene monomer unit and an alkylene structural unit, The ratio of the nitrile group-containing monomer unit in the polymer is 5% by mass or more and 35% by mass or less, and the sum of the ratio of the conjugated diene monomer unit and the ratio of the alkylene structural unit in the polymer is , 30% by mass or more and 90% by mass or less. The above-mentioned polymer can be dissolved well in the solvent of the binder composition, and can be well adsorbed on the conductive material or the like to disperse them satisfactorily (that is, excellent in dispersing ability for the conductive material or the like). Then, by using the polymer, the swelling of the electrode mixture layer in the electrolytic solution can be further suppressed while sufficiently securing the viscosity stability of the binder composition.

  Another object of the present invention is to advantageously solve the above-mentioned problems, and a conductive material paste composition for a non-aqueous secondary battery electrode according to the present invention includes a conductive material and any one of the above-described non-aqueous-based materials. And a binder composition for a secondary battery electrode. If a conductive material and a conductive material paste composition containing any of the binder compositions described above are prepared, and a slurry composition is prepared by adding an electrode active material or the like to the conductive material paste composition, an electrolytic solution In addition to being able to form an electrode mixture layer in which swelling is suppressed, the secondary battery can exhibit excellent cycle characteristics.

  Another object of the present invention is to advantageously solve the above-mentioned problems, and a slurry composition for a non-aqueous secondary battery electrode of the present invention comprises: an electrode active material; It comprises a binder composition for a secondary battery electrode or the above-mentioned conductive material paste for a non-aqueous secondary battery electrode. As described above, by using the electrode active material and the slurry composition containing any of the binder compositions or the conductive material paste described above, it is possible to form an electrode mixture layer in which swelling in the electrolytic solution is suppressed. In addition, the secondary battery can exhibit excellent cycle characteristics.

  Another object of the present invention is to advantageously solve the above-described problems, and the electrode for a non-aqueous secondary battery of the present invention is formed using the above-described slurry composition for a non-aqueous secondary battery electrode. It is characterized by having an electrode mixture layer formed. As described above, the electrode mixture layer obtained using the above-described slurry composition is suppressed from swelling in the electrolytic solution, and the electrode including the electrode mixture layer has excellent cycle characteristics for a secondary battery. Can be demonstrated.

  In addition, an object of the present invention is to solve the above problems advantageously, a non-aqueous secondary battery of the present invention includes a positive electrode, a negative electrode, an electrolytic solution and a separator, at least one of the positive electrode and the negative electrode Is an electrode for a non-aqueous secondary battery described above. Thus, the non-aqueous secondary battery including the above-described electrode has excellent cycle characteristics.

ADVANTAGE OF THE INVENTION According to this invention, the binder composition for non-aqueous secondary battery electrodes which is excellent in viscosity stability and can form the electrode mixture layer in which the swelling in the electrolytic solution was suppressed is obtained.
Further, according to the present invention, a non-aqueous secondary battery capable of forming an electrode mixture layer in which swelling in an electrolytic solution is suppressed and exhibiting excellent cycle characteristics to a non-aqueous secondary battery is provided. A conductive material paste composition for a secondary battery electrode and a slurry composition for a non-aqueous secondary battery electrode are obtained.
Furthermore, according to the present invention, for a non-aqueous secondary battery, which comprises an electrode mixture layer in which swelling in an electrolytic solution is suppressed, and which can exhibit excellent cycle characteristics to a non-aqueous secondary battery An electrode is obtained.
According to the present invention, a non-aqueous secondary battery having excellent cycle characteristics can be obtained.

Hereinafter, embodiments of the present invention will be described in detail.
Here, the binder composition for a non-aqueous secondary battery electrode of the present invention can be used when preparing a slurry composition for a non-aqueous secondary battery electrode. In addition, the binder composition for a non-aqueous secondary battery electrode of the present invention is mixed with a conductive material, and a conductive material paste for a non-aqueous secondary battery electrode containing the binder composition for a non-aqueous secondary battery electrode and a conductive material. After the composition, it can be used for preparing a slurry composition for a non-aqueous secondary battery electrode. The slurry composition for a non-aqueous secondary battery electrode prepared using the binder composition for a non-aqueous secondary battery electrode of the present invention is used for forming an electrode of a non-aqueous secondary battery such as a lithium ion secondary battery. Can be used. Furthermore, a non-aqueous secondary battery of the present invention is characterized by using an electrode for a non-aqueous secondary battery formed using the slurry composition for a non-aqueous secondary battery electrode of the present invention.
The binder composition for a non-aqueous secondary battery electrode, the conductive material paste composition for a non-aqueous secondary battery electrode, and the slurry composition for a non-aqueous secondary battery electrode of the present invention form the positive electrode of a non-aqueous secondary battery. In particular, it can be suitably used.

(Binder composition for non-aqueous secondary battery electrode)
The binder composition for a non-aqueous secondary battery electrode of the present invention includes a polymer having a functional group capable of binding to a cationic group (hereinafter sometimes referred to as “polymer (A)”) and two or more polymers. (Hereinafter, sometimes referred to as “polyvalent cationic organic compound (B)”), and optionally other components that can be blended in the electrode of the secondary battery. contains. Here, in the binder composition for a non-aqueous secondary battery electrode of the present invention, the above-mentioned polyvalent cationic organic compound (B) has a molecular weight of 8,000 or less. The binder composition for a non-aqueous secondary battery electrode of the present invention usually further contains a solvent such as an organic solvent.

And since the binder composition of this invention contains the polymer which has the functional group which can couple | bond with a cationic group, and the polyvalent cationic organic compound (B) whose molecular weight is 8000 or less, it was preserved for a long period of time. Even in this case, the change in viscosity is small and swelling of the electrode mixture layer in the electrolytic solution can be suppressed.
The reason why the binder composition of the present invention has excellent viscosity stability and can suppress the swelling of the electrode mixture layer in the electrolytic solution is not clear, but is presumed to be as follows.
That is, in the binder composition of the present invention, the functional group in the polymer (A) and the cationic group in the polyvalent cationic organic compound (B) can favorably interact in a solvent. The change in viscosity over time is suppressed as compared with the case where the combination (A) and the polyvalent metal compound containing the predetermined ligand described in Patent Document 1 are used in combination. Further, since the binder composition of the present invention contains the polymer (A) and the polyvalent cationic organic compound (B), the slurry composition containing the binder composition is dried or the like to form an electrode mixture layer. Is formed, the functional group in the polymer (A) and the cationic group in the polyvalent cationic organic compound (B) interact more strongly by crosslinking or the like. Due to this strong interaction, a rigid network is formed, and the electrode mixture layer does not swell excessively in the electrolytic solution. In addition, since the above-mentioned polyvalent cationic organic compound (B) has a molecular weight of 8000 or less, the polyvalent cationic organic compound (B) does not excessively increase the viscosity of the binder composition. The change in viscosity over time is further suppressed.
Therefore, according to the present invention, while ensuring the viscosity stability of the binder composition, the swelling of the electrode mixture layer in the electrolytic solution can be suppressed, and the secondary battery can exhibit excellent cycle characteristics. .

<Polymer (A)>
The polymer (A) is obtained by forming an electrode mixture layer on a current collector using a slurry composition for a non-aqueous secondary battery electrode prepared using a binder composition. The components contained in the material layer are held so as not to be detached from the electrode mixture layer (that is, an adhesive polymer that functions as a binder).

<< functional group capable of binding to a cationic group >>
The functional group capable of binding to the cationic group of the polymer (A) (hereinafter, may be referred to as “binding functional group”) is not particularly limited, but can interact well with the cationic group. Carboxylic, sulfonic, phosphoric, and hydroxyl groups are included. Among these, a carboxylic acid group, a sulfonic acid group, and a phosphoric acid group are more preferable, and a carboxylic acid group is particularly preferable. When the polymer (A) having these functional groups is used, the swelling of the electrode mixture layer in the electrolytic solution is further suppressed while sufficiently securing the viscosity stability of the binder composition, and Cycle characteristics can be further improved. In addition, the polymer (A) may have only one kind of binding functional group, or may have two or more kinds of binding functional groups.

<< composition of polymer (A) >>
Here, the method for introducing a binding functional group into the polymer (A) is not particularly limited, and the polymer containing the binding functional group (monomer containing a binding functional group) described above is used. May be prepared to obtain a polymer (A) containing a monomer unit having a binding functional group, or a polymer having a binding functional group at the terminal by modifying the terminal of an arbitrary polymer. Combined (A) may be obtained, but the former is preferred. And the polymer (A) containing a monomer unit having a binding functional group may contain a repeating unit other than the monomer unit having a binding functional group.

[Binding functional group-containing monomer unit]
Here, the binding functional group-containing monomer capable of forming the binding functional group-containing monomer unit is preferably a monomer having a carboxylic acid group, a monomer having a sulfonic acid group, or a phosphorus-containing monomer. Examples include monomers having an acid group and monomers having a hydroxyl group.

Examples of the monomer having a carboxylic acid group include monocarboxylic acids and derivatives thereof, dicarboxylic acids and acid anhydrides thereof, and derivatives thereof.
Monocarboxylic acids include acrylic acid, methacrylic acid, crotonic acid and the like.
Examples of the monocarboxylic acid derivative include 2-ethylacrylic acid, isocrotonic acid, α-acetoxyacrylic acid, β-trans-aryloxyacrylic acid, α-chloro-β-E-methoxyacrylic acid, and β-diaminoacrylic acid. No.
Examples of the dicarboxylic acid include maleic acid, fumaric acid, and itaconic acid.
Examples of the dicarboxylic acid derivative include methyl maleic acid, dimethyl maleic acid, phenyl maleic acid, chloromaleic acid, dichloromaleic acid, fluoromaleic acid, monobutyl maleate, monononyl maleate, monodecyl maleate, monododecyl maleate, and maleic acid Monoesters of maleic acid such as monooctadecyl and monofluoroalkyl maleate are exemplified.
Examples of the acid anhydride of dicarboxylic acid include maleic anhydride, acrylic anhydride, methyl maleic anhydride, dimethyl maleic anhydride and the like.
Further, as the monomer having a carboxylic acid group, an acid anhydride which generates a carboxyl group by hydrolysis can also be used.

Examples of the monomer having a sulfonic acid group include vinylsulfonic acid, methylvinylsulfonic acid, (meth) allylsulfonic acid, 3-allyloxy-2-hydroxypropanesulfonic acid, and 2-acrylamido-2-methylpropane. Sulfonic acid and the like.
In the present invention, “(meth) allyl” means allyl and / or methallyl.

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

Examples of the monomer having a hydroxyl group include ethylenically unsaturated alcohols such as (meth) allyl alcohol, 3-buten-1-ol and 5-hexen-1-ol; 2-hydroxyethyl acrylate, acrylic acid 2-hydroxypropyl acid, 2-hydroxyethyl methacrylate, 2-hydroxypropyl methacrylate, di-2-hydroxyethyl maleate, di-4-hydroxybutyl maleate, di-2-hydroxypropyl itaconate and the like alkanol esters of ethylenically unsaturated carboxylic acids; general ^{_{formula: CH 2 = CR Z -COO- (}} C n H 2n O) m -H ( wherein, m is 2-9 integer, n represents 2-4 Wherein R ^Z represents hydrogen or a methyl group) and esters of (meth) acrylic acid 2-hydroxyethyl-2 ′-(meth) acryloyloxyphthalate, 2-hydroxyethyl-2 ′-(meth) acryloyloxysuccinate, etc .; mono (meth) acrylates of dihydroxyesters of dicarboxylic acids; Vinyl ethers such as hydroxyethyl vinyl ether and 2-hydroxypropyl vinyl ether; (meth) allyl-2-hydroxyethyl ether, (meth) allyl-2-hydroxypropyl ether, (meth) allyl-3-hydroxypropyl ether, (meth) Mono (meth) alkylene glycols such as allyl-2-hydroxybutyl ether, (meth) allyl-3-hydroxybutyl ether, (meth) allyl-4-hydroxybutyl ether and (meth) allyl-6-hydroxyhexyl ether ) Allyl ethers; polyoxyalkylene glycol mono (meth) allyl ethers such as diethylene glycol mono (meth) allyl ether and dipropylene glycol mono (meth) allyl ether; glycerin mono (meth) allyl ether, (meth) allyl-2 Mono- (meth) allyl ethers of halogen- and hydroxy-substituted (poly) alkylene glycols such as -chloro-3-hydroxypropyl ether and (meth) allyl-2-hydroxy-3-chloropropyl ether; eugenol, isoeugenol and the like Mono (meth) allyl ethers of polyhydric phenols and halogen-substituted products thereof; alkylene glycols such as (meth) allyl-2-hydroxyethylthioether and (meth) allyl-2-hydroxypropylthioether (Meth) allyl thioethers;
In the present invention, “(meth) acryl” means acryl and / or methacryl.

Among these, the polymer (A) interacts favorably with the polyvalent cationic organic compound (B), and the swelling of the electrode mixture layer in the electrolyte while sufficiently securing the viscosity stability of the binder composition. From the viewpoint of further improving the cycle characteristics of the secondary battery, as the bonding functional group-containing monomer, a monomer having a carboxylic acid group, a monomer having a sulfonic acid group, and A monomer having a phosphate group is preferred, and a monomer having a carboxylic acid group is more preferred. That is, the binding functional group-containing monomer unit is selected from the group consisting of a monomer unit having a carboxylic acid group, a monomer unit having a sulfonic acid group, and a monomer unit having a phosphate group. It is preferably at least one, and more preferably a monomer unit having a carboxylic acid group.
In addition, as the bonding functional group-containing monomer, one type may be used alone, or two or more types may be used in combination at an arbitrary ratio.

  The proportion of the monomer unit having a binding functional group contained in the polymer (A) is preferably 0.1% by mass or more, more preferably 0.5% by mass or more, and more preferably 1% by mass. %, More preferably 20% by mass or less, more preferably 10% by mass or less, even more preferably 6% by mass or less. When the proportion of the monomer unit having a binding functional group contained in the polymer (A) is not more than the above upper limit, the polymer (A) excessively interacts with the polyvalent cationic organic compound (B). Nor. Therefore, aggregation of these components can be suppressed to sufficiently secure the viscosity stability of the binder composition, and the cycle characteristics of the secondary battery can be further improved. When the ratio of the monomer unit having a binding functional group contained in the polymer (A) is equal to or more than the lower limit, the electrolyte solution of the electrode mixture layer while sufficiently securing the viscosity stability of the binder composition. Swelling in the battery can be further suppressed, and the cycle characteristics of the secondary battery can be further improved.

[Repeating unit other than monomer unit having binding functional group]
The repeating unit other than the bonding functional group-containing monomer unit which may be contained in the polymer (A) is not particularly limited, and may be a conjugated diene monomer unit, an alkylene structural unit, or a nitrile group-containing monomer. And a (meth) acrylate monomer unit and an aromatic vinyl monomer unit.

-Conjugated diene monomer unit-
Here, examples of the conjugated diene monomer capable of forming the conjugated diene monomer unit include 1,3-butadiene, isoprene, 2,3-dimethyl-1,3-butadiene, and 1,3-pentadiene. Conjugated diene compounds having 4 or more carbon atoms are exemplified. Among them, 1,3-butadiene is preferred.
These can be used alone or in combination of two or more.

-Alkylene structural unit-
Further, the alkylene structural units has the general formula: -C n H _2n - _[where, n is an integer of 2 or more is a repeating unit composed of only alkylene structure represented by.
Here, the alkylene structural unit may be linear or branched, but from the viewpoint of improving the dispersion stability of the slurry composition for a non-aqueous secondary battery electrode, the alkylene structural unit is straight. It is preferably a 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, the carbon number of the alkylene structural unit is 4 or more (that is, n in the above general formula is an integer of 4 or more. Is preferred.

The method of introducing the alkylene structural unit into the polymer (A) is not particularly limited, but for example, the following method (1) or (2):
(1) A method of preparing a copolymer from a monomer composition containing a conjugated diene monomer and hydrogenating the copolymer to convert a conjugated diene monomer unit into an alkylene structural unit (2) 1) A method of preparing a copolymer from a monomer composition containing a 1-olefin monomer. Among them, the method (1) is preferable because the production of the polymer (A) is easy.

The conjugated diene monomer used in the above method (1) includes C4 or more such as 1,3-butadiene, isoprene, 2,3-dimethyl-1,3-butadiene and 1,3-pentadiene. Examples thereof include conjugated diene compounds, and among them, 1,3-butadiene is preferable. That is, the alkylene structural unit is preferably a structural unit (hydrogenated conjugated diene unit) obtained by hydrogenating a conjugated diene monomer unit, and is preferably 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 by using a known method such as an oil layer hydrogenation method or an aqueous layer hydrogenation method.
The 1-olefin monomer used in the method (2) includes, for example, 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.

-Nitrile group-containing monomer unit-
Further, examples of the nitrile group-containing monomer capable of forming the 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, acrylonitrile and methacrylonitrile are preferred as the nitrile group-containing monomer, and acrylonitrile is more preferred.
These can be used alone or in combination of two or more.

-(Meth) acrylate monomer unit-
Examples of the (meth) acrylate monomer capable of forming the (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, and stearyl acrylate Esters: methyl methacrylate, ethyl methacrylate, n-propyl methacrylate, isopropyl methacrylate, n-butyl Methacrylate, t-butyl methacrylate, isobutyl methacrylate, n-pentyl methacrylate, isopentyl methacrylate, hexyl methacrylate, heptyl methacrylate, octyl methacrylate, 2-ethylhexyl methacrylate, nonyl methacrylate, decyl methacrylate, lauryl methacrylate, n-tetradecyl methacrylate, stearyl methacrylate And methacrylic acid alkyl esters. Among them, methyl acrylate, ethyl acrylate, n-butyl acrylate, 2-ethylhexyl acrylate, methyl methacrylate, ethyl methacrylate, n-butyl methacrylate, 2-ethylhexyl methacrylate are preferable, and n-butyl acrylate, ethyl methacrylate, and 2-ethylhexyl acrylate are more preferable. preferable.
These can be used alone or in combination of two or more.

-Aromatic vinyl monomer unit-
Further, examples of the aromatic vinyl monomer capable of forming an aromatic vinyl monomer unit include styrene, α-methylstyrene, butoxystyrene, and vinylnaphthalene. Among them, styrene is preferred.
These can be used alone or in combination of two or more.

  Among the repeating units other than the above-mentioned bonding functional group-containing monomer unit, the solubility of the polymer (A) in the solvent of the binder composition and the dispersibility in the conductive material and the like are enhanced, and as a result, the binder composition From the viewpoint of further improving the cycle characteristics of the secondary battery by further suppressing the swelling of the electrode mixture layer in the electrolyte while ensuring the sufficient viscosity stability of the polymer (A), the polymer (A) is composed of a nitrile group. It is preferable to include a monomer unit containing at least one of a conjugated diene monomer unit and an alkylene structural unit, and more preferably a monomer unit containing a nitrile group and an alkylene structural unit.

  And the ratio of the nitrile group-containing monomer unit contained in the polymer (A) is preferably at least 5 mass%, more preferably at least 7 mass%, further preferably at least 9 mass%. The content is particularly preferably 10% by mass or more, particularly preferably 35% by mass or less, more preferably 29% by mass or less, and even more preferably 23% by mass or less. When the ratio of the nitrile group-containing monomer unit contained in the polymer (A) is equal to or less than the above upper limit, the swelling of the electrode mixture layer in the electrolyte is further suppressed, and the cycle characteristics of the secondary battery are improved. Can be even higher. When the proportion of the nitrile group-containing monomer unit contained in the polymer (A) is at least the above lower limit, the solubility of the polymer (A) in the solvent of the binder composition is increased, and Viscosity stability can be sufficiently ensured.

  Further, the total of the ratio of the conjugated diene monomer unit and the alkylene structural unit contained in the polymer (A) is preferably 30% by mass or more, more preferably 40% by mass or more, and 90% by mass. Or less, more preferably 75% by mass or less. If the sum of the proportions of the conjugated diene monomer unit and the alkylene structural unit contained in the polymer (A) is equal to or less than the upper limit, the solubility of the polymer (A) in the solvent of the binder composition may be impaired. In addition, the viscosity stability of the binder composition can be sufficiently ensured. Further, when the total of the ratio of the conjugated diene monomer unit and the alkylene structural unit contained in the polymer (A) is equal to or more than the above lower limit, the dispersing ability for the polymer (A) conductive material and the like increases. Then, the viscosity stability of the binder composition can be sufficiently ensured, and the cycle characteristics of the secondary battery can be further improved.

  The proportion of the repeating unit other than the bonding functional group-containing monomer unit, the conjugated diene monomer unit, the alkylene structural unit, and the nitrile group-containing monomer unit contained in the polymer (A) is 0% by mass. It can be not less than 60% by mass.

[Method for Preparing Polymer (A)]
The method for preparing the above-mentioned polymer (A) is not particularly limited, but the polymer (A) may be obtained, for example, by polymerizing a monomer composition containing the above-described monomer to obtain a copolymer. Can be prepared by hydrogenating (hydrogenating) the obtained copolymer.

Here, the content ratio of each monomer in the monomer composition used for preparing the polymer (A) can be determined according to the content ratio of each repeating unit in the polymer (A).
The polymerization method 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. Further, as the polymerization reaction, any reaction such as ionic polymerization, radical polymerization, and living radical polymerization can be used.
Furthermore, the method for hydrogenating the copolymer is not particularly limited, and a general method using a catalyst (for example, see WO2012 / 165120, WO2013 / 080989, and JP-A-2013-8485). Can be used.

<Polyvalent cationic organic compound (B)>
The polyvalent cationic organic compound (B) is not particularly limited as long as it is an organic compound having a plurality of cationic groups in one molecule. The cationic group, for example, a substituted or unsubstituted amino group _{^{(-NH 2, -NHR 1, -NR}} 1 R 2, -N + R 1 R 2 R 3. ^Here, R 1 to R ³ is optionally , A substituted or unsubstituted imino group (= NH, ４NR ^4, wherein R ⁴ represents an arbitrary substituent), a nitrogen-containing functional group such as an oxazoline group (an amide group is represented by Excluding). Among these, the polyvalent cationic organic compound (B) interacts well with the polymer (A), and the swelling of the electrode mixture layer in the electrolyte while ensuring the sufficient viscosity stability of the binder composition. the was further suppressed, from the viewpoint of further improving the cycle characteristics of the secondary battery, a primary amino group (unsubstituted amino group, -NH _2), secondary amino group (-NHR ^1), a substituted or Unsubstituted imino groups are preferred. The polyvalent cationic organic compound (B) may have only one kind of cationic group, or may have two or more kinds of cationic groups.
In the present invention, when the polymer, which is an organic compound having two or more cationic groups, has a functional group capable of binding to the cationic group, the polymer is not a polymer (A) but a polyvalent polymer. It shall correspond to the cationic organic compound (B).

<Molecular weight of polyvalent cationic organic compound (B)>
Here, the molecular weight of the polyvalent cationic organic compound (B) (when the polyvalent cationic organic compound (B) is a polymer, indicates the “number average molecular weight”) must be 8000 or less. Yes, it is preferably 2000 or less, more preferably 1800 or less, still more preferably 1600 or less, and particularly preferably 1500 or less. When the molecular weight of the polyvalent cationic organic compound (B) exceeds 8,000, the binder composition excessively thickens, it is not possible to sufficiently secure the viscosity stability, and the cycle characteristics of the secondary battery deteriorate. On the other hand, the molecular weight of the polyvalent cationic organic compound (B) is 60 or more from the viewpoint of sufficiently suppressing the swelling of the electrode mixture layer in the electrolytic solution and further improving the cycle characteristics of the secondary battery. It is more preferably 100 or more.
In the present invention, when the polyvalent cationic organic compound (B) is a polymer, the number average molecular weight can be determined as a polystyrene-equivalent molecular weight measured by gel permeation chromatography (developing solvent: tetrahydrofuran). it can.

<Example of polyvalent cationic organic compound (B)>
As the polyvalent cationic organic compound (B), a non-polymeric polyvalent cationic organic compound (B) can be used as long as the molecular weight is within the above-mentioned range, and a polyvalent cationic organic compound (B) can be used. The organic compound (B) can also be used.
Here, as the non-polymeric polyvalent cationic organic compound (B), ethylenediamine, diethylenetriamine, triethylenetetramine, phenyldiamine, 4,4′-diaminodiphenylether, N, N′-bis (3-phenyl- 2-propenylidene) -1,6-hexanediamine, bisanilines and the like.
Examples of the polyvalent cationic organic compound (B) which is a polymer include polyethyleneimine; polyethyleneimine derivatives such as poly-N-hydroxylethyleneimine and sodium salt of carboxymethylated polyethyleneimine; polypropyleneimine; Polyallylamine; Polyallylamine derivatives such as polydimethyldiallylammonium halide; Aminoethylated acrylic polymer obtained by aminoethylating acrylic acid polymer; Substituted or unsubstituted amino group Cationized cellulose obtained by modifying a cellulose derivative (hydroxyethyl cellulose, carboxymethyl cellulose, etc.) with a cationizing agent is exemplified.
These can be used alone or in combination of two or more. Among these, from the viewpoint of further suppressing the swelling of the electrode mixture layer in the electrolyte while sufficiently securing the viscosity stability of the binder composition, from the viewpoint of further improving the cycle characteristics of the secondary battery, polyethyleneimine is used. , Polyethyleneimine derivatives, N, N'-bis (3-phenyl-2-propenylidene) -1,6-hexanediamine, polyallylamine, and diethylenetriamine are more preferred.

<Blending amount of polyvalent cationic organic compound (B)>
The compounding amount of the polyvalent cationic organic compound (B) having a molecular weight within the above range is preferably 0.1 part by mass or more per 100 parts by mass of the polymer (A), and more preferably 0.2 part by mass. The amount is more preferably at least 0.5 part by mass, still more preferably at least 2 parts by mass, particularly preferably at most 20 parts by mass, and preferably at most 10 parts by mass. More preferably, it is even more preferably 6 parts by mass or less. When the amount of the polyvalent cationic organic compound (B) is excessive, the viscosity stability of the binder composition is rather lowered. However, when the amount of the polyvalent cationic organic compound (B) is 20 parts by mass or less, the viscosity stability of the binder composition can be sufficiently ensured. When the compounding amount of the polyvalent cationic organic compound (B) is 0.1 parts by mass or more, the polymer (A) and the polyvalent cationic organic compound (B) are more rigid in the electrode mixture layer. A network can be formed. Therefore, the swelling of the electrode mixture layer in the electrolytic solution can be further suppressed, and the cycle characteristics of the secondary battery can be further improved.

<Solvent>
As the solvent of the binder composition for a non-aqueous secondary battery electrode, an organic solvent is preferable. The organic solvent is not particularly limited and includes, for example, methanol, ethanol, n-propanol, isopropanol, n-butanol, isobutanol, t-butanol, pentanol, hexanol, heptanol, octanol, nonanol, decanol, amyl alcohol Alcohols such as acetone; ketones such as acetone, methyl ethyl ketone and cyclohexanone; esters such as ethyl acetate and butyl acetate; ethers such as diethyl ether, dioxane and tetrahydrofuran; N, N-dimethylformamide, N-methylpyrrolidone (NMP) Amide-based polar organic solvents; aromatic hydrocarbons such as toluene, xylene, chlorobenzene, orthodichlorobenzene, and paradichlorobenzene; and the like. These may be used alone or as a mixture of two or more.
Among them, as the 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 includes, in addition to the above components, a binder (polyvinylidene fluoride, polyacrylonitrile, polyacrylate, etc.) other than the polymer (A), a reinforcing material, Components such as a leveling agent, a viscosity modifier, and an electrolyte additive may be contained in the binder composition. These are not particularly limited as long as they do not affect the battery reaction, and known ones, for example, those described in International Publication WO 2012/115096 can be used. One of these components may be used alone, or two or more thereof may be used in combination at an arbitrary ratio.

<Swelling degree of electrolyte solution of film composed of binder composition>
The electrolyte swelling degree of the film obtained by drying the binder composition of the present invention containing the above components is preferably less than 2000% by mass, more preferably less than 1000% by mass, and more preferably 800% by mass. %, More preferably less than 600% by mass. When the degree of swelling of the electrolyte solution of the film composed of the binder composition is less than 2000% by mass, the cycle characteristics of the secondary battery can be sufficiently improved. Further, the degree of swelling of the electrolyte solution of the film composed of the binder composition is usually 100% by mass or more.
In addition, the degree of swelling of the electrolyte solution of the film composed of the binder composition can be measured using the method described in Examples of the present specification.

(Slurry composition for non-aqueous secondary battery electrode)
The slurry composition for a non-aqueous secondary battery electrode of the present invention includes an electrode active material and the binder composition described above, and optionally further includes a conductive material and other components. That is, the slurry composition of the present invention contains an electrode active material, the above-mentioned polymer (A), the above-mentioned polyvalent cationic organic compound (B), and a solvent, and optionally contains a conductive material, It further contains other components. And since the slurry composition of the present invention contains the binder composition described above, the electrode mixture layer formed using the slurry composition of the present invention is suppressed from swelling in the electrolytic solution, and Excellent cycle characteristics can be exhibited in the secondary battery.

<Electrode active material>
Here, the electrode active material is a material that transfers electrons at the electrode of the non-aqueous secondary battery. For example, when the non-aqueous secondary battery is a lithium ion secondary battery, a material capable of occluding and releasing lithium is usually used as the electrode active material.
In the following, a case where the slurry composition for a non-aqueous secondary battery electrode is a slurry composition for a lithium ion secondary battery electrode will be described as an example, but the present invention is not limited to the following example.

The positive electrode active material for the lithium ion secondary battery is not particularly limited, and includes lithium-containing cobalt oxide (LiCoO ₂ ), lithium manganate (LiMn ₂ O ₄ ), and lithium-containing nickel oxide (LiNiO _2). ), lithium-containing composite oxide of Co-Ni-Mn (Li ( Co Mn Ni) O 2), lithium-containing composite oxide of _Ni-Mn-Al, lithium-containing composite oxide of Ni-Co-Al, olivine lithium iron phosphate (LiFePO _4), lithium represented by the 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) excess spinel _{compound, Li [Ni 0.17 Li 0.2 Co} 0.07 Mn 0.56] O 2, LiNi Known positive electrode active material such _.5 Mn _1.5 O ₄ and the like.
The amount and particle size of the positive electrode active material are not particularly limited, and may be the same as those of the conventionally used positive electrode active material.

  Examples of the negative electrode active material for a 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 a main skeleton of carbon, into which lithium can be inserted (also referred to as “doping”). Examples of the carbon-based negative electrode active material include a carbonaceous material and graphite. Quality material.
Examples of the carbonaceous material include easily graphitic carbon and non-graphitizable carbon having a structure close to an amorphous structure represented by glassy carbon.
Here, as the graphitizable carbon, for example, a carbon material obtained from tar pitch obtained from petroleum or coal is used. Specific examples include coke, mesocarbon microbeads (MCMB), mesophase pitch-based carbon fibers, and pyrolysis vapor grown carbon fibers.
Examples of the non-graphitizable carbon include a phenol resin fired body, polyacrylonitrile-based carbon fiber, pseudo isotropic carbon, a furfuryl alcohol resin fired body (PFA), and hard carbon.

Furthermore, examples of the graphite material include natural graphite and artificial graphite.
Here, examples of artificial graphite include, for example, artificial graphite obtained by heat-treating carbon containing graphitizable carbon mainly at 2800 ° C. or more, graphitized MCMB heat-treated MCMB at 2000 ° C. or more, and mesophase pitch-based carbon fiber at 2000 ° C. Graphitized mesophase pitch-based carbon fibers heat-treated as described above can be mentioned.

  The metal-based negative electrode active material is an active material containing a metal, and usually includes a lithium-insertable element in its structure, and has a theoretical electric capacity per unit mass of 500 mAh / in which lithium is inserted. The active material is g or more. As the metal-based active material, for example, a lithium metal, a simple metal capable of forming a lithium alloy (eg, Ag, Al, Ba, Bi, Cu, Ga, Ge, In, Ni, P, Pb, Sb, Si, Sn) , Sr, Zn, Ti, etc.) and their alloys, and their oxides, sulfides, nitrides, silicides, carbides, phosphides and the like. Among these, an active material containing silicon (silicon-based negative electrode active material) is preferable as the metal-based negative electrode active material. The use of a silicon-based negative electrode active material can increase the capacity of a lithium ion secondary battery.

As the silicon-based negative electrode active material, for example, silicon (Si), an alloy containing silicon, SiO, SiO _x , a composite of a conductive carbon and a Si-containing material obtained by coating or complexing the conductive material with a conductive carbon And the like. One of these silicon-based negative electrode active materials may be used alone, or two or more thereof may be used in combination.
The amount and the particle size of the negative electrode active material are not particularly limited, and may be the same as those of a conventionally used negative electrode active material.

<Binder composition for non-aqueous secondary battery electrode>
As the binder composition for a non-aqueous secondary battery electrode, a binder composition for a non-aqueous secondary battery electrode containing the polymer (A) and the polyvalent cationic organic compound (B) described above is used.

  Here, the content ratio of the binder composition in the slurry composition for a non-aqueous secondary battery electrode is such that the amount of the polymer (A) is 0.1 parts by mass or more per 100 parts by mass of the electrode active material. The amount is preferably 0.3 parts by mass or more, more preferably 3 parts by mass or less, and even more preferably 1.5 parts by mass or less. When the slurry composition contains the binder composition in such an amount that the amount of the polymer (A) falls within the above range, the swelling of the electrode mixture layer in the electrolyte is further suppressed, and the Cycle characteristics can be further improved.

<Conductive material>
The conductive material is for ensuring electrical contact between the electrode active materials. Examples of the conductive material include carbon black (eg, acetylene black, Ketjen Black (registered trademark), furnace black, etc.), single-wall or multi-wall carbon nanotubes (multi-wall carbon nanotubes include a cup-stacked 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 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.

  The content ratio of the conductive material in the slurry composition for a non-aqueous secondary battery electrode is preferably at least 0.1 part by mass, more preferably at least 0.5 part by mass, per 100 parts by mass of the electrode active material. Is more preferably 5 parts by mass or less, and more preferably 3 parts by mass or less. When the amount of the conductive material is within the above range, sufficient electrical contact between the electrode active materials can be ensured, and the secondary battery can exhibit excellent battery characteristics (such as cycle characteristics).

<Other ingredients>
The other components that can be added to the slurry composition are not particularly limited, and include the same components as the other components that can be added to the binder composition described above. As the other components, one type may be used alone, or two or more types may be used in combination at an arbitrary ratio.

<Preparation of slurry composition>
The above-mentioned slurry composition can be prepared by dissolving or dispersing the above components in a solvent such as an organic solvent. Specifically, a ball mill, a sand mill, a bead mill, a pigment disperser, a crusher, an ultrasonic disperser, a homogenizer, a planetary mixer, by mixing the above components and a solvent using a mixer such as a fill mix. , A slurry composition can be prepared. In addition, you may use the solvent contained in a binder composition as a solvent used for preparation of a slurry composition.

Here, the order of mixing the above components in the solvent is not particularly limited, and may be any order. Specifically, when preparing the slurry composition, the above components can be mixed, for example, in any order of the following (1) to (3).
(1) The above components are mixed at once.
(2) A binder composition containing the polymer (A) and the polyvalent cationic organic compound (B) is mixed with a conductive material to obtain a conductive material paste composition for a non-aqueous secondary battery electrode. The electrode active material is added to and mixed with the conductive material paste composition for an aqueous secondary battery electrode.
(3) After mixing the conductive material and the electrode active material, a binder composition containing the polymer (A) and the polyvalent cationic organic compound (B) is added to the obtained mixture and mixed.

Among the above, it is preferable that the above components are mixed in the order of the above (1) or (2). When the order of (2) is adopted, that is, the binder composition and the conductive material are mixed in advance, and the conductive material and the binder composition described above are included (that is, the conductive material, the polymer (A), When the conductive material paste composition for a non-aqueous secondary battery electrode (including the polyvalent cationic organic compound (B) and the solvent) is used, the polymer (A) is adsorbed on the surface of the conductive material to form the conductive material. It can be dispersed well. As a result, the secondary battery can exhibit excellent battery characteristics (such as cycle characteristics).
In the present invention, the conductive material paste composition for a non-aqueous secondary battery electrode is an intermediate product for preparing the slurry composition for a non-aqueous secondary battery electrode of the present invention. It is a paste-like composition containing a material, a polymer (A), a polyvalent cationic organic compound (B), and a solvent, but not containing an electrode active material.

(Electrode for non-aqueous secondary battery)
The secondary battery electrode of the present invention includes a current collector and an electrode mixture layer formed on the current collector, and the electrode mixture layer is formed using the above-described slurry composition for a non-aqueous secondary battery electrode. Is formed. That is, the electrode mixture layer contains at least the electrode active material, the polymer (A), and the polyvalent cationic organic compound (B) having a molecular weight of a predetermined value or less. Here, the polymer (A) and the polyvalent cationic organic compound (B) may form a crosslinked structure. That is, the electrode mixture layer may contain a crosslinked product of the polymer (A) and the polyvalent cationic organic compound (B). In addition, each component contained in the electrode mixture layer was included in the slurry composition for a non-aqueous secondary battery electrode, and the preferred abundance ratio of each component was determined in the slurry composition. It is the same as the preferred abundance ratio of each of the components.
In the electrode for a non-aqueous secondary battery of the present invention, since the slurry composition containing the binder composition for a non-aqueous secondary battery electrode of the present invention is used, the polymer (A) and the polycationic organic compound are used. A rigid electrode mixture layer in which the compound (B) interacts strongly can be favorably formed on the current collector. Therefore, when the electrode is used, swelling of the electrode mixture layer in the electrolytic solution is suppressed, and a secondary battery having excellent battery characteristics such as cycle characteristics can be obtained.

<Method of manufacturing electrode>
In addition, the electrode for a non-aqueous secondary battery of the present invention includes, for example, a step of applying the above-mentioned slurry composition on a current collector (application step), and drying the slurry composition applied on the current collector. To form an electrode mixture layer on the current collector (drying step).

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

  Here, as the current collector to which the slurry composition is applied, a material having electrical conductivity and being electrochemically durable is used. Specifically, for example, a current collector made of iron, copper, aluminum, nickel, stainless steel, titanium, tantalum, gold, platinum, or the like can be used as the current collector. One of the above materials may be used alone, or two or more thereof may be used in combination at an arbitrary ratio.

<< 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, warm air, hot air, a drying method using low-humidity air, a vacuum drying method, an infrared ray, an electron beam, or the like can be used. A drying method by irradiation may be used. By drying the slurry composition on the current collector in this way, an electrode mixture layer is formed on the current collector, and a secondary battery electrode including the current collector and the electrode mixture layer can be obtained. it can. The drying temperature is preferably from 60C to 200C, more preferably from 90C to 150C.
For example, a polymer having at least one of a carboxylic acid group, a sulfonic acid group, and a phosphoric acid group is used as the polymer (A), and a compound containing an amino group is used as the polyvalent cationic organic compound (B). In this case, the polymer (A) and the polyvalent cationic organic compound (B) are cross-linked by an amide bond, thereby further suppressing the swelling of the electrode mixture layer in the electrolytic solution, thereby reducing the cycle of the secondary battery. The characteristics can be further improved.

  After the drying step, the electrode mixture layer may be subjected to a pressure treatment using a die press or a roll press. The pressure treatment can improve the adhesion between the electrode mixture layer and the current collector. When the electrode mixture layer contains a curable polymer, the polymer is preferably cured after the formation of the electrode mixture layer.

(Non-aqueous secondary battery)
The non-aqueous secondary battery of the present invention includes a positive electrode, a negative electrode, an electrolytic solution, and a separator, and uses the secondary battery electrode of the present invention as at least one of the positive electrode and the negative electrode. And since the non-aqueous secondary battery of the present invention includes the electrode for a non-aqueous secondary battery of the present invention, it has excellent battery characteristics such as cycle characteristics.
In the following, a case where the non-aqueous 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 above-mentioned non-aqueous secondary battery electrode that can be used for the non-aqueous secondary battery of the present invention is not particularly limited, and is a known electrode used in the manufacture of a secondary battery. Electrodes can be used. Specifically, as an electrode other than the above-mentioned non-aqueous secondary battery electrode, an electrode obtained by forming an electrode mixture layer on a current collector by using a known manufacturing method can be used.

<Electrolyte>
As the electrolyte, an organic electrolyte obtained by dissolving a supporting electrolyte in an organic solvent is usually used. As a supporting electrolyte of the lithium ion secondary battery, for example, a lithium salt is used. As the lithium salt, for example, LiPF ₆ , LiAsF ₆ , LiBF ₄ , LiSbF ₆ , LiAlCl ₄ , LiClO ₄ , CF ₃ SO ₃ Li, C ₄ F ₉ SO ₃ Li, CF ₃ COOLi, (CF ₃ CO) ₂ NLi , (CF ₃ SO ₂ ) ₂ NLi, (C ₂ F ₅ SO ₂ ) NLi, and the like. Among them, LiPF ₆ , LiClO ₄ , and CF ₃ SO ₃ Li are preferred because they are easily soluble in a solvent and exhibit a high degree of dissociation, and LiPF ₆ is particularly preferred. One type of electrolyte may be used alone, or two or more types may be used in combination at an arbitrary ratio. In general, the higher the dissociation degree of the supporting electrolyte, the higher the lithium ion conductivity tends to be. Therefore, the lithium ion conductivity can be adjusted depending on the type of the supporting electrolyte.

The organic solvent used for 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; and sulfur-containing compounds such as sulfolane and dimethyl sulfoxide. And the like are preferably used. Further, a mixture of these solvents may be used. Among them, carbonates are preferably used because they have a high dielectric constant and a wide stable potential region.
Note that the concentration of the electrolyte in the electrolytic solution can be appropriately adjusted. Further, known additives can be added to the electrolytic solution.

<Separator>
The separator is not particularly limited, and for example, a separator described in JP-A-2012-204303 can be used. Among these, polyolefin-based (from the viewpoint that the thickness of the entire separator can be reduced, and thereby the capacity per volume can be increased by increasing the ratio of the electrode active material in the secondary battery, A microporous membrane made of a resin such as polyethylene, polypropylene, polybutene, or polyvinyl chloride) is preferred.

<Method of manufacturing secondary battery>
In the secondary battery of the present invention, for example, a positive electrode and a negative electrode are overlapped with a separator interposed therebetween, and if necessary, wound or folded according to the shape of the battery, placed in a battery container, and electrolyzed in the battery container. It can be manufactured by injecting a liquid and sealing it. If necessary, a fuse, an overcurrent prevention element such as a PTC element, an expanded metal, a lead plate, or the like may be provided in order to prevent an increase in the pressure inside the secondary battery and the occurrence of overcharge and overdischarge. The shape of the secondary battery may be, for example, any of a coin type, a button type, a sheet type, a cylindrical type, a square type, a flat type, and the like.

Hereinafter, the present invention will be specifically described based on examples, but the present invention is not limited to these examples. In the following description, “%”, “ppm” and “parts” representing amounts are based on mass unless otherwise specified.
Further, in a polymer produced by copolymerizing a plurality of types of monomers, unless otherwise specified, the ratio of monomer units formed by polymerizing a certain monomer is usually And the ratio of the certain monomer to all the monomers used in the polymerization of the polymer (preparation ratio).
In Examples and Comparative Examples, the viscosity stability of the binder composition, the degree of swelling of the electrolyte solution of the film made of the binder composition, and the cycle characteristics of the secondary battery were evaluated by the following methods.

<Viscosity stability>
The viscosity M0 immediately after the preparation of the binder composition and the viscosity M1 after storage at 60 ° C. for 7 days were measured. The viscosity was measured using a B-type viscometer at a temperature of 25 ° C. 4. Rotor rotation speed: 60 rpm
Then, the viscosity change rate ΔM (= M1 / M0 × 100 (%)) was calculated and evaluated according to the following criteria. The smaller the value of the viscosity change rate ΔM, the higher the viscosity stability of the binder composition.
A: Viscosity change rate ΔM is less than 110% B: Viscosity change rate ΔM is 110% or more and less than 120% C: Viscosity change rate ΔM is 120% or more and less than 130% D: Viscosity change rate ΔM is 130% or more and less than 150% E : Viscosity change rate ΔM is 150% or more <electrolyte swelling degree>
The binder composition in the Teflon (registered trademark) petri dish was dried at 120 ° C. for 12 hours to obtain a film having a thickness of 1 mm. The film was punched into a circle having a diameter of 1.6 mm to form a measurement sample (pseudo-electrode mixture layer), and the weight W0 of the measurement sample was measured.
After the obtained data for measurement was stored in an electrolyte at 60 ° C. for 72 hours, the electrolyte adhering to the sample for measurement was wiped off, and the weight W1 of the sample for measurement was measured.
As the electrolyte, ethylene carbonate (EC), propylene carbonate (PC), ethyl methyl carbonate (EMC), and propyl propionate (PP) were used as EC: PC: EMC: PP = 2: 1. LiPF ₆ was dissolved at a concentration of 1 mol / L in a mixed solvent obtained by mixing at a ratio of 1: 1: 6 (mass ratio), and a mixture obtained by adding 1.5 vol% of vinylene carbonate as an additive was used.
Then, the electrolyte swelling degree ΔW (= W1 / W0 × 100 (%)) was calculated and evaluated according to the following criteria. It shows that the smaller the value of the electrolytic solution swelling ΔW is, the more the swelling of the electrode mixture layer obtained using the binder composition in the electrolytic solution can be suppressed.
A: Electrolyte swelling degree ΔW is less than 600% B: Electrolyte swelling degree ΔW is 600% or more and less than 800% C: Electrolyte swelling degree ΔW is 800% or more and less than 1000% D: Electrolyte swelling degree ΔW is 1000% or more E: less than 2000% E: electrolyte swelling degree ΔW is 2000% or more <Cycle characteristics>
The operation of charging the produced secondary battery to 4.35 V at 0.2 C and discharging it to 3.0 V in a 25 ° C. environment was repeated three times. Thereafter, an operation of charging at 1 CmA until the battery voltage becomes 4.35 V and discharging at 1 CmA until the battery voltage becomes 3.0 V under a 45 ° C. environment was repeated 100 times. Then, a capacity retention ratio ΔC = (C1 / C0) × 100 (%) was calculated from the first discharge capacity (C0) and the 100th discharge capacity (C1), and evaluated based on the following criteria. The higher the value of the capacity retention ratio, the smaller the decrease in the discharge capacity and the more excellent the cycle characteristics.
A: Capacity maintenance rate ΔC is 85% or more B: Capacity maintenance rate ΔC is 80% or more and less than 85% C: Capacity maintenance rate ΔC is 75% or more and less than 80% D: Capacity maintenance rate ΔC is 70% or more and less than 75% E : Capacity maintenance ratio ΔC is less than 70%

(Example 1)
<Preparation of polymer (A)>
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 methacrylic acid as a monomer containing a binding functional group, and acrylonitrile 10 as a monomer containing a nitrile group , 25 parts of 2-ethylhexyl acrylate as a (meth) acrylate monomer, and 0.5 part of t-dodecyl mercaptan as a molecular weight modifier were sequentially charged, and the inside gas was replaced with nitrogen three times. After that, 60 parts of 1,3-butadiene as a conjugated diene monomer was added. While keeping the metal bottle at 5 ° C., 0.1 part of cumene hydroperoxide as a polymerization initiator was added, and polymerization was carried out for 16 hours while rotating the metal bottle. Then, after adding 0.1 part of a 10% by mass aqueous solution of hydroquinone as a polymerization terminator to terminate the polymerization reaction, residual monomers were removed using a rotary evaporator at a water temperature of 60 ° C., and an aqueous dispersion of the polymer was obtained. (Solid content: about 30% by mass).
Then, the aqueous dispersion prepared above and the palladium catalyst (1% by mass) were placed in an autoclave such that the palladium content based on the dry weight of the polymer contained in the aqueous dispersion obtained above became 750 ppm. (A solution in which a palladium acetate acetone solution and ion-exchanged water were mixed at a ratio of 1: 1 (mass ratio)) was added. Then, a hydrogenation reaction was performed at a hydrogen pressure of 3 MPa and a temperature of 50 ° C. for 6 hours to obtain a hydrogenated polymer.
Subsequently, NMP as a solvent was added to the obtained aqueous dispersion of the hydrogenated polymer so that the solid content concentration of the hydrogenated polymer became 7%. Then, vacuum distillation was performed at 90 ° C. to remove water and excess NMP, and an NMP solution (solid content: 8%) of the polymer (A) (hydrogenated polymer) was obtained.
<Preparation of polyvalent cationic organic compound (B)>
Polyethyleneimine (number average molecular weight: 600, "Epomin SP-006", manufactured by Nippon Shokubai Co., Ltd.) was prepared as the polyvalent cationic organic compound (B). Then, an NMP solution of this polyethyleneimine (solid concentration: 8%) was prepared.
<Preparation of binder composition for positive electrode>
The above-mentioned NMP solution of the polymer (A) and the NMP solution of polyethyleneimine were mixed so that the mixing ratio was 100: 5 in terms of solid content, to obtain a binder composition for a positive electrode. Using this binder composition for a positive electrode, the viscosity stability and the degree of swelling of the electrolytic solution were evaluated. Table 1 shows the results.
<Preparation of slurry composition for positive electrode>
100 parts of lithium cobalt oxide (LiCoO ₂ , volume average particle diameter: 12 μm) as a positive electrode active material and Ketjen black (Lion Co., Ltd., special oil furnace carbon powder) as a conductive material: number particle diameter 40 nm, specific surface area 800 m ^{2 /} g) 1.5 parts of the polymer (A), 0.6 parts (in terms of solid content) of the binder composition for the positive electrode, and NMP of polyvinylidene fluoride (PVDF) as a binder A slurry composition for a positive electrode was prepared by mixing 0.6 part (in terms of solid content) of the solution and NMP as an additional solvent with a planetary mixer. In addition, the amount of additional NMP is in the range of 5000 ± 200 mPa · s when the viscosity of the obtained slurry composition for a positive electrode (using a B-type viscometer; temperature: 25 ° C., rotor: No. 4, rotor speed: 60 rpm). Adjusted to be inside.
<Preparation of positive electrode>
The obtained positive electrode slurry composition was applied to one surface of a current collector made of an aluminum foil having a thickness of 15 μm so that the applied amount after drying was 20 mg / cm ² . Then, the applied slurry composition was dried at 90 ° C. for 20 minutes and at 120 ° C. for 20 minutes, and then heat-treated at 150 ° C. for 2 hours to obtain a positive electrode raw material. Then, the obtained positive electrode raw material was rolled by a roll press to obtain a positive electrode having a positive electrode mixture layer having a density of 3.7 g / cm ^{3 on} an aluminum foil (current collector).
<Preparation of negative electrode>
100 parts of spherical artificial graphite (volume average particle diameter: 12 μm) as a negative electrode active material, 1 part of a styrene-butadiene copolymer as a binder, 1 part of carboxymethyl cellulose as a thickener, and an appropriate amount as a dispersion medium Was mixed with a planetary mixer to prepare a slurry composition for a negative electrode.
The obtained negative electrode slurry composition was applied to one surface of a current collector made of a copper foil having a thickness of 15 μm so that the application amount after drying was 10 mg / cm ² . Then, the applied slurry composition was dried at 60 ° C. for 20 minutes and at 120 ° C. for 20 minutes to obtain a negative electrode raw material. Then, the obtained negative electrode raw material was rolled by a roll press to obtain a negative electrode having a negative electrode mixture layer having a density of 1.5 g / cm ^{3 on} a copper foil (current collector).
<Preparation of separator>
A single-layer polypropylene separator (width 65 mm, length 500 mm, thickness 25 μm, manufactured by a dry method, porosity 55%) was cut into a square of 4.4 cm × 4.4 cm.
<Manufacture of secondary batteries>
An aluminum packaging exterior was prepared as the exterior of the battery. Then, the positive electrode obtained above was cut into a square of 4 cm × 4 cm, and arranged so that the surface on the side of the current collector was in contact with the exterior of the aluminum packaging material. The square separator obtained above was disposed on the positive electrode mixture layer of the positive electrode. Further, the negative electrode obtained above was cut into a 4.2 cm × 4.2 cm square, and this was disposed on a separator such that the surface of the negative electrode mixture layer side faced the separator. Further, the battery was filled with an electrolytic solution, and then heat sealed at 150 ° C. to close the opening of the aluminum packaging material, and the aluminum packaging material was closed to obtain a lithium ion secondary battery. As the electrolyte, ethylene carbonate (EC), propylene carbonate (PC), ethyl methyl carbonate (EMC), and propyl propionate (PP) were used as EC: PC: EMC: PP = 2: 1. LiPF ₆ was dissolved at a concentration of 1 mol / L in a mixed solvent obtained by mixing at a ratio of 1: 1: 6 (mass ratio), and a mixture obtained by adding 1.5 vol% of vinylene carbonate as an additive was used.
Then, the cycle characteristics were evaluated using the obtained lithium ion secondary battery. Table 1 shows the results.

(Examples 2, 4 to 15)
In the preparation of the polymer (A), the polymer (A), the binder composition for the positive electrode, the slurry composition for the positive electrode, and the positive electrode were prepared in the same manner as in Example 1 except that the monomer composition shown in Table 1 was used. , A negative electrode, and a secondary battery. Then, evaluation was performed in the same manner as in Example 1. Table 1 shows the results.

(Example 3)
In preparing the polymer (A), the monomer composition shown in Table 1 was adopted, and in preparing the binder composition for the positive electrode, N, N′-bis was replaced with an NMP solution of polyethyleneimine. Polymer (A) was prepared in the same manner as in Example 1 except that an NMP solution (solid content: 8%) of (3-phenyl-2-propenylidene) -1,6-hexanediamine (molecular weight: 344) was used. , A positive electrode binder composition, a positive electrode slurry composition, a positive electrode, a negative electrode, and a secondary battery. Then, evaluation was performed in the same manner as in Example 1. Table 1 shows the results.

(Examples 16 and 17)
When preparing the binder composition for the positive electrode, the polymer (A) and the binder for the positive electrode were prepared in the same manner as in Example 1, except that the amount of the polyvalent cationic organic compound (B) was changed as shown in Table 1. A composition, a slurry composition for a positive electrode, a positive electrode, a negative electrode, and a secondary battery were produced. Then, evaluation was performed in the same manner as in Example 1. Table 1 shows the results.

(Examples 18 and 19)
In preparing the binder composition for the positive electrode, polyethyleneimine (number average molecular weight: 1200, “Epomin SP-012”, manufactured by Nippon Shokubai Co., Ltd.) or polyethylene is used instead of an NMP solution of polyethyleneimine (number average molecular weight: 600). Except for using an NMP solution (solid concentration 8%) of imine (number average molecular weight: 1800, “Epomin SP-018”, manufactured by Nippon Shokubai Co., Ltd.), the polymer (A) was prepared in the same manner as in Example 1. A binder composition for a positive electrode, a slurry composition for a positive electrode, a positive electrode, a negative electrode, and a secondary battery were produced. Then, evaluation was performed in the same manner as in Example 1. Table 1 shows the results.

(Examples 20 to 23)
In preparing the binder composition for a positive electrode, N, N′-bis (3-phenyl-2-propenylidene) -1,6-hexanediamine (N-N′-bis (3-phenyl-2-propenylidene)) was used instead of an NMP solution of polyethyleneimine (number average molecular weight: 600). NMP solution of polyallylamine (molecular weight: 344), polyallylamine (number average molecular weight: 1600, "PAA-01", manufactured by Nittobo Medical), diethylenetriamine (molecular weight: 103), or ethylenediamine (molecular weight: 60) (solid content: 8%) The polymer (A), the binder composition for the positive electrode, the slurry composition for the positive electrode, the positive electrode, the negative electrode, and the secondary battery were produced in the same manner as in Example 1 except that was used. Then, evaluation was performed in the same manner as in Example 1. Table 1 shows the results.

(Comparative Example 1)
In the preparation of the positive electrode binder composition, the polymer (A), the positive electrode binder composition, and the positive electrode slurry composition were prepared in the same manner as in Example 1 except that the polyvalent cationic organic compound (B) was not used. The product, the positive electrode, the negative electrode, and the secondary battery were manufactured. Then, evaluation was performed in the same manner as in Example 1. Table 1 shows the results.

(Comparative Example 2)
In preparing the binder composition for the positive electrode, instead of the NMP solution of polyethyleneimine (number average molecular weight: 600), NMP of polyethyleneimine (number average molecular weight: 10,000, “Epomin SP-200”, manufactured by Nippon Shokubai) was used. A polymer (A), a binder composition for a positive electrode, a slurry composition for a positive electrode, a positive electrode, a negative electrode, and a secondary battery were prepared in the same manner as in Example 1 except that a solution (solid content concentration: 8%) was used. did. Then, evaluation was performed in the same manner as in Example 1. Table 1 shows the results.

(Comparative Example 3)
In the preparation of the polymer (A), the polymer (A), the binder composition for the positive electrode, the slurry composition for the positive electrode, and the positive electrode were prepared in the same manner as in Example 1 except that the monomer composition shown in Table 1 was used. , A negative electrode, and a secondary battery. Then, evaluation was performed in the same manner as in Example 1. Table 1 shows the results.

(Comparative Example 4)
In preparing the binder composition for the positive electrode, aluminum chelate (manufactured by Kawaken Fine Chemical Co., product name "Aluminum Chelate A (W)", aluminum tris (acetylacetonate)) is used instead of the polyvalent cationic organic compound (B). A polymer (A), a binder composition for a positive electrode, a slurry composition for a positive electrode, a positive electrode, a negative electrode, and a secondary battery were produced in the same manner as in Example 1 except for using the same. Then, evaluation was performed in the same manner as in Example 1. Table 1 shows the results.

In Table 1 shown below,
"COOH" represents a carboxylic acid group,
"AA" represents an acrylic acid unit,
"IA" represents itaconic acid unit,
"MAA" represents a methacrylic acid unit,
"MBM" indicates monobutyl maleate unit,
"MMA" indicates methyl methacrylate unit,
"EA" indicates an ethyl acrylate unit,
"BA" represents n-butyl acrylate unit,
"2-EHA" represents 2-ethylhexyl acrylate unit,
"AN" represents acrylonitrile unit,
"BD" represents 1,3-butadiene unit or 1,3-butadiene hydride unit,
"PEI" indicates polyethyleneimine,
"NBH" represents N, N'-bis (3-phenyl-2-propenylidene) -1,6-hexanediamine;
"PAA" refers to polyallylamine,
"DETA" indicates diethylenetriamine,
"ED" represents ethylenediamine,
"AL" indicates aluminum chelate.

From Table 1, in Examples 1 to 23 using a binder composition containing a polymer (A) having a binding functional group and a polyvalent cationic organic compound (B) having a molecular weight of a predetermined value or less, A binder composition having excellent viscosity stability, and obtaining a slurry composition capable of forming an electrode mixture layer in which swelling in an electrolytic solution is suppressed, to produce a secondary battery having excellent cycle characteristics You can see what you can do.
On the other hand, from Table 1, in Comparative Example 1 using the binder composition containing the polymer (A) having a binding functional group and containing no polyvalent cationic organic compound (B) having a molecular weight of a predetermined value or less. In addition, it can be seen that the swelling of the electrode mixture layer in the electrolyte cannot be sufficiently suppressed, and the cycle characteristics of the secondary battery deteriorate.
Further, from Table 1, the polymer (A) having a binding functional group and the polyvalent cationic organic compound (B) are included, and the molecular weight of the polyvalent cationic organic compound (B) exceeds a predetermined value. In Comparative Example 2 using the binder composition, it can be seen that the binder composition is inferior in viscosity stability and the cycle characteristics of the secondary battery are reduced.
Further, from Table 1, in Comparative Example 3 using a binder composition containing a polymer having no binding functional group and a polyvalent cationic organic compound (B) having a molecular weight of not more than a predetermined value, an electrode was used. It can be seen that the swelling of the mixture layer in the electrolyte cannot be sufficiently suppressed, and the cycle characteristics of the secondary battery deteriorate.
Furthermore, from Table 1, in Comparative Example 4 using the polymer (A) having a binding functional group and the binder composition containing an aluminum chelate, the binder composition was inferior in viscosity stability and the cycle characteristics of the secondary battery It can be seen that is reduced. It is presumed that these performance decreases are due to aluminum ions derived from the aluminum chelate. Specifically, the decrease in viscosity stability is presumed to be due to the high mobility of aluminum ions in the solvent, which causes a crosslinking reaction with the polymer (A) to increase the viscosity of the polymer (A). You. In addition, the decrease in cycle characteristics is caused by a temperature increase due to shearing during the preparation of the slurry composition, so that aluminum ions cause a crosslinking reaction with the polymer (A), and as a result, the polymer (A) becomes difficult to coat the conductive material. It is presumed that the dispersibility of the conductive material was impaired.

ADVANTAGE OF THE INVENTION According to this invention, the binder composition for non-aqueous secondary battery electrodes which is excellent in viscosity stability and can form the electrode mixture layer in which the swelling in the electrolytic solution was suppressed is obtained.
Further, according to the present invention, a non-aqueous secondary battery capable of forming an electrode mixture layer in which swelling in an electrolytic solution is suppressed and exhibiting excellent cycle characteristics to a non-aqueous secondary battery is provided. A conductive material paste composition for a secondary battery electrode and a slurry composition for a non-aqueous secondary battery electrode are obtained.
Furthermore, according to the present invention, for a non-aqueous secondary battery, which comprises an electrode mixture layer in which swelling in an electrolytic solution is suppressed, and which can exhibit excellent cycle characteristics to a non-aqueous secondary battery An electrode is obtained.
According to the present invention, a non-aqueous secondary battery having excellent cycle characteristics can be obtained.

Claims (9)

  A binder composition for a non-aqueous secondary battery electrode, comprising: a polymer having a functional group capable of binding to a cationic group; and an organic compound having two or more cationic groups and having a molecular weight of 8000 or less.   The non-aqueous secondary battery according to claim 1, wherein the functional group capable of binding to the cationic group is at least one selected from the group consisting of a carboxylic acid group, a sulfonic acid group, a phosphoric acid group, and a hydroxyl group. An electrode binder composition.   The non-aqueous secondary according to claim 1, wherein the polymer includes a monomer unit having a functional group capable of binding to a cationic group at a ratio of 0.1% by mass or more and 20% by mass or less. A binder composition for a battery electrode.   4. The binder composition for a non-aqueous secondary battery electrode according to claim 1, wherein the binder composition contains 0.1 to 20 parts by mass of the organic compound per 100 parts by mass of the polymer. 5. The polymer includes a nitrile group-containing monomer unit and at least one of a conjugated diene monomer unit and an alkylene structural unit,
A ratio of the nitrile group-containing monomer unit in the polymer is 5% by mass or more and 35% by mass or less, and a total of a ratio of the conjugated diene monomer unit and a ratio of the alkylene structural unit in the polymer; The binder composition for a non-aqueous secondary battery electrode according to any one of claims 1 to 4, wherein the content is 30% by mass or more and 90% by mass or less.   A conductive material paste composition for a non-aqueous secondary battery electrode, comprising a conductive material and the binder composition for a non-aqueous secondary battery electrode according to claim 1.   A non-aqueous battery comprising the electrode active material and the binder composition for a non-aqueous secondary battery electrode according to any one of claims 1 to 5 or the conductive material paste composition for a non-aqueous secondary battery electrode according to claim 6. A slurry composition for an aqueous secondary battery electrode.   An electrode for a non-aqueous secondary battery, comprising an electrode mixture layer formed using the slurry composition for a non-aqueous secondary battery electrode according to claim 7. Equipped with a positive electrode, negative electrode, electrolyte and separator,
A non-aqueous secondary battery, wherein at least one of the positive electrode and the negative electrode is the electrode for a non-aqueous secondary battery according to claim 8.