KR20190122690A - Binder composition for non-aqueous secondary battery electrodes, conductive material paste composition for non-aqueous secondary battery electrodes, slurry composition for non-aqueous secondary battery electrodes, electrode for non-aqueous secondary battery and non-aqueous secondary battery - Google Patents

Abstract

An object of this invention is to provide the binder composition for non-aqueous secondary battery electrodes which is excellent in viscosity stability and can form the electrode mixture layer in which swelling in the electrolyte solution was suppressed. The binder composition of this invention contains the polymer which has a functional group couple | bonded with a cationic group, and the organic compound which has a 2 or more cationic group, and whose molecular weight is 8000 or less.

Description

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

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

Non-aqueous secondary batteries (hereinafter, simply abbreviated as "secondary batteries"), such as lithium ion secondary batteries, are small in size, light in weight, have a high energy density, and can be repeatedly charged and discharged. Widely used. Therefore, in recent years, improvement of battery members, such as an electrode, is examined for the purpose of further high performance of a non-aqueous secondary battery.

Here, the electrode used for secondary batteries, such as a lithium ion secondary battery, is normally equipped with an electrical power collector and the electrode mixture layer (positive electrode mixture layer or negative electrode mixture layer) formed on the electrical power collector. And this electrode mixture layer is formed by apply | coating the slurry composition containing an electrode active material, the binder composition containing a binder, etc. on a collector, for example, and drying the apply | coated slurry composition.

Therefore, in recent years, in order to achieve the further improvement of the performance of a secondary battery, improvement of the binder composition used for formation of an electrode mixture layer is tried.

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

Japanese Unexamined Patent Publication No. 2008-166058

However, the viscosity stability of the said conventional binder composition could not be said to be satisfactory enough. In addition, the electrode mixture layer obtained using the said conventional binder composition will swell excessively in electrolyte solution. And in the electrode provided with the electrode mixture layer obtained from such a binder composition, it was difficult to show the cycling characteristics excellent in a secondary battery. That is, there existed room for improvement in the said conventional binder composition that the swelling in the electrolyte solution of an electrode mixture layer is suppressed, and the cycling characteristics of a secondary battery are fully raised, ensuring viscosity stability.

Therefore, an object of this invention is to provide the binder composition for non-aqueous secondary battery electrodes which is excellent in viscosity stability and can form the electrode mixture layer in which swelling in the electrolyte solution was suppressed.

Moreover, this invention can form the electrode mixture layer by which the swelling in the electrolyte solution was suppressed, and can also exhibit the outstanding cycling characteristics to a nonaqueous secondary battery, The electrically conductive material paste composition for nonaqueous secondary battery electrodes, and a nonaqueous secondary It is an object to provide a slurry composition for battery electrodes.

Moreover, an object of this invention is to provide the electrode for nonaqueous secondary batteries which is equipped with the electrode mixture layer in which swelling in electrolyte solution was suppressed, and which can exhibit the outstanding cycling characteristics to a nonaqueous secondary battery.

And an object of this invention is to provide the non-aqueous secondary battery which has the outstanding cycling characteristics.

MEANS TO SOLVE THE PROBLEM This inventor earnestly examined for the purpose of solving the said subject. And this inventor is excellent in viscosity stability, and the binder composition containing the polymer which has a functional group couple | bonded with a cationic group, and the organic compound which has two or more cationic groups, and whose molecular weight is below a predetermined value is excellent in the said When the binder composition was used, it discovered that the electrode mixture layer by which swelling in the electrolyte solution was suppressed was formed, and completed this invention.

That is, this invention aims at solving the said subject advantageously, The binder composition for non-aqueous secondary battery electrodes of this invention has the polymer which has a functional group couple | bonded with a cationic group, and two or more cationic groups. And an organic compound having a molecular weight of 8000 or less. Thus, the binder composition containing the polymer which has a functional group couple | bonded with a cationic group, and the organic compound which has two or more cationic groups and whose molecular weight is below a predetermined value is excellent in viscosity stability, and when the said binder composition is used, The electrode mixture layer in which swelling in the electrolyte is suppressed can be formed.

In addition, in this invention, a "cationic group" means the functional group which can exhibit cationicity by being present in a solvent individually or together with the substance which supplies an electrostatic charge. In addition, in this invention, a "functional group which can couple | bond with a cationic group" means the functional group which can interact with a cationic group by an ionic bond, a hydrogen bond, a covalent bond, etc. in a solvent.

Here, it is preferable that the binder composition for non-aqueous secondary battery electrodes of this invention is at least 1 sort (s) selected from the group which the functional group couple | bonded with the said cationic group becomes from a carboxylic acid group, a sulfonic acid group, a phosphoric acid group, and a hydroxyl group. When the polymer which has a predetermined functional group mentioned above is used, swelling in the electrolyte solution of an electrode mixture layer can be further suppressed, ensuring the viscosity stability of a binder composition fully.

Moreover, it is preferable that the binder composition for non-aqueous secondary battery electrodes of this invention contains the monomer unit containing the functional group couple | bonded with a cationic group in the ratio of 0.1 mass% or more and 20 mass% or less. By using the polymer containing the monomeric unit containing the functional group couple | bonded with a cationic group in the quantity mentioned above, swelling in the electrolyte solution of the electrode mixture layer can be further suppressed, ensuring sufficient viscosity stability of a binder composition. .

In addition, in this invention, "containing a monomeric unit" means "the repeating unit derived from a monomer is contained in the polymer obtained using the monomer." On the other hand, the ratio containing each monomer unit and / or a structural unit being a polymer can be measured by using a nuclear magnetic resonance (NMR) method such as ¹ H-NMR and ¹³ C-NMR.

Moreover, it is preferable that the binder composition for non-aqueous secondary battery electrodes of this invention contains 0.1 mass part or more and 20 mass parts or less of the said organic compound per 100 mass parts of said polymers. When the compounding quantity of an organic compound is in the above-mentioned range, swelling in the electrolyte solution of an electrode mixture layer can be further suppressed, ensuring the viscosity stability of a binder composition fully.

Here, in the binder composition for non-aqueous secondary battery electrodes of this invention, the said polymer contains the nitrile-group containing monomeric unit, the conjugated diene monomeric unit, and the alkylene structural unit, and the said nitrile-group containing monomer in the said polymer It is preferable that the ratio of a unit is 5 mass% or more and 35 mass% or less, and the sum total of the ratio of the said conjugated diene monomeric unit in the said polymer, and the ratio of the said alkylene structural unit is 30 mass% or more and 90 mass% or less. The above-mentioned polymer can be dissolved in the solvent of the binder composition satisfactorily and adsorbed satisfactorily to the conductive material and the like, and can disperse them well (that is, excellent dispersibility to the conductive material and the like). And by using the said polymer, swelling in the electrolyte solution of an electrode mixture layer can be further suppressed, ensuring the viscosity stability of a binder composition fully.

Moreover, this invention aims at solving the said subject advantageously, The electrically conductive material paste composition for non-aqueous secondary battery electrodes of this invention is an electrically conductive material and the binder for any one non-aqueous secondary battery electrode mentioned above. It is characterized by comprising a composition. When the electrically conductive material and the electrically conductive material paste composition containing any of the binder compositions mentioned above are prepared, and an electrode active material etc. are added to the said electrically conductive material paste composition, and a slurry composition is prepared, the electrode mixture by which swelling in electrolyte solution was suppressed was suppressed. The layer can be formed, and the secondary battery can exhibit excellent cycle characteristics.

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, the binder composition for any one of non-aqueous secondary battery electrodes mentioned above, or It is characterized by including the above-mentioned electrically conductive material paste for nonaqueous secondary battery electrodes. Thus, when the slurry composition containing an electrode active material and any one of the above-mentioned binder compositions or electrically conductive material pastes can be used, the electrode mixture layer by which swelling in electrolyte solution was suppressed can be formed, and it exhibits the outstanding cycling characteristic to a secondary battery. You can.

Moreover, this invention aims at solving the said subject advantageously, The electrode for non-aqueous secondary batteries of this invention is equipped with the electrode mixture layer formed using the slurry composition for non-aqueous secondary battery electrodes mentioned above. It is characterized by. Thus, in the electrode mixture layer obtained using the slurry composition mentioned above, swelling in electrolyte solution is suppressed, and the electrode provided with this electrode mixture layer can exhibit the outstanding cycling characteristics to a secondary battery.

Moreover, this invention aims at solving the said subject advantageously, The non-aqueous secondary battery of this invention is equipped with the positive electrode, the negative electrode, electrolyte solution, and the separator, At least one of the said positive electrode and the negative electrode mentioned above ratio It is an electrode for aqueous secondary batteries, It is characterized by the above-mentioned. Thus, the non-aqueous secondary battery provided with the electrode mentioned above has the outstanding cycling characteristic.

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

Moreover, according to this invention, the electrically conductive material paste composition for non-aqueous secondary battery electrodes which can form the electrode mixture layer in which swelling in electrolyte solution was suppressed, and can exhibit the outstanding cycling characteristic to a non-aqueous secondary battery, and a non-aqueous system are also provided. The slurry composition for secondary battery electrodes is obtained.

Moreover, according to this invention, the electrode for non-aqueous secondary batteries is provided which is equipped with the electrode mixture layer in which swelling in electrolyte solution was suppressed, and which can exhibit the outstanding cycling characteristic to a non-aqueous secondary battery.

And according to this invention, the non-aqueous secondary battery which has the outstanding cycling characteristics is obtained.

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

Here, the binder composition for nonaqueous secondary battery electrodes of this invention can be used when preparing the slurry composition for nonaqueous secondary battery electrodes. Moreover, the binder composition for nonaqueous secondary battery electrodes of this invention mixes with a electrically conductive material, and sets it as the electrically conductive material paste composition for non-aqueous secondary battery electrodes containing the binder composition and electrically conductive material for a non-aqueous secondary battery electrode, and is a non-aqueous system. It can be used for preparation of the slurry composition for 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 this invention can be used when forming the electrode of non-aqueous secondary batteries, such as a lithium ion secondary battery. Moreover, the non-aqueous secondary battery of this invention used the electrode for non-aqueous secondary batteries formed using the slurry composition for non-aqueous secondary battery electrodes of this invention.

On the other hand, the binder composition for nonaqueous secondary battery electrodes, the electrically conductive material paste composition for nonaqueous secondary battery electrodes, and the slurry composition for nonaqueous secondary battery electrodes of the present invention can be particularly suitably used when forming the positive electrode of the nonaqueous secondary battery. have.

(Binder Composition for Non-aqueous Secondary Battery Electrode)

The binder composition for non-aqueous secondary battery electrodes of this invention is a polymer (henceforth called "polymer (A)") which has a functional group couple | bonded with a cationic group, and the organic compound which has two or more cationic groups ( Hereinafter, the "polyvalent cationic organic compound (B)" may be referred to.), And optionally further include other components that can be blended into the electrode of the secondary battery. Here, in the binder composition for non-aqueous secondary battery electrodes of this invention, the molecular weight of the polyvalent cationic organic compound (B) mentioned above is 8000 or less. In addition, the binder composition for non-aqueous secondary battery electrodes of the present invention further contains a solvent such as an organic solvent.

And since the binder composition of this invention contains the polymer which has a functional group couple | bonded with a cationic group, and the polyvalent cationic organic compound (B) whose molecular weight is 8000 or less, even if it is stored for a long time, a viscosity change is small and an electrode Swelling in the electrolyte solution of the mixture layer can be suppressed.

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

That is, in the binder composition of this invention, the functional group in a polymer (A) and the cationic group in a polyvalent cationic organic compound (B) can interact favorably, For example, a polymer (A) and the said patent document 1 The viscosity change with time is suppressed compared with the case where the polyvalent metal compound containing the predetermined ligand of description is used together. Moreover, since the binder composition of this invention contains a polymer (A) and a polyvalent cationic organic compound (B), when a slurry composition containing a binder composition is dried, an electrode mixture layer is formed, a polymer (A The functional group in) and the cationic group in the polyvalent cationic organic compound (B) interact more strongly by crosslinking or the like. By this firm interaction, a rigid network is formed, and the electrode mixture layer is not excessively swollen in the electrolyte solution. In addition, since the molecular weight of the polyvalent cationic organic compound (B) mentioned above is 8000 or less, the polyvalent cationic organic compound (B) does not excessively thicken a binder composition, and the viscosity change by time of a binder composition is furthermore. Suppressed.

Therefore, according to this invention, swelling in the electrolyte solution of an electrode mixture layer can be suppressed, ensuring the stability of the viscosity of a binder composition, and the cycling characteristics excellent in a secondary battery can be exhibited.

<Polymer (A)>

Polymer (A) is an electrode produced by forming an electrode mixture layer on a current collector using a slurry composition for non-aqueous secondary battery electrodes prepared using a binder composition, wherein a component included in the electrode mixture layer is an electrode mixture layer. It is maintained so as not to detach from (ie, an adhesive polymer that functions as a binder).

<< functional group which can be combined with cationic group >>

The functional group (hereinafter, sometimes referred to as a "bonding functional group") capable of bonding with the cationic group possessed by the polymer (A) is not particularly limited, but may be a carboxylic acid group or a sulfonic acid group that can interact with the cationic group satisfactorily. , A phosphoric acid group, and a hydroxyl group. Among these, a carboxylic acid group, a sulfonic acid group, and a phosphoric acid group are more preferable, and a carboxylic acid group is especially preferable. When the polymer (A) which has these functional groups is used, swelling in the electrolyte solution of an electrode mixture layer can further be suppressed, ensuring the viscosity stability of a binder composition fully, and the cycle characteristic of a secondary battery can be improved further. In addition, the polymer (A) may have only one type of bonding functional group, and may have two or more types.

<< composition of polymer (A) >>

Here, the method of introducing a bondable functional group into the polymer (A) is not particularly limited, and the polymer is prepared using the monomer (bondable functional group-containing monomer) containing the above-mentioned bondable functional group to form a bondable functional group-containing monomer unit. Although the polymer (A) to be included may be obtained, and the polymer (A) which has the above-mentioned bond functional group at the terminal may be obtained by carrying out terminal modification of arbitrary polymers, etc., the former is preferable. And the polymer (A) containing a bond functional group containing monomeric unit may contain repeating units other than a bond functional group containing monomeric unit.

Binding functional group containing monomeric unit

Here, as a bond functional group containing monomer which can form a bond functional group containing monomeric unit, Preferably, the monomer which has a carboxylic acid group, the monomer which has a sulfonic acid group, the monomer which has a phosphoric acid group, and the monomer which has a hydroxyl group are preferable. Can be mentioned.

As a monomer which has a carboxylic acid group, monocarboxylic acid and its derivative (s), dicarboxylic acid and its acid anhydride, derivatives thereof, etc. are mentioned.

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

As monocarboxylic acid derivative, 2-ethylacrylic acid, isocrotonic acid, (alpha)-acetoxyacrylic acid, (beta) -trans- aryloxyacrylic acid, (alpha)-chloro- (beta) -E-methoxyacrylic acid, (beta)-diaminoacrylic acid, etc. are mentioned. Can be mentioned.

Examples of the dicarboxylic acid include maleic acid, fumaric acid and itaconic acid.

As the dicarboxylic acid derivative, methyl maleic acid, dimethyl maleic acid, phenyl maleic acid, chloro maleic acid, dichloro maleic acid, fluoro maleic acid, monobutyl maleate, monomonyl maleate, monodecyl maleate, male And maleic acid monoesters such as acid monododecyl, monooctadecyl maleate, and monofluoroalkyl maleate.

Examples of the acid anhydride of the dicarboxylic acid include maleic anhydride, acrylic acid anhydride, methyl maleic anhydride, and dimethyl maleic anhydride.

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

As the monomer having a sulfonic acid group, for example, vinylsulfonic acid, methylvinylsulfonic acid, (meth) allylsulfonic acid, 3-allyloxy-2-hydroxypropanesulfonic acid, 2-acrylamido-2-methylpropanesulfonic acid and the like Can be mentioned.

In addition, in this invention, "(meth) allyl" means allyl and / or metallyl.

Moreover, as a monomer which has a phosphoric acid group, For example, 2- (meth) acryloyloxyethyl phosphate, methyl-2- (meth) acryloyloxyethyl phosphate, ethyl- (meth) acryloyloxy phosphate Ethyl and the like.

In addition, in this invention, "(meth) acryloyl" means acryloyl and / or methacryloyl.

And as a monomer which has a hydroxyl group, Ethylenic unsaturated alcohols, such as (meth) allyl alcohol, 3-butene-1-ol, 5-hexen-1-ol; 2-hydroxyethyl acrylate, 2-hydroxypropyl acrylate, 2-hydroxyethyl methacrylate, 2-hydroxypropyl methacrylate, di-hydroxyethyl maleic acid, di-maleic acid-4- Alkanol esters of ethylenically unsaturated carboxylic acids such as hydroxybutyl and di-2-hydroxypropyl itaconic acid; General formula: CH ₂ = CR ^Z -COO- (C _n H _2n O) _m -H (wherein m is an integer from 2 to 9, n is an integer from 2 to 4, R ^Z represents hydrogen or a methyl group) Esters of polyalkylene glycols represented by (meth) acrylic acid; Mono of dihydroxy esters of dicarboxylic acids such as 2-hydroxyethyl-2 '-(meth) acryloyloxyphthalate and 2-hydroxyethyl-2'-(meth) acryloyloxysuccinate Meth) acrylic acid esters; Vinyl ethers such as 2-hydroxyethyl vinyl ether and 2-hydroxypropyl vinyl ether; (Meth) allyl-2-hydroxyethyl ether, (meth) allyl-2-hydroxypropyl ether, (meth) allyl-3-hydroxypropyl ether, (meth) allyl-2-hydroxybutyl ether, (meth Mono (meth) allyl ethers of alkylene glycols such as allyl-3-hydroxybutyl ether, (meth) allyl-4-hydroxybutyl ether, and (meth) allyl-6-hydroxyhexyl ether; Polyoxyalkylene glycol mono (meth) allyl ethers such as diethylene glycol mono (meth) allyl ether and dipropylene glycol mono (meth) allyl ether; Halogen of (poly) alkylene glycols such as glycerin mono (meth) allyl ether, (meth) allyl-2-chloro-3-hydroxypropyl ether, (meth) allyl-2-hydroxy-3-chloropropyl ether And mono (meth) allyl ethers of hydroxy substituents; Mono (meth) allyl ethers of polyhydric phenols such as eugenol and isoeugenol and halogen substituents thereof; (Meth) allylthio ethers of alkylene glycols such as (meth) allyl-2-hydroxyethylthioether and (meth) allyl-2-hydroxypropylthioether; Etc. can be mentioned.

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

Among these, the polymer (A) interacts with the polyvalent cationic organic compound (B) satisfactorily, and the swelling in the electrolyte of the electrode mixture layer is further suppressed while sufficiently securing the viscosity stability of the binder composition, and the cycle of the secondary battery is achieved. From a viewpoint of further improving a characteristic, as a coupling | bonding functional group containing monomer, the monomer which has a carboxylic acid group, the monomer which has a sulfonic acid group, and the monomer which has a phosphoric acid group are preferable, and the monomer which has a carboxylic acid group is more preferable. That is, the bondable functional group-containing monomer unit is preferably at least one selected from the group consisting of a monomer unit having a carboxylic acid group, a monomer unit having a sulfonic acid group, and a monomer unit having a phosphoric acid group, and a monomer unit having a carboxylic acid group. It is more preferable that is.

In addition, a bond functional group containing monomer may be used individually by 1 type, and may be used combining two or more types by arbitrary ratios.

And it is preferable that the ratio of the coupling | bonding functional group containing monomeric unit which a polymer (A) contains is 0.1 mass% or more, It is more preferable that it is 0.5 mass% or more, It is further more preferable that it is 1 mass% or more, It is 20 mass% or less It is preferable that it is 10 mass% or less, and it is more preferable that it is 6 mass% or less. When the ratio of the coupling | bonding functional group containing monomeric unit which a polymer (A) contains is below the said upper limit, a polymer (A) does not interact excessively with a polyvalent cationic organic compound (B). Therefore, aggregation of these components can be suppressed, sufficient viscosity stability of a binder composition can be fully ensured, and the cycling characteristics of a secondary battery can be improved further. Moreover, if the ratio of the binder functional group containing monomeric unit which a polymer (A) contains is more than the said minimum, swelling in the electrolyte solution of an electrode mixture layer can be further suppressed, ensuring sufficient viscosity stability of a binder composition, and a secondary battery Can further improve the cycle characteristics.

[Repeating Units Other Than Binding Functional Group-Containing Monomer Unit]

Moreover, it does not specifically limit as repeating units other than the bondable functional group containing monomeric unit which a polymer (A) can contain, A conjugated diene monomeric unit, an alkylene structural unit, a nitrile-group containing monomeric unit, (meth) acrylic acid Ester monomer units, aromatic vinyl monomer units, and the like.

-Conjugated diene monomeric unit-

Here, as a conjugated diene monomer which can form a conjugated diene monomeric unit, For example, carbon number, such as 1, 3- butadiene, isoprene, 2, 3- dimethyl- 1, 3- butadiene, 1, 3- pentadiene 4 or more conjugated diene compound is mentioned. Especially, 1, 3- butadiene is preferable.

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

Alkylene structural units

In addition, an alkylene structural unit is a repeating unit comprised only with the alkylene structure represented by general formula: -C _n H _2n- [n is an integer of 2 or more].

Here, although the alkylene structural unit may be linear or branched, from the viewpoint of improving the dispersion stability of the slurry composition for non-aqueous secondary battery electrodes, the alkylene structural unit is linear, that is, a straight alkylene structural unit. desirable. Moreover, it is preferable that carbon number of an alkylene structural unit is four or more (namely, n is an integer of four or more) from a viewpoint of further improving the dispersion stability of the slurry composition for non-aqueous secondary battery electrodes.

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

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

(2) Method to prepare copolymer from monomer composition containing 1-olefin monomer

Can be mentioned. Among these, the method of (1) is preferable because manufacture of a polymer (A) is easy.

On the other hand, as a conjugated diene monomer used by the method of said (1), C4 or more conjugated dienes, such as 1, 3- butadiene, isoprene, 2, 3- dimethyl- 1, 3- butadiene, and 1, 3- pentadiene A compound is mentioned, Especially, 1, 3- butadiene is preferable. That is, the alkylene structural unit is preferably a structural unit (conjugated diene hydride unit) obtained by hydrogenating a conjugated diene monomer unit, and a structural unit (1,3-butadiene hydride obtained by hydrogenating a 1,3-butadiene unit Unit). And selective hydrogenation of a conjugated diene monomeric unit can be performed using well-known methods, such as an oil layer hydrogenation method and a water layer hydrogenation method.

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

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

Nitrile-group containing monomer unit

Moreover, (alpha), (beta)-ethylenically unsaturated nitrile monomer is mentioned as a nitrile-group containing monomer which can form a nitrile-group containing monomeric unit. 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. Examples thereof include acrylonitrile; α-halogeno acrylonitrile such as α-chloroacrylonitrile and α-bromoacrylonitrile; Α-alkylacrylonitrile such as methacrylonitrile and α-ethylacrylonitrile; Etc. can be mentioned. Among these, as a nitrile-group containing monomer, an acrylonitrile and methacrylonitrile are preferable, and an acrylonitrile is more preferable.

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

-(Meth) acrylic acid ester monomeric unit-

Moreover, as a (meth) acrylic acid ester monomer which can form a (meth) acrylic acid ester monomeric unit, methyl acrylate, ethyl acrylate, n-propyl acrylate, isopropyl acrylate, n-butyl acrylate, t- Butyl acrylate, isobutyl acrylate, n-pentyl acrylate, isopentyl acrylate, hexyl acrylate, heptyl acrylate, octyl acrylate, 2-ethylhexyl acrylate, nonyl acrylate, decyl acrylate, lauryl acryl Acrylic acid alkyl esters such as latex, n-tetradecyl acrylate and stearyl acrylate; Methyl methacrylate, ethyl methacrylate, n-propyl methacrylate, isopropyl methacrylate, n-butyl methacrylate, t-butyl methacrylate, isobutyl methacrylate, n-pentyl methacrylate, Isopentyl methacrylate, hexyl methacrylate, heptyl methacrylate, octyl methacrylate, 2-ethylhexyl methacrylate, nonyl methacrylate, decyl methacrylate, lauryl methacrylate, n-tetradecyl methacrylate Methacrylic acid alkyl esters such as acrylate and stearyl methacrylate; Etc. can be mentioned. Especially, methyl acrylate, ethyl acrylate, n-butyl acrylate, 2-ethylhexyl acrylate, methyl methacrylate, ethyl methacrylate, n-butyl methacrylate, and 2-ethylhexyl methacrylate are preferable. And n-butyl acrylate, ethyl methacrylate, and 2-ethylhexyl acrylate are more preferable.

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

Aromatic vinyl monomer unit

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

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

Also in repeating units other than the above-mentioned binding functional group containing monomeric unit, the electrode mixture is made to improve the solubility of the binder composition of the polymer (A) to the solvent, the dispersibility to an electrically conductive material, etc. as a result, fully ensuring the viscosity stability of a binder composition. The polymer (A) contains a nitrile-group containing monomeric unit, a conjugated diene monomeric unit, and at least one of an alkylene structural unit from a viewpoint of further improving cycling characteristics of a secondary battery by further suppressing swelling in the electrolyte solution of a layer. It is preferable to, and it is more preferable to include a nitrile-group containing monomeric unit and an alkylene structural unit.

And it is preferable that the ratio of the nitrile-group containing monomeric unit which a polymer (A) contains is 5 mass% or more, It is more preferable that it is 7 mass% or more, It is further more preferable that it is 9 mass% or more, Especially it is 10 mass% or more It is preferable that it is 35 mass% or less, It is more preferable that it is 29 mass% or less, It is further more preferable that it is 23 mass% or less. When the ratio of the nitrile group containing monomeric unit which a polymer (A) contains is below the said upper limit, swelling in the electrolyte solution of an electrode mixture layer can be further suppressed, and the cycling characteristics of a secondary battery can be further improved. Moreover, when the ratio of the nitrile-group containing monomeric unit which a polymer (A) contains is more than the said lower limit, the solubility to the solvent of the binder composition of a polymer (A) becomes high, and the viscosity stability of a binder composition can fully be ensured.

Moreover, it is preferable that the sum total of the ratio of the conjugated diene monomeric unit and alkylene structural unit which a polymer (A) contains is 30 mass% or more, It is more preferable that it is 40 mass% or more, It is preferable that it is 90 mass% or less, 75 It is more preferable that it is mass% or less. When the sum total of the ratio of the conjugated diene monomeric unit and alkylene structural unit which a polymer (A) contains is below the said upper limit, the solubility to the solvent of the binder composition of a polymer (A) will not be impaired, and the viscosity stability of a binder composition We can secure enough. Moreover, when the sum total of the ratio of the conjugated diene monomeric unit and alkylene structural unit which a polymer (A) contains is more than the said minimum, the dispersibility to a polymer (A) electrically conductive material etc. becomes high. And while ensuring the viscosity stability of a binder composition sufficiently, the cycling characteristics of a secondary battery can be improved further.

In addition, the ratio of the repeating unit other than the coupling | bonding functional group containing monomeric unit, conjugated diene monomeric unit, alkylene structural unit, and nitrile-group containing monomeric unit which a polymer (A) contains shall be 0 mass% or more and 60 mass% or less. Can be.

[Method for Preparing Polymer (A)]

Although the preparation method of the polymer (A) mentioned above is not specifically limited, A polymer (A) polymerizes the monomer composition containing the monomer mentioned above, for example, obtains a copolymer, and then hydrogenates the obtained copolymer as needed. It can prepare by adding hydrogen.

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

The polymerization mode may be any method such as a solution polymerization method, suspension polymerization method, bulk polymerization method or emulsion polymerization method without particular limitation. In addition, any reaction, such as ionic polymerization, radical polymerization, a living radical polymerization, can be used as a polymerization reaction.

In addition, the hydrogenation method of a copolymer is the general method using a catalyst without a restriction | limiting in particular (for example, refer international publication 2012/165120, international publication 2013/080989, and Japanese Unexamined-Japanese-Patent No. 2013-8485). Can be used.

<Polycationic 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. As the cationic group, for example, a substituted or unsubstituted amino group (-NH ₂ , -NHR ¹ , -NR ¹ R ² , -N ⁺ R ¹ R ² R ³ , wherein R ¹ to R ³ are arbitrary substituents ), A substituted or unsubstituted imino group (= NH, = NR ⁴ , where R ⁴ represents an arbitrary substituent), and nitrogen-containing functional groups (except amide groups) such as oxazoline groups. . Among them, the polyvalent cationic organic compound (B) interacts with the polymer (A) satisfactorily to further suppress swelling in the electrolyte of the electrode mixture layer while sufficiently securing the viscosity stability of the binder composition, thereby cycling the secondary battery. From the viewpoint of further improving the characteristics, that the primary amino group (unsubstituted amino group, -NH _2), secondary amino group (-NHR ^1), a substituted or unsubstituted imino group are preferred. In addition, a polyvalent cationic organic compound (B) may have only one type of cationic group, and may have two or more types of cationic groups.

In addition, in this invention, when the polymer which is an organic compound which has two or more cationic groups has a functional group couple | bonded with a cationic group, the polymer corresponds to a polyvalent cationic organic compound (B) instead of a polymer (A). I shall do it.

<Molecular Weight of Polyvalent Cationic Organic Compound (B)>

Here, the molecular weight (when a polyvalent cationic organic compound (B) is a polymer, points out "number average molecular weight") of a polyvalent cationic organic compound (B) needs to be 8000 or less, It is preferable that it is 2000 or less, It is 1800. It is more preferable that it is the following, It is still more preferable that it is 1600 or less, It is especially preferable that it is 1500 or less. When the molecular weight of a polyvalent cationic organic compound (B) exceeds 8000, a binder composition will thicken excessively, sufficient viscosity stability cannot be ensured, and also the cycling characteristics of a secondary battery will fall. On the other hand, the molecular weight of the polyvalent cationic organic compound (B) is preferably 60 or more, more preferably 100 or more, from the viewpoint of sufficiently suppressing swelling of the electrode mixture layer in the electrolyte solution and further improving cycle characteristics of the secondary battery. Do.

In addition, in this invention, when a polyvalent cationic organic compound (B) is a polymer, the number average molecular weight can be calculated | required as polystyrene conversion molecular weight measured by gel permeation chromatography (developing solvent: tetrahydrofuran). .

<Example of Polyvalent Cationic Organic Compound (B)>

As a polyvalent cationic organic compound (B), if the molecular weight is in the above-mentioned range, the polyvalent cationic organic compound (B) which is a nonpolymer may be used, and the polyvalent cationic organic compound (B) which is a polymer can also be used.

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

Moreover, as a polyvalent cationic organic compound (B) which is a polymer, Polyethylenimine; Polyethyleneimine derivatives such as poly N-hydroxyethylene imine and carboxymethylated polyethylene imine and sodium salt; Polypropyleneimine; Polypropylene imine derivatives such as poly N-2-dihydroxypropylene imine; Polyallylamine; Polyallylamine derivatives such as polydimethyldiallylammonium halide; Aminoethylated acrylic polymer obtained by aminoethylating an acrylic acid polymer; And cationized cellulose obtained by modifying a cellulose derivative (hydroxyethyl cellulose, carboxymethyl cellulose, etc.) with a cationic agent having a substituted or unsubstituted amino group.

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

<The compounding quantity of a polyvalent cationic organic compound (B)>

And it is preferable that the compounding quantity of the polyvalent cationic organic compound (B) whose molecular weight exists in the above-mentioned range is 0.1 mass part or more per 100 mass parts of polymers (A), It is more preferable that it is 0.2 mass part or more, It is further more that it is 0.5 mass part or more. It is preferable, It is especially preferable that it is 2 mass parts or more, It is preferable that it is 20 mass parts or less, It is more preferable that it is 10 mass parts or less, It is further more preferable that it is 6 mass parts or less. When the amount of the polyvalent cationic organic compound (B) is excessive, the viscosity stability of the binder composition is lowered. However, the viscosity stability of a binder composition can fully ensure that the compounding quantity of a polyvalent cationic organic compound (B) is 20 mass parts or less. Moreover, when the compounding quantity of a polyvalent cationic organic compound (B) is 0.1 mass part or more, a polymer (A) and a polyvalent cationic organic compound (B) can form a more rigid network in an electrode mixture layer. Therefore, swelling in the electrolyte solution of the electrode mixture layer can be further suppressed, and the cycle characteristics of the secondary battery can be further improved.

<Solvent>

As a solvent of the binder composition for non-aqueous secondary battery electrodes, an organic solvent is preferable. It does not specifically limit as an organic solvent, For example, methanol, ethanol, n-propanol, isopropanol, n-butanol, isobutanol, t-butanol, pentanol, hexanol, heptanol, octanol, nonanol, Alcohols such as decanol and amyl alcohol; Ketones such as acetone, methyl ethyl ketone and cyclohexanone; Esters such as ethyl acetate and butyl acetate; Ethers such as diethyl ether, dioxane and tetrahydrofuran; Amide polar organic solvents such as N, N-dimethylformamide and N-methylpyrrolidone (NMP); Aromatic hydrocarbons such as toluene, xylene, chlorobenzene, orthodichlorobenzene, paradichlorobenzene; Etc. can be mentioned. These may be used individually by 1 type and may mix and use two or more types.

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

<Other ingredients>

On the other hand, in the binder composition for non-aqueous secondary battery electrodes of the present invention, in addition to the above components, a binder (polyvinylidene fluoride, polyacrylonitrile, polyacrylate, etc.) other than the polymer (A), a reinforcing material, a leveling agent, and a viscosity You may contain components, such as a regulator and electrolyte solution additive, in a binder composition. These are not specifically limited as long as it does not affect battery reaction, A well-known thing, for example, the thing of international publication 2012/115096 can be used. In addition, these components may be used individually by 1 type, and may be used combining two or more types by arbitrary ratios.

<Electrolytic Solution Swelling Degree of Film Made of Binder Composition>

And it is preferable that the electrolyte solution swelling degree of the film obtained by drying the binder composition of this invention containing the above-mentioned component is less than 2000 mass%, It is more preferable that it is less than 1000 mass%, It is further more preferable that it is less than 800 mass%, 600 It is especially preferable that it is less than mass%. If the electrolyte solution swelling degree of the film which consists of a binder composition is less than 2000 mass%, the cycling characteristics of a secondary battery can fully be improved. In addition, the electrolyte solution swelling degree of the film which consists of a binder composition is 100 mass% or more normally.

In addition, the electrolyte solution swelling degree of the film which consists of a binder composition can be measured using the method as described in the Example of this specification.

(Slurry Composition for Non-Aqueous Secondary Battery Electrode)

The slurry composition for non-aqueous secondary battery electrodes of this invention contains an electrode active material and the binder composition mentioned above, and further contains an electrically conductive material and another component. That is, the slurry composition of this invention contains an electrode active material, the polymer (A) mentioned above, the polyvalent cationic organic compound (B) mentioned above, and a solvent, and also contain an electrically conductive material and other components arbitrarily. do. And since the slurry composition of this invention contains the binder composition mentioned above, the electrode mixture layer formed using the slurry composition of this invention suppresses swelling in electrolyte solution, and also provides the cycling battery the outstanding cycling characteristics. I can exercise it.

<Electrode active material>

Here, an electrode active material is a substance which exchanges electrons in the electrode of a non-aqueous secondary battery. For example, when a nonaqueous secondary battery is a lithium ion secondary battery, the substance which can occlude and discharge | release lithium is normally used as an electrode active material.

In addition, below, 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, but this invention is not limited to the following example.

The positive electrode active material for a 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 ), and 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, lithium excess spinel compound represented by Li _{1 + x} Mn _2-x O ₄ (0 <X <2), Li [Ni _0.17 Li _0.2 Known positive electrode active materials such as Co _0.07 Mn _0.56 ] O ₂ and LiNi _0.5 Mn _1.5 O ₄ may be mentioned.

In addition, the compounding quantity and particle diameter of a positive electrode active material are not specifically limited, It can make it the same as the positive electrode active material conventionally used.

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

Here, the carbon-based negative electrode active material refers to an active material containing 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 materials. Can be.

As the carbonaceous material, for example, non-graphite carbon and non-graphite carbon having a structure close to an amorphous structure represented by glassy carbon may be mentioned.

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

Examples of the non-graphite carbon include phenol resin fired bodies, polyacrylonitrile-based carbon fibers, pseudoisotropic carbon, furfuryl alcohol resin fired bodies (PFA), hard carbon, and the like.

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

Here, as artificial graphite, for example, artificial graphite obtained by heat-treating carbon containing digraphite carbon mainly at 2800 ° C. or higher, graphitized MCMB obtained by heat treatment of MCMB at 2000 ° C. or higher, and mesophase pitch-based carbon fiber at 2000 ° C. or higher, for example. Graphitized mesophase pitch type carbon fiber etc. which were heat-processed at are mentioned.

In addition, a metal type negative electrode active material is an active material containing a metal, and usually means the active material which contains the element which can insert lithium, and whose theoretical electric capacity per unit mass when lithium is inserted is 500 mAh / g or more. . As the metal-based active material, for example, lithium metal, 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 its alloys, and their oxides, sulfides, nitrides, silicides, carbides, phosphides and the like are used. Among these, as a metallic negative electrode active material, the active material containing a silicon (silicone negative electrode active material) is preferable. This is because the lithium ion secondary battery can be increased in capacity by using a silicon negative electrode active material.

Examples of the silicon-based negative electrode active material include silicon (Si), an alloy containing silicon, a composite material of Si-containing material and conductive carbon formed by coating or compounding SiO, SiO _x , and Si-containing material with conductive carbon. Can be. In addition, these silicone negative electrode active materials may be used individually by 1 type, and may be used in combination of 2 or more type.

In addition, the compounding quantity and particle diameter of a negative electrode active material are not specifically limited, It can make it the same as the negative electrode active material conventionally used.

<Binder Composition for Non-aqueous Secondary Battery Electrode>

As a binder composition for nonaqueous secondary battery electrodes, the binder composition for nonaqueous secondary battery electrodes containing the above-mentioned polymer (A) and a polyvalent cationic organic compound (B) is used.

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

<Challenge>

The conductive material is for securing electrical contact between the electrode active materials. As the conductive material, carbon black (for example, acetylene black, Ketjen black (registered trademark), furnace black, etc.), single layer or multilayer carbon nanotubes (multi-layer carbon nanotubes include a cup stack type), Conductive carbon materials such as a carbon nonwoven fabric sheet obtained by firing a carbon nanohorn, a vapor-grown carbon fiber, a milled carbon fiber obtained by crushing a polymer fiber after firing, a single layer or multilayer graphene, and a nonwoven fabric made of a polymer fiber; Fibers or foils of various metals can be used.

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

On the other hand, it is preferable that the content rate of the electrically conductive material in the slurry composition for non-aqueous secondary battery electrodes is 0.1 mass part or more per 100 mass parts of electrode active materials, It is more preferable that it is 0.5 mass part or more, It is preferable that it is 5 mass parts or less, It is 3 mass parts It is more preferable that it is below. When the amount of the conductive material is within the above range, electrical contact between the electrode active materials can be sufficiently secured, and battery characteristics (cycle characteristics, etc.) excellent in the secondary battery can be exhibited.

<Other ingredients>

As another component which can be mix | blended with a slurry composition, it does not specifically limit, The same thing as the other component which can be mix | blended with the binder composition mentioned above is mentioned. In addition, another component may be used individually by 1 type, and may be used combining two or more types by arbitrary ratios.

<Preparation of slurry composition>

The slurry composition mentioned above can be prepared by dissolving or disperse | distributing said each component in solvent, such as an organic solvent. Specifically, the slurry composition is mixed by mixing the above components and the solvent using a mixer such as a ball mill, a sand mill, a bead mill, a pigment disperser, a brain trajectory, an ultrasonic disperser, a homogenizer, a planetary mixer, a peel mix, and the like. 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 each said component in a solvent is not specifically limited, It can be set as arbitrary orders. Specifically, when preparing a slurry composition, each said component can be mixed in any order of following (1)-(3), for example.

(1) The said components are mixed at once.

(2) A binder composition containing a polymer (A) and a polyvalent cationic organic compound (B) and a conductive material are mixed to obtain a conductive material paste composition for a non-aqueous secondary battery electrode, and then a conductive material for a non-aqueous secondary battery electrode. The electrode active material is added to and mixed with the paste composition.

(3) After mixing a electrically conductive material and an electrode active material, the binder composition containing a polymer (A) and a polyvalent cationic organic compound (B) is added and mixed with the obtained mixture.

Among the above-mentioned, it is preferable to mix each said component in order of said (1) or (2). On the other hand, when the procedure of (2) is adopted, that is, the binder composition and the conductive material are mixed in advance, and the conductive material and the binder composition described above (that is, the conductive material, the polymer (A) and the polyvalent cationic) When the electrically conductive material paste composition for non-aqueous secondary battery electrodes containing an organic compound (B) and a solvent is used, a polymer (A) can be made to adsorb | suck to the surface of an electrically conductive material, and a electrically conductive material can be disperse | distributed favorably. As a result, the battery characteristics (cycle characteristics etc.) excellent in a secondary battery can be exhibited.

In the present invention, the conductive material paste composition for non-aqueous secondary battery electrodes is an intermediate product for preparing the slurry composition for non-aqueous secondary battery electrodes of the present invention. As described above, the conductive material and the polymer (A ), A polyvalent cationic organic compound (B), and a solvent, and a paste-like composition containing no electrode active material.

(Electrode for non-aqueous secondary battery)

The electrode for secondary batteries of this invention is equipped with an electrical power collector and the electrode mixture layer formed on the electrical power collector, and an electrode mixture layer is formed using the said slurry composition for non-aqueous secondary battery electrodes. That is, the electrode mixture layer contains at least an electrode active material, a polymer (A), and a polyvalent cationic organic compound (B) having a molecular weight of less than or equal to a predetermined value. 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 contained in the said slurry composition for non-aqueous secondary battery electrodes, and the suitable abundance ratio of these components is the same as the suitable abundance ratio of each component in a slurry composition.

And in the electrode for nonaqueous secondary batteries of this invention, since the slurry composition containing the binder composition for nonaqueous secondary battery electrodes of this invention is used, a polymer (A) and a polyvalent cationic organic compound (B) firmly mutually interact. The functioning, rigid electrode mixture layer can be favorably formed on the collector. Therefore, when the said electrode is used, swelling in the electrolyte solution of an electrode mixture layer is suppressed, and the secondary battery excellent in battery characteristics, such as cycling characteristics, is obtained.

<Method for Producing Electrode>

On the other hand, the electrode for non-aqueous secondary batteries of this invention is a process (coating process) of apply | coating the slurry composition mentioned above on an electrical power collector, and drying the slurry composition apply | coated on an electrical power collector, for example, on an electrical power collector It manufactures through the process (drying process) of forming a mixture layer.

<< coating process >>

It does not specifically limit as a method of apply | coating the said slurry composition on an electrical power collector, A well-known method can be used. Specifically, 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 and the like can be used as the coating method. At this time, a slurry composition may be apply | coated only to the single side | surface of an electrical power collector, and may be apply | coated to both surfaces. The thickness of the slurry film on the collector after drying after coating can be appropriately set in accordance with the thickness of the electrode mixture layer obtained by drying.

Here, as a collector which apply | coats a slurry composition, the material which has electroconductivity and is electrochemically durable is used. Specifically, as an electrical power collector, the electrical power collector which consists of iron, copper, aluminum, nickel, stainless steel, titanium, tantalum, gold, platinum, etc. can be used, for example. In addition, said material may be used individually by 1 type, and may be used combining two or more types by arbitrary ratios.

<< drying process >>

It does not specifically limit as a method of drying the slurry composition on an electrical power collector, A well-known method can be used, For example, the drying method by a warm air, a hot air, the low humidity wind drying method, the vacuum drying method, the irradiation method of infrared rays, an electron beam, etc. Can be mentioned. Thus, by drying the slurry composition on an electrical power collector, an electrode mixture layer is formed on an electrical power collector, and the electrode for secondary batteries provided with an electrical power collector and an electrode mixture layer can be obtained. 60 degreeC or more and 200 degrees C or less are preferable, and 90 degreeC or more and 150 degrees C or less of a drying temperature are more preferable.

On the other hand, when the polymer which has at least any one of a carboxylic acid group, a sulfonic acid group, and a phosphoric acid group is used as a polymer (A), for example, and the compound containing an amino group as a polyvalent cationic organic compound (B) is used, a polymer (A) and a polyvalent cationic organic compound (B) are bridge | crosslinked by an amide bond, the swelling in the electrolyte solution of an electrode mixture layer is further suppressed, and the cycling characteristics of a secondary battery can be improved further.

In addition, after a drying process, you may pressurize an electrode mixture layer using a metal mold | die press, a roll press, etc. By the pressure treatment, the adhesion between the electrode mixture layer and the current collector can be improved. Moreover, when an electrode mixture layer contains a curable polymer, it is preferable to harden the said polymer after formation of an electrode mixture layer.

(Non-aqueous Secondary Battery)

The nonaqueous secondary battery of this invention is equipped with a positive electrode, a negative electrode, electrolyte solution, and a separator, and uses the electrode for secondary batteries of this invention as at least one of a positive electrode and a negative electrode. And since the nonaqueous secondary battery of this invention is equipped with the electrode for nonaqueous secondary batteries of this invention, it is excellent in battery characteristics, such as cycling characteristics.

In addition, below, although the case where a non-aqueous secondary battery is a lithium ion secondary battery is demonstrated as an example, this invention is not limited to the following example.

<Electrode>

Here, the electrode other than the above-mentioned non-aqueous secondary battery electrode which can be used for the non-aqueous secondary battery of the present invention is not particularly limited, and a known electrode used for the production of the secondary battery can be used. Specifically, as an electrode other than the electrode for nonaqueous secondary batteries mentioned above, the electrode formed by forming an electrode mixture layer on an electrical power collector using a well-known manufacturing method can be used.

<Electrolyte amount>

As electrolyte solution, the organic electrolyte solution which melt | dissolved the supporting electrolyte in the organic solvent is used normally. As a supporting electrolyte of a lithium ion secondary battery, lithium salt is used, for example. Examples of lithium salts include LiPF ₆ , LiAsF ₆ , LiBF ₄ , LiSbF ₆ , LiAlCl ₄ , LiClO ₄ , CF ₃ SO ₃ Li, C ₄ F ₉ SO ₃ Li, CF ₃ COOLi, (CF ₃ CO) ₂ NLi, (CF ₃ SO ₂ ) ₂ NLi, (C ₂ F ₅ SO ₂ ) NLi, and the like. Among them, LiPF ₆ , LiClO ₄ , CF ₃ SO ₃ Li are preferable, and LiPF ₆ is particularly preferable because it dissolves easily in a solvent and exhibits high dissociation degree. In addition, an electrolyte may be used individually by 1 type and may be used combining two or more types by arbitrary ratios. Usually, lithium ion conductivity tends to increase as the support electrolyte having a high dissociation degree is used, and thus lithium ion conductivity can be adjusted by the type of the supporting electrolyte.

The organic solvent to be used for the electrolyte is not particularly limited as long as it can dissolve the supporting electrolyte. Examples thereof include dimethyl carbonate (DMC), ethylene carbonate (EC), diethyl carbonate (DEC), and propylene carbonate (PC). Carbonates such as butylene carbonate (BC) and ethyl methyl carbonate (EMC); esters such as γ-butyrolactone and methyl formate; Ethers such as 1,2-dimethoxyethane and tetrahydrofuran; Sulfur-containing compounds such as sulfolane and dimethyl sulfoxide; Etc. are used suitably. Moreover, you may use the liquid mixture of these solvent. Especially, since dielectric constant is high and a stable electric potential area | region is wide, it is preferable to use carbonates.

In addition, the density | concentration of the electrolyte in electrolyte solution can be adjusted suitably. Moreover, a known additive can be added to electrolyte solution.

<Separator>

It does not specifically limit as a separator, For example, the thing of Unexamined-Japanese-Patent No. 2012-204303 can be used. Among these, the polyolefin type (polyethylene, polypropylene, polybutene, poly) can be made thin in the thickness of a separator, by which the ratio of the electrode active material in a secondary battery can be made high, and the capacity per volume can be made high. The microporous membrane which consists of resin of vinyl chloride) is preferable.

<Method for Manufacturing Secondary Battery>

In the secondary battery of the present invention, for example, the positive electrode and the negative electrode overlap each other via a separator, and if necessary, the secondary battery is wound, folded, or the like according to the shape of the battery, placed in a battery container, and the electrolyte is injected into and sealed in the battery container. It can manufacture. In order to prevent an increase in pressure inside the secondary battery, overcharge and discharge, and the like, an overcurrent preventing element such as a fuse or a PTC element, an expanded metal, a lead plate, or the like may be provided as necessary. The shape of the secondary battery may be any of a coin type, a button type, a sheet type, a cylindrical shape, a square shape, and a flat type.

EXAMPLE

EMBODIMENT OF THE INVENTION Hereinafter, although this invention is demonstrated concretely based on an Example, this invention is not limited to these Examples. In addition, in the following description, "%", "ppm", and "part" which represent quantity are a mass reference | standard unless there is particular notice.

In addition, in the polymer manufactured by copolymerizing a plurality of types of monomers, the proportion in the polymer of the monomer unit formed by polymerizing any monomer is generally used for polymerization of the polymer unless otherwise stated. It corresponds to the ratio (injection ratio) of any of said monomers to monomer.

In the Example and the comparative example, the viscosity stability of the binder composition, the electrolyte swelling degree of the film which consists of a binder composition, and the cycling characteristics of the secondary battery were evaluated by the following method.

<Viscosity stability>

The viscosity M0 immediately after preparation of a binder composition and the viscosity M1 after storing for 7 days at 60 degreeC were measured. In addition, the viscosity was measured on condition of temperature: 25 degreeC, rotor: No. 4, and rotor rotation speed: 60 rpm using a Brookfield viscometer.

And the viscosity change rate (DELTA) M (= M1 / M0x100 (%)) was computed and it evaluated on the following reference | standard. 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 but less than 120%

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

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

E: Viscosity change rate ΔM is 150% or more

<Electrolyte Swelling Degree>

The binder composition in a Teflon® chalet was dried at 120 ° C for 12 hours to obtain a film having a thickness of 1 mm. The film was blanked in a circular shape having a diameter of 1.6 mm to obtain a sample for measurement (similar electrode mixture layer), and the weight W0 of the sample for measurement was measured.

After storing the obtained measurement sample for 72 hours in 60 degreeC electrolyte solution, the electrolyte solution adhered to the measurement sample was wiped off and the weight W1 of the measurement sample was measured.

On the other hand, as the electrolyte, ethylene carbonate (EC), propylene carbonate (PC), ethyl methyl carbonate (EMC), and propyl propionate (PP) were selected from EC: PC: EMC: PP = 2: 1: 1: LiPF ₆ was dissolved at a concentration of 1 mol / liter in a mixed solvent formed by mixing at 6 (mass ratio), and 1.5 vol% of vinylene carbonate was added as an additive.

And electrolyte solution swelling degree (DELTA) W (= W1 / W0x100 (%)) was computed and it evaluated on the following reference | standard. It shows that the swelling in the electrolyte solution of the electrode mixture layer obtained using a binder composition can be suppressed so that the value of electrolyte solution swelling degree (DELTA) W is small.

A: electrolyte swelling degree (DELTA) W is less than 600%

B: electrolyte swelling degree (DELTA) W is 600% or more and less than 800%

C: electrolyte swelling degree (DELTA) W is 800% or more and less than 1000%

D: electrolyte swelling degree (DELTA) W is 1000% or more and less than 2000%

E: electrolyte swelling degree (DELTA) W is 2000% or more

<Cycle characteristics>

With respect to the produced secondary battery, the operation of charging to 0.25 C at 4.35 V and discharging to 3.0 V in a 25 ° C. environment was repeated three times. Thereafter, the battery was charged at 1 CmA until the battery voltage became 4.35 V, and the operation of discharging until the battery voltage became 3.0 V at 1 CmA was repeated 100 times. From the first discharge capacity C0 and the 100th discharge capacity C1, the capacity retention rate ΔC = (C1 / C0) × 100 (%) was calculated and evaluated according to the following criteria. The higher the value of the capacity retention rate, the smaller the decrease in discharge capacity, indicating that the cycle characteristics are excellent.

A: Capacity retention rate ΔC is 85% or more

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

C: capacity retention ΔC is 75% or more but less than 80%

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

E: capacity retention ΔC is less than 70%

(Example 1)

<Preparation of Polymer (A)>

In a metal bottle, 180 parts of ion-exchanged water, 25 parts of sodium dodecylbenzenesulfonate aqueous solution of 10 mass% of concentration, 5 parts of methacrylic acid as a coupling functional group containing monomer, 10 parts of acrylonitrile as a nitrile-group containing monomer, (meth) 25 parts of 2-ethylhexyl acrylates as acrylate ester monomers and 0.5 parts of t-dodecyl mercaptans as molecular weight modifiers were sequentially added, and the internal gas was substituted three times with nitrogen, and then 1,3-as a conjugated diene monomer. 60 parts of butadiene were added. The metal bottle was kept at 5 degreeC, 0.1 part of cumene hydroperoxides as a polymerization initiator were added, and it superposed | polymerized for 16 hours, rotating a metal bottle. Subsequently, 0.1 part of hydroquinone aqueous solution of 10 mass% concentration is added as a polymerization terminator, and a polymerization reaction is stopped, residual monomer is removed using the rotary evaporator of 60 degreeC of water temperature, and the aqueous dispersion of a polymer (solid content concentration about 30 mass%).

Subsequently, the aqueous dispersion prepared above and the palladium catalyst (1 mass% palladium acetate acetone solution and ion exchanged water) were placed in an autoclave so that the palladium content of the polymer contained in the aqueous dispersion obtained above was 750 ppm. 1: 1 (mass ratio mixed solution) was added. Then, 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 aqueous dispersion of the obtained hydrogenated polymer so that the solid content concentration of the hydrogenated polymer might be 7%. And distillation under reduced pressure was carried out at 90 degreeC, water and excess NMP were removed, and the NMP solution (solid content concentration 8%) of the polymer (A) (hydrogenated polymer) was obtained.

<Preparation of polyvalent cationic organic compound (B)>

As a polyvalent cationic organic compound (B), polyethyleneimine (number average molecular weight: 600, "Epomin SP-006", the Nippon Catalyst company make) was prepared. And NMP solution (solid content concentration 8%) of this polyethyleneimine was prepared.

<Preparation of the binder composition for positive electrodes>

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

<Preparation of the slurry composition for positive electrodes>

100 parts of lithium cobaltate (LiCoO ₂ , volume average particle diameter: 12 μm) as a positive electrode active material, and Ketjen Black (product of 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, a binder composition for the positive electrode in which the polymer (A) is 0.6 parts (in terms of solid content), 0.6 parts (in terms of solid content) of NMP solution of polyvinylidene fluoride (PVDF) as a binder, and additional solvent The slurry composition for positive electrodes was prepared by mixing NMP as a planetary mixer. On the other hand, the amount of additional NMP is such that the viscosity of the slurry composition for the positive electrode obtained (uses a type B viscometer. Temperature: 25 ° C., rotor: No. 4, rotor speed: 60 rpm) is within a range of 5000 ± 200 mPa · s. Adjusted.

<Production of positive electrode>

The obtained slurry composition for positive electrodes was apply | coated so that the coating amount after drying might be set to 20 mg / cm <^2> on the single side | surface of the electrical power collector which consists of aluminum foil of 15 micrometers in thickness. And the apply | coated slurry composition was dried at 90 degreeC for 20 minutes, and 120 degreeC for 20 minutes, Then, it heat-processed at 150 degreeC for 2 hours, and obtained the positive electrode original fabric. And the obtained positive electrode original fabric was rolled by the roll press, and the positive electrode provided with the positive electrode mixture layer of density 3.7g / cm <^3> on an aluminum foil (current collector) was obtained.

<Production of negative electrode>

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

The obtained slurry composition for negative electrodes was apply | coated so that the coating amount after drying might be set to 10 mg / cm <^2> on the single side | surface of the electrical power collector which consists of copper foil of 15 micrometers in thickness. And the apply | coated slurry composition was dried for 20 minutes at 60 degreeC, and 20 minutes at 120 degreeC, and the negative electrode original fabric was obtained. And the obtained negative electrode original fabric was rolled by the roll press, and the negative electrode which equips the copper foil (current collector) with the negative electrode mixture layer of density 1.5g / cm <^3> was obtained.

<Preparation of separator>

A single layer polypropylene separator (65 mm wide, 500 mm long, 25 μm thick, manufactured by the dry method, porosity 55%) was cut out into a square of 4.4 cm × 4.4 cm.

<Production of Secondary Battery>

As the exterior of the battery, an aluminum packaging exterior was prepared. And the positive electrode obtained above was cut out to square of 4 cm x 4 cm, and it arrange | positioned so that the surface of the electrical power collector side may be in contact with an aluminum packaging material exterior. The square separator obtained above was arrange | positioned on the positive electrode mixture layer of a positive electrode. Moreover, the negative electrode obtained above was cut out in square of 4.2 cm x 4.2 cm, and this was arrange | positioned on the separator so that the surface of the negative electrode mixture layer side might face a separator. In addition, in order to fill the electrolyte solution and then seal the opening of the aluminum packaging exterior, 150 degreeC heat sealing was done and the aluminum packaging exterior was closed, and the lithium ion secondary battery was obtained. On the other hand, as the electrolyte, ethylene carbonate (EC), propylene carbonate (PC), ethyl methyl carbonate (EMC), and propyl propionate (PP) were selected from EC: PC: EMC: PP = 2: 1: 1: LiPF ₆ was dissolved at a concentration of 1 mol / liter in a mixed solvent formed by mixing at 6 (mass ratio), and 1.5 vol% of vinylene carbonate was added as an additive.

And cycle characteristics were evaluated using the obtained lithium ion secondary battery. The results are shown in Table 1.

(Example 2, 4-15)

At the time of preparation of the polymer (A), 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 the monomer composition of Table 1 was employed. It was. And it evaluated similarly to Example 1. The results are shown in Table 1.

(Example 3)

The monomer composition of Table 1 is employ | adopted at the time of preparation of a polymer (A), and at the time of preparation of the binder composition for positive electrodes, N, N'-bis (3-phenyl-2- pro instead of the NMP solution of polyethyleneimine. A polymer (A), a binder composition for a positive electrode, and a slurry for a positive electrode were produced in the same manner as in Example 1, except that an NMP solution (solid content concentration of 8%) of phenylidene) -1,6-hexanediamine (molecular weight: 344) was used. The composition, the positive electrode, the negative electrode, and the secondary battery were produced. And it evaluated similarly to Example 1. The results are shown in Table 1.

(Examples 16 and 17)

At the time of preparation of the binder composition for positive electrodes, it carried out similarly to Example 1 except having changed the quantity of the polyvalent cationic organic compound (B) as Table 1, and the polymer (A), the binder composition for positive electrodes, and the slurry for positive electrodes The composition, the positive electrode, the negative electrode, and the secondary battery were produced. And it evaluated similarly to Example 1. The results are shown in Table 1.

(Examples 18 and 19)

At the time of preparation of the binder composition for the positive electrode, instead of the NMP solution of polyethyleneimine (number average molecular weight: 600), polyethyleneimine (number average molecular weight: 1200, "Epomin SP-012", manufactured by Nippon Catalyst Co., Ltd.) or polyethyleneimine ( The number average molecular weight: 1800, except that the NMP solution (8% of solid content concentration) of "Epomin SP-018" and the Nippon Catalyst Co., Ltd. product was used, It carried out similarly to Example 1, and the binder composition for polymers (A) and positive electrodes The slurry composition for positive electrodes, the positive electrode, the negative electrode, and the secondary battery were produced. And it evaluated similarly to Example 1. The results are shown in Table 1.

(Examples 20-23)

At the time of preparation of the binder composition for the positive electrode, N, N'-bis (3-phenyl-2-propenylidene) -1,6-hexanediamine (molecular weight) instead of the NMP solution of polyethyleneimine (number average molecular weight: 600) 344), NMP solution (solid content) of polyallylamine (number average molecular weight: 1600, "PAA-01", manufactured by Nittobo Medical Co., Ltd.), diethylenetriamine (molecular weight: 103), or ethylenediamine (molecular weight: 60) A polymer (A), a binder composition for a positive electrode, a slurry composition for a positive electrode, a positive electrode, a negative electrode, and a secondary battery were produced in the same manner as in Example 1 except that 8%) was used. And it evaluated similarly to Example 1. The results are shown in Table 1.

(Comparative Example 1)

Except not using a polyvalent cationic organic compound (B) at the time of preparation of the binder composition for positive electrodes, it carried out similarly to Example 1, and the polymer (A), the binder composition for positive electrodes, the slurry composition for positive electrodes, a positive electrode, and a negative electrode , And a secondary battery was produced. And it evaluated similarly to Example 1. The results are shown in Table 1.

(Comparative Example 2)

At the time of preparation of the binder composition for the positive electrode, instead of the NMP solution of polyethyleneimine (number average molecular weight: 600), an NMP solution of polyethyleneimine (number average molecular weight: 10000, "Epomin SP-200", manufactured by Nippon Catalyst Co., Ltd.) Except having used solid content concentration 8%), it carried out similarly to Example 1, and produced the polymer (A), the binder composition for positive electrodes, the slurry composition for positive electrodes, the positive electrode, the negative electrode, and the secondary battery. And it evaluated similarly to Example 1. The results are shown in Table 1.

(Comparative Example 3)

At the time of preparation of the polymer (A), 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 the monomer composition of Table 1 was employed. It was. And it evaluated similarly to Example 1. The results are shown in Table 1.

(Comparative Example 4)

Except having used aluminum chelate (Kawaken Fine Chemical Co., Ltd. product name "Aluminate chelate A (W)", aluminum tris (acetylacetonate)) instead of the polyvalent cationic organic compound (B) for preparation of the positive electrode binder composition. In the same manner as in Example 1, a polymer (A), a binder composition for a positive electrode, a slurry composition for a positive electrode, a positive electrode, a negative electrode, and a secondary battery were produced. And it evaluated similarly to Example 1. The results are shown in Table 1.

On the other hand, in Table 1 shown below,

"COOH" represents a carboxylic acid group,

"AA" represents an acrylic acid unit,

"IA" represents an itaconic acid unit,

"MAA" represents a methacrylic acid unit,

"MBM" represents the monobutyl maleate unit,

"MMA" represents a methyl methacrylate unit,

"EA" represents an ethylacrylate unit,

"BA" represents an n-butylacrylate unit,

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

"AN" represents an acrylonitrile unit,

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

"PEI" represents polyethyleneimine,

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

"PAA" represents polyallylamine,

"DETA" represents diethylenetriamine,

"ED" represents ethylenediamine,

"AL" represents an aluminum chelate.

From Table 1, in Examples 1-23 using the binder composition containing the polymer (A) which has a binding functional group, and the molecular weight is below a predetermined value, the polyvalent cationic organic compound (B), binder composition is excellent in viscosity stability. Furthermore, it turns out that the secondary battery which has the outstanding cycling characteristics can be manufactured by obtaining the slurry composition which can form the electrode mixture layer in which the swelling in electrolyte solution was suppressed.

On the other hand, in Comparative Example 1 using the binder composition which contains the polymer (A) which has a binding functional group from Table 1, and does not contain the polyvalent cationic organic compound (B) whose molecular weight is below a predetermined value, It can be seen that the swelling in the electrolytic solution cannot be sufficiently suppressed and the cycle characteristics of the secondary battery are reduced.

In addition, from Table 1, although the polymer (A) and the polyvalent cationic organic compound (B) which have a binding functional group are included, the binder composition whose molecular weight of the said polyvalent cationic organic compound (B) exceeds a predetermined value is shown. In the used comparative example 2, it turns out that a binder composition is inferior in viscosity stability, and the cycling characteristics of a secondary battery fall.

And from Table 1, in the comparative example 3 using the binder composition containing the polymer which does not have a binding functional group, and the polyvalent cationic organic compound (B) whose molecular weight is below a predetermined value, swelling in the electrolyte solution of an electrode mixture layer is shown. It cannot be fully suppressed and it turns out that the cycling characteristics of a secondary battery fall.

In addition, from Table 1, in Comparative Example 4 using the polymer (A) having a bonding functional group and a binder composition containing aluminum chelate, the binder composition is inferior in viscosity stability, and the cycle characteristics of the secondary battery are deteriorated. Can be. It is inferred that the degradation of these performances is due to aluminum ions derived from aluminum chelate. Specifically, the decrease in viscosity stability is inferred because the mobility of the aluminum ions in the solvent is high, causing a crosslinking reaction with the polymer (A) to thicken the polymer (A). In addition, the decrease in cycle characteristics causes the aluminum ions to crosslink with the polymer (A) due to the temperature rise due to the shearing at the time of preparing the slurry composition, and as a result, the polymer (A) becomes difficult to coat the conductive material, resulting in the separation of the conductive material. Inferred because the acid is damaged.

[Industry availability]

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

Moreover, according to this invention, the electrically conductive material paste composition for non-aqueous secondary battery electrodes which can form the electrode mixture layer in which swelling in electrolyte solution was suppressed, and can exhibit the outstanding cycling characteristic to a non-aqueous secondary battery, and a non-aqueous system are also provided. The slurry composition for secondary battery electrodes is obtained.

Moreover, according to this invention, the electrode for non-aqueous secondary batteries is provided which is equipped with the electrode mixture layer in which swelling in electrolyte solution was suppressed, and which can exhibit the outstanding cycling characteristic to a non-aqueous secondary battery.

And according to this invention, the non-aqueous secondary battery which has the outstanding cycling characteristics is obtained.

Claims (9)

A binder composition for non-aqueous secondary battery electrodes comprising a polymer having a functional group capable of bonding with a cationic group, and an organic compound having two or more cationic groups and having a molecular weight of 8000 or less. The method of claim 1,
The binder composition for non-aqueous secondary battery electrodes which is a functional group couple | bonded with the said cationic group is at least 1 sort (s) chosen from the group which consists of a carboxylic acid group, a sulfonic acid group, a phosphoric acid group, and a hydroxyl group. The method according to claim 1 or 2,
The binder composition for non-aqueous secondary battery electrodes in which the said polymer contains the monomer unit containing the functional group couple | bonded with a cationic group in the ratio of 0.1 mass% or more and 20 mass% or less. The method according to any one of claims 1 to 3,
The binder composition for non-aqueous secondary battery electrodes containing 0.1 mass part or more and 20 mass parts or less of said organic compound per 100 mass parts of said polymers. The method according to any one of claims 1 to 4,
The polymer includes a nitrile group-containing monomer unit, at least one of a conjugated diene monomer unit and an alkylene structural unit,
The ratio of the said nitrile-group containing monomeric unit in the said polymer is 5 mass% or more and 35 mass% or less, and the sum total of the ratio of the said conjugated diene monomeric unit in the said polymer, and the ratio of the said alkylene structural unit is 30 mass% or more and 90 mass The binder composition for non-aqueous secondary battery electrodes which is% or less. The electrically conductive material paste composition for nonaqueous secondary battery electrodes containing a electrically conductive material and the binder composition for nonaqueous secondary battery electrodes of any one of Claims 1-5. A nonaqueous secondary battery electrode containing an electrode active material and the binder composition for nonaqueous secondary battery electrodes of any one of Claims 1-5, or the electrically conductive material paste composition for nonaqueous secondary battery electrodes of Claim 6. Slurry composition. The electrode for non-aqueous secondary batteries provided with the electrode mixture layer formed using the slurry composition for non-aqueous secondary battery electrodes of Claim 7. It is provided with a positive electrode, a negative electrode, electrolyte solution, and a separator,
At least one of the said positive electrode and a negative electrode is a non-aqueous secondary battery electrode of Claim 8.