KR20200024791A - Binder composition for electrochemical device, slurry composition for electrochemical device functional layer, slurry composition for electrochemical device adhesive layer, and composite film - Google Patents

Abstract

Provided is a binder composition for an electrochemical device which is excellent in binding property and can form a functional layer capable of improving rate characteristics and cycle characteristics of an electrochemical device (for example, a secondary battery). The binder composition for an electrochemical device of the present invention contains a binder and a hydrogen carbonate salt, and the binder is selected from the group consisting of a carboxyl group, a hydroxyl group, a cyano group, an amino group, an epoxy group, an oxazoline group, an isocyanate group, and a sulfonic acid group. A polymer having at least one functional group selected.

Description

Binder composition for electrochemical device, slurry composition for electrochemical device functional layer, slurry composition for electrochemical device adhesive layer, and composite membrane

The present invention relates to a binder composition for an electrochemical device, a slurry composition for an electrochemical device functional layer, a slurry composition for an electrochemical device adhesive layer, and a composite film.

Conventionally, as an electrochemical element, non-aqueous batteries, such as a lithium ion secondary battery, an electric double layer capacitor, and a lithium ion capacitor are used for a wide range of uses.

Here, non-aqueous secondary batteries (hereinafter, simply abbreviated as "secondary batteries"), such as lithium ion secondary batteries, have the characteristics of being compact, lightweight, high in energy density, and capable of repeated charging and discharging. . In general, a nonaqueous secondary battery includes an electrode (a positive electrode and a negative electrode) and a battery member such as a separator that isolates the positive electrode and the negative electrode and prevents a short circuit between the positive electrode and the negative electrode.

Here, the battery member of the secondary battery is provided with a functional layer including a binder and optionally including particles (hereinafter referred to as "functional particles") blended in order to exhibit a desired function to the battery member. The member to be used is used.

As a separator of a secondary battery, the separator provided with the adhesive layer containing a binder and the porous membrane layer containing a binder and nonelectroconductive particles as functional particles are used on a separator base material specifically ,. In addition, as an electrode of a secondary battery, on an electrical power collector, on an electrode provided with an electrode mixture layer containing a binder and electrode active material particles as functional particles, or on an electrode base material provided with an electrode mixture layer on an electrical power collector, The electrode further provided with the adhesive layer and porous film layer mentioned above is used.

And in order to achieve the further improvement of the performance of a secondary battery, improvement of the binder composition containing a binder is tried conventionally. For example, in patent document 1, the technique of improving the adhesiveness with respect to the electrical power collector of an electrode mixture layer is proposed by using a predetermined binder composition.

Japanese Unexamined Patent Publication No. 2016-009544

However, in the above conventional technique, it is difficult to sufficiently secure the adhesiveness (fill strength) of the electrode mixture layer, and further, the secondary battery cannot exhibit excellent rate characteristics and cycle characteristics. Therefore, the said prior art had room for improvement in providing the adhesiveness (fill strength) excellent to functional layers, such as an electrode mixture layer, and improving the rate characteristic and cycling characteristics of a secondary battery.

Accordingly, the present invention provides a functional layer (electrode mixture layer, porous membrane layer, adhesive layer) or composite membrane which is excellent in binding property and capable of improving rate characteristics and cycle characteristics of an electrochemical device (for example, a secondary battery). It is an object to provide a binder composition for an electrochemical device which can be formed.

In addition, the present invention provides a functional layer (electrode mixture layer) having excellent adhesion (fill strength, process adhesion) and capable of improving rate characteristics and cycle characteristics of an electrochemical device (for example, a secondary battery). It is an object to provide a slurry composition for an electrochemical device functional layer which can form a porous film layer, an adhesive layer) or a composite film.

Moreover, an object of this invention is to provide the composite film which has the outstanding adhesiveness (fill strength) and can improve the rate characteristic and cycling characteristics of an electrochemical element (for example, a secondary battery).

MEANS TO SOLVE THE PROBLEM This inventor earnestly examined for the purpose of solving the said subject. Then, the present inventors form a functional layer (electrode mixture layer, porous membrane layer, adhesive layer) or a composite membrane using a binder composition containing a predetermined binder and hydrogen carbonate salt, and then obtain a functional layer (electrode mixture layer, porous membrane). Layer, adhesive layer) or composite film (adhesive strength, process adhesion) can be improved, and an electrochemical device (eg, secondary battery) comprising a functional layer (electrode mixture layer, porous film layer, adhesive layer) or composite film ), It was found that excellent rate characteristics and cycle characteristics can be exhibited, thereby completing the present invention.

That is, this invention aims at solving the said subject advantageously, The binder composition for electrochemical elements of this invention contains a binder and hydrogencarbonate, The said binder is a carboxyl group, a hydroxyl group, a cyanide. It is a polymer which has at least 1 sort (s) of functional group chosen from the group which consists of a furnace group, an amino group, an epoxy group, an oxazoline group, an isocyanate group, and a sulfonic acid group. Thus, since the binder composition containing a specific binder and hydrogen carbonate is excellent in binding property, when the said binder composition is used, the functional layer excellent in adhesiveness (fill strength) can be obtained. And when the element member (battery member) provided with the said functional layer is used, the rate characteristic and cycling characteristics excellent in an electrochemical element (for example, a secondary battery) can be exhibited.

Here, in the binder composition for electrochemical elements of this invention, it is preferable that content of the said hydrogen carbonate is 5 mass% or more and 85 mass% or less with respect to the said binder. When content of the said hydrogen carbonate is 5 mass% or more and 85 mass% or less with respect to the said binder, binding property of a binder composition will be improved further, the slurry stability of the slurry composition obtained will be raised, and the adhesiveness of a functional layer (fill strength) ) And an electrochemical element (for example, a secondary battery) can be further improved.

Moreover, in the binder composition for electrochemical elements of this invention, the said binder contains at least any one of a carboxyl group and a cyano group, The content of the carboxyl group in the said binder and content of the cyano group in the said binder The sum is preferably 0.1 mmol or more and 50 mmol or less per 1 g of the binder. When the sum of the content of the carboxyl group in the binder and the content of the cyano group in the binder is 0.1 mmol or more and 50 mmol or less per 1 g of the binder, the slurry stability of the resulting slurry composition is increased and the functional layer The adhesive property (fill strength) of the and the rate characteristic of an electrochemical element (for example, a secondary battery) can be improved further.

Moreover, in the binder composition for electrochemical elements of this invention, it is preferable that the said binder contains a cyano group, and content of the cyano group in the said binder is 1 mmol or more and 40 mmol or less per 1 g of said binders. . If content of the cyano group in the said binder is 1 mmol or more and 40 mmol or less per 1 g of said binders, the rate characteristic of an electrochemical element (for example, a secondary battery) can be improved further.

Moreover, this invention aims at solving the said subject advantageously, The electrochemical element functional layer slurry composition of this invention contains the above-mentioned any one binder composition for electrochemical elements. When a functional layer is formed from the slurry composition for electrochemical element functional layers mentioned above, the adhesiveness (fill strength) of a functional layer can be improved. And when the element member (battery member) provided with the said functional layer is used, the rate characteristic and cycling characteristics excellent in an electrochemical element (for example, a secondary battery) can be exhibited.

In addition, the slurry composition for electrochemical device functional layers of the present invention may further include an electrode active material. When the slurry composition mentioned above contains an electrode active material further, when the said slurry composition is used, the electrode mixture layer which is excellent in adhesiveness and can exhibit the outstanding rate characteristic and cycling characteristics to a secondary battery can be formed.

In addition, the slurry composition for the electrochemical device functional layer of the present invention may further include non-conductive particles.

Moreover, this invention aims at solving the said subject advantageously, The slurry composition for electrochemical element bonding layers of this invention contains the binder composition for any one of the electrochemical elements mentioned above, An electrode active material and a specific figure It is characterized by not containing a malleable particle. When an adhesive layer is formed from the slurry composition for electrochemical element adhesive layers mentioned above, the adhesiveness (fill strength, process adhesiveness) of an adhesive layer can be improved. And when the element member (battery member) provided with the said contact bonding layer is used, the rate characteristic and cycling characteristics excellent in an electrochemical element (for example, a secondary battery) can be exhibited.

In addition, the slurry composition for porous films contains the binder composition for any one of the electrochemical elements mentioned above. When a porous film is formed from the slurry composition for porous films mentioned above, the adhesiveness (fill strength) of a porous film can be improved. And when the element member (battery member) provided with the said porous film is used, the rate characteristic and cycling characteristics excellent in an electrochemical element (for example, a secondary battery) can be exhibited.

Moreover, this invention aims at solving the said subject advantageously, The composite membrane of this invention uses the slurry composition for porous film layers or the slurry composition for contact bonding layers which are the slurry compositions for electrochemical element functional layers mentioned above on a separator base material. It was laminated | stacked on or introduce | transduced in the separator base material, It is characterized by the above-mentioned. When the slurry composition for porous film layers or the slurry composition for adhesive layers which are the slurry compositions for electrochemical element functional layers mentioned above is laminated | stacked on a separator base material, or introduce | transduced in a separator base material, a composite membrane can be reliably formed.

In addition, in this specification, the functional layer containing a binder and electrode active material particle is called an "electrode mixture layer", and the functional layer containing a binder and nonelectroconductive particle is called a "porous membrane layer", and contains a binder, The functional layer containing neither electrode active material particles nor non-conductive particles is referred to as "adhesive layer". Moreover, the film | membrane in which a porous film layer or an adhesive layer was formed on the separator base material or in the separator base material by apply | coating etc. the slurry composition for porous film layers or the slurry composition for adhesive layers to a separator base material is called "composite membrane."

According to the present invention, a functional layer (electrode mixture layer, porous film layer, adhesive layer) or composite film which is excellent in binding property and can improve rate characteristics and cycle characteristics of an electrochemical device (for example, a secondary battery) is formed. Possible binder compositions for electrochemical devices can be provided.

Moreover, according to this invention, the functional layer (electrode mixture layer) which has the outstanding adhesiveness (fill strength, process adhesiveness), and can improve the rate characteristic and cycling characteristics of an electrochemical element (for example, a secondary battery). , Porous membrane layer, adhesive layer) or a slurry composition for an electrochemical device functional layer which can form a composite membrane can be provided.

Moreover, according to this invention, the composite film which has the outstanding adhesiveness (fill strength) and can improve the rate characteristic and cycling characteristics of an electrochemical element (for example, a secondary battery) can be provided.

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

Here, the binder composition for electrochemical elements of this invention is used for the manufacture use of an electrochemical element (for example, a secondary battery), For example, the electrochemical element functional layer (electrode mixture layer, many) of this invention It can be used for preparation of the slurry composition for sclera layers, adhesive layers). And the slurry composition for electrochemical element functional layers (electrode mixture layer, porous film layer, adhesive layer) of this invention is arbitrary functional layers which are responsible for the function, such as transfer of an electron, reinforcement, or adhesion in an electrochemical element. (For example, an electrode mixture layer, a porous film layer, an adhesive layer) or a composite film can be used. And an electrochemical element (for example, a secondary battery) is an element which has a functional layer for electrochemical elements (electrode mixture layer, a porous film layer, an adhesive layer) formed by the slurry composition for electrochemical element functional layers of this invention, or a composite film. A member (battery member) is provided.

(Binder Composition for Electrochemical Devices)

The binder composition of the present invention is a composition in which a binder and a hydrogen carbonate are dissolved and / or dispersed in a solvent. In addition, the binder composition of this invention may contain other components other than a binder, hydrogencarbonate, and a solvent.

The binder composition of the present invention is inferred because the hydrogen carbonate interacts with the binder, and the binder composition of the present invention exhibits excellent binding properties by including the hydrogen carbonate. And when using the binder composition of this invention, the outstanding adhesiveness (fill strength, process adhesiveness) is exhibited to the functional layer (electrode mixture layer, porous film layer, adhesive layer) or composite membrane obtained, and an electrochemical element (for example, For example, element characteristics (battery characteristics) of the secondary battery can be improved. Moreover, the binder composition of this invention can manufacture the electrochemical element excellent in the rate characteristic, cycling characteristics, etc ..

<Binder>

A binder is a component which expresses binding property to a binder composition, In the functional layer formed on the base material using the slurry composition containing a binder composition, while keeping components, such as a functional particle, from detaching from a functional layer, It is possible to bond the battery members via the functional layer. The glass transition temperature of a binder is less than 250 degreeC, it is preferable that it is 100 degrees C or less, and it is more preferable that it is 25 degrees C or less.

[Types of Binder]

Here, as a binder, if it can be used in electrochemical elements, such as a secondary battery, it will not specifically limit. For example, as a binder, the polymer (synthetic polymer, for example, addition polymer obtained by addition polymerization) obtained by superposing | polymerizing the monomer composition containing the monomer which can express binding property can be used. Such polymers include, for example, (i) diene polymers (aliphatic conjugated diene / aromatic vinyl copolymers (polymers mainly comprising aliphatic conjugated diene monomer units and aromatic vinyl monomer units), aliphatic conjugated diene homopolymers), (ii) an acrylate polymer (polymer mainly containing (meth) acrylic acid ester monomer unit), (iii) fluorine polymer (polymer mainly containing fluorine-containing monomer unit), (iv) polycarboxylic acid polymer ((meth ) Acrylic acid / (meth) acrylamide copolymer (polymer mainly comprising (meth) acrylic acid monomer unit and (meth) acrylamide monomer unit), (meth) acrylic acid homopolymer), (v) cyano polymer (acrylo) Nitrile-based polymers (polymers mainly containing (meth) acrylonitrile monomer units)). These may be used individually by 1 type and may be used combining two or more types by arbitrary ratios.

Here, (i) an aliphatic conjugated diene monomer capable of forming an aliphatic conjugated diene monomer unit of a diene polymer, (i) an aromatic vinyl monomer capable of forming an aromatic vinyl monomer unit of a diene polymer, (ii) an acrylate type (Meth) acrylic acid ester monomer capable of forming a (meth) acrylic acid ester monomer unit of a polymer, (iii) a fluorine-containing monomer capable of forming a fluorine-containing monomer unit of a fluorine-based polymer, (iv) a polycarboxylic acid polymer ( (Meth) acrylic acid monomer capable of forming a (meth) acrylic acid monomer unit, (iv) acrylamide monomer capable of forming a (meth) acrylamide monomeric unit of a polycarboxylic acid polymer, (v) cyano based polymer Known can be used for the (meth) acrylonitrile monomer which can form the (meth) acrylonitrile monomeric unit.

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."

In addition, in this invention, "containing mainly 1 type or several types of monomeric units" means "when the quantity of all the monomeric units contained in a polymer is 100 mass%, It means that the total of the content rate or the content rate of the said multiple types of monomeric unit exceeds 50 mass%. "

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

[Functional group of binder]

Here, the polymer used as a binder contains a functional group. As a functional group contained in a binder, a carboxyl group (carboxylic acid group), a hydroxyl group, a cyano group (nitrile group), an amino group from a viewpoint of improving the adhesiveness (fill strength) of a functional layer and the rate characteristic of an electrochemical element. , An epoxy group, an oxazoline group, an isocyanate group, and a sulfonic acid group (hereinafter, these functional groups may be collectively referred to as a "specific functional group"), and at least any one of them may be a carboxyl group (carboxylic acid group), hydroxyl group, or cyan. It is preferable that it is at least any one of a no group (nitrile group), a sulfonic acid group, and an epoxy group, and it is more preferable that it is a cyano group (nitrile group). These may be used individually by 1 type and may be used combining two or more types by arbitrary ratios.

When the binder contains at least one of a carboxyl group (carboxylic acid group) and a cyano group, the sum of the content of the carboxyl group in the binder and the content of the cyano group in the binder is 0.1 mmol or more per 1 g of the binder. It is more preferable that it is 0.5 mmol or more per 1 g of binders, It is still more preferable that it is 0.57 mmol or more per 1 g of binders, It is still more preferable that it is 1 mmol or more per 1 g of binders, 4 per g of binders Particularly preferred is at least mmol, most preferably at least 7.35 mmol per g of binder, preferably at most 50 mmol per g of binder, more preferably at most 35 mmol per g of binder, per g of binder It is more preferable that it is 28.37 mmol or less, It is still more preferable that it is 20 mmol or less per 1 g of binders, It is especially preferable that it is 16.05 mmol or less per 1 g of binders, 15 mmol or less per g binders Is most preferred.

When the sum of the content of the carboxyl group in the binder and the content of the cyano group in the binder is 0.1 mmol or more per 1 g of the binder, the binder and the hydrogen carbonate are sufficiently interacted with each other, thereby making the adhesive layer (phil) Strength) can be further improved, and the slurry stability of the slurry composition can be improved by being 50 mmol or less per 1 g of the binder.

In addition, content of the carboxyl group (carboxylic acid group) in a binder can be computed from preparation amount, and can also calculate by measuring the acid amount of a binder by titration. On the other hand, content of the cyano group (nitrile group) in a binder can be calculated from preparation amount, and can also be computed by measuring the amount of nitrogen in a binder by the improved Duma method.

In the case where the binder contains a cyano group (nitrile group), the content of the cyano group (nitrile group) in the binder is preferably 1 mmol or more per 1 g of the binder, more preferably 2.57 mmol or more per 1 g of the binder. It is more preferred that it is at least 3 mmol per g of binder, particularly preferably at least 4 mmol per g of binder, most preferably at least 6.10 mmol per g of binder, 40 mmol per g of binder. It is preferable that it is below, It is more preferable that it is 35 mmol or less per 1 g of binders, It is more preferable that it is 27.99 mmol or less per 1 g of binders, It is still more preferable that it is 20 mmol or less per 1 g of binders, Per 1 g of binders Particularly preferred is 14.84 mmol or less, most preferably 13 mmol or less per g of binder.

When content of the cyano group (nitrile group) in a binder is 1 mmol or more and 40 mmol or less per 1 g of binders, the rate characteristic of an electrochemical element can be improved more.

The method of introducing a specific functional group into the polymer is not particularly limited, and the polymer may be prepared using the monomer (specific functional group-containing monomer) containing the specific functional group described above to obtain a polymer containing a specific functional group-containing monomer unit, optionally Although the polymer which has the above-mentioned specific functional group at the terminal may be obtained by modifying the polymer of (especially terminal modification), the former is preferable. That is, the polymer used as a binder is a carboxyl group (carboxylic acid group) containing monomeric unit, a hydroxyl group containing monomeric unit, a cyano group (nitrile group) containing monomeric unit, an amino group containing monomeric unit, and an epoxy group as a specific functional group containing monomeric unit. It contains at least any one of a containing monomeric unit, an oxazoline group containing monomeric unit, an isocyanate group containing monomeric unit, and a sulfonic acid group containing monomeric unit, and contains a carboxyl group (carboxylic acid group) containing monomeric unit, a hydroxyl group containing monomeric unit, and a cyano group It is preferable to contain at least any one of a (nitrile group) containing monomeric unit, a sulfonic acid group containing monomeric unit, and an epoxy group containing monomeric unit, and it is more preferable to contain a cyano group (nitrile group) containing monomeric unit.

Here, as a carboxyl group (carboxylic acid group) containing monomer which can form a carboxyl group (carboxylic acid group) containing monomeric unit, monocarboxylic acid and its derivative (s), dicarboxylic acid and its acid anhydride, derivatives thereof, etc. are mentioned. Can be.

Acrylic acid, methacrylic acid, crotonic acid, etc. are mentioned as monocarboxylic acid.

Examples of the monocarboxylic acid derivatives include 2-ethylacrylic acid, isocrotonic acid, α-acetoxy acrylic acid, β-trans-aryloxyacrylic acid, α-chloro-β-E-methoxyacrylic acid, and the like.

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

Examples of the dicarboxylic acid derivatives include methyl maleic acid, dimethyl maleic acid, phenyl maleic acid, chloro maleic acid, dichloro maleic acid, fluoro maleic acid, nonyl maleic acid, maleic acid decyl, maleic acid dodecyl and octadecyl maleate. And maleic acid monoesters such as fluoroalkyl 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 carboxyl group (carboxylic acid group) containing monomer, the acid anhydride which produces | generates a carboxyl group (carboxylic acid group) by hydrolysis can also be used. Especially, acrylic acid and methacrylic acid are preferable as a carboxyl group (carboxylic acid group) containing monomer. In addition, a carboxyl group (carboxylic acid group) containing monomer may be used individually by 1 type, and may be used combining two or more types by arbitrary ratios.

As a hydroxyl group containing monomer which can form a hydroxyl group containing monomeric unit, 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 _a -COO- (C _q H _2q O) _p -H (wherein p is an integer from 2 to 9, q is an integer from 2 to 4, Ra represents a hydrogen atom 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 and (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; Amides having hydroxyl groups such as N-hydroxymethyl acrylamide (N-methylol acrylamide), N-hydroxymethyl methacrylamide, N-hydroxyethyl acrylamide, and N-hydroxyethyl methacrylamide Etc. can be mentioned. In addition, a hydroxyl group containing monomer may be used individually by 1 type, and may be used combining two or more types by arbitrary ratios.

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

As a cyano group (nitrile group) containing monomer which can form a cyano group (nitrile group) containing monomeric unit, an acrylonitrile, methacrylonitrile, fumaronitrile, allyl cyanide, 2-methylene glutaronitrile, a cyanide Noacrylates and the like. In addition, a cyano group (nitrile group) containing monomeric unit may be used individually by 1 type, and may be used combining two or more types by arbitrary ratios.

As an amino-group containing monomer which can form an amino-group containing monomeric unit, dimethylaminoethyl (meth) acrylate, diethylaminoethyl (meth) acrylate, aminoethyl vinyl ether, dimethylaminoethyl vinyl ether, etc. are mentioned. In addition, an amino group containing monomer may be used individually by 1 type, and may be used combining two or more types by arbitrary ratios.

In addition, in this invention, "(meth) acrylate" means an acrylate and / or a methacrylate.

As an epoxy group containing monomer which can form an epoxy group containing monomeric unit, the monomer containing a carbon-carbon double bond and an epoxy group is mentioned.

As a monomer containing a carbon-carbon double bond and an epoxy group, For example, unsaturated glycy, such as vinylglycidyl ether, allyl glycidyl ether, butenyl glycidyl ether, o-allylphenyl glycidyl ether, etc. Dil ether; Dienes such as butadiene monoepoxide, chloroprene monoepoxide, 4,5-epoxy-2-pentene, 3,4-epoxy-1-vinylcyclohexene, 1,2-epoxy-5,9-cyclododecadiene or Monoepoxides of polyenes; Alkenylepoxides such as 3,4-epoxy-1-butene, 1,2-epoxy-5-hexene and 1,2-epoxy-9-decene; Glycidyl acrylate, glycidyl methacrylate, glycidyl crotonate, glycidyl-4-heptenoate, glycidyl sorbate, glycidyl linoleate, glycidyl-4-methyl- Glycidyl esters of unsaturated carboxylic acids such as 3-pentenoate, glycidyl ester of 3-cyclohexene carboxylic acid, and glycidyl ester of 4-methyl-3-cyclohexene carboxylic acid; Can be mentioned. In addition, an epoxy group containing monomer may be used individually by 1 type, and may be used combining two or more types by arbitrary ratios.

As an oxazoline group containing monomer which can form an oxazoline group containing monomeric unit, 2-vinyl-2- oxazoline, 2-vinyl-4-methyl-2- oxazoline, 2-vinyl-5-methyl-2 Oxazoline, 2-isopropenyl-2-oxazoline, 2-isopropenyl-4-methyl-2-oxazoline, 2-isopropenyl-5-methyl-2-oxazoline, 2-isopropenyl -5-ethyl-2-oxazoline etc. are mentioned. In addition, an oxazoline group containing monomer may be used individually by 1 type, and may be used combining two or more types by arbitrary ratios.

2-acryloyloxyethyl isocyanate, 2-methacryloyloxyethyl isocyanate, etc. are mentioned as an isocyanate group containing monomer which can form an isocyanate group containing monomeric unit. In addition, an isocyanate group containing monomeric unit may be used individually by 1 type, and may be used combining two or more types by arbitrary ratios.

As the sulfonic acid group-containing monomer capable of forming the sulfonic acid group-containing monomer unit, vinylsulfonic acid, methylvinylsulfonic acid, (meth) allylsulfonic acid, styrenesulfonic acid, 2-acrylamido-2-methylpropanesulfonic acid, 3-allyloxy- 2-hydroxypropanesulfonic acid etc. are mentioned. In addition, a sulfonic acid 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 it is 1 mass% or more, and, as for the content rate of the specific functional group containing monomeric unit in the polymer when the quantity of all the monomer units contained in a polymer is 100 mass%, it is more preferable that it is 20 mass% or more, It is preferable that it is 95 mass% or less, and it is more preferable that it is 90 mass% or less. If the content rate of the specific functional group containing monomeric unit in a polymer exists in the range mentioned above, the adhesiveness (fill strength) of a functional layer and the rate characteristic of an electrochemical element can be improved.

[Method of Preparing Binder]

The preparation method of the polymer as a binder is not specifically limited. The polymer as a binder is manufactured by polymerizing the monomer composition containing the monomer mentioned above in an aqueous solvent, for example. In addition, the content rate of each monomer in a monomer composition can be determined according to the content rate of the desired monomeric unit (repeating unit) in a polymer.

In addition, a polymerization mode can also use any method, such as a solution polymerization method, suspension polymerization method, block polymerization method, and emulsion polymerization method, without a restriction | limiting in particular. As the polymerization reaction, any reaction such as ionic polymerization, radical polymerization, living radical polymerization, various condensation polymerization or addition polymerization can be used. And at the time of superposition | polymerization, a known emulsifier and a polymerization initiator can be used as needed.

<Hydrocarbonate>

Hydrogen carbonate is a component which can improve binding property of a binder composition by adding it to the binder composition containing a binder.

Further, as specific examples of a hydrogencarbonate example, but not limited to, sodium bicarbonate (NaHCO _3), potassium bicarbonate (KHCO _3), sodium hydrogen carbonate, calcium _{(Ca (HCO 3) 2)} , ammonium bicarbonate (NH ₄ HCO ₃ ) etc. can be mentioned.

Hydrogen carbonate may be used individually by 1 type, and may be used combining two or more types by arbitrary ratios. And, among these, from the viewpoint of the adhesiveness (fill strength) of the functional layer and the cycle characteristics of the electrochemical device, sodium bicarbonate (NaHCO ₃ ), potassium bicarbonate (KHCO ₃ ), ammonium bicarbonate (NH ₄ HCO ₃ ) This is preferable, and sodium hydrogencarbonate (NaHCO ₃ ) is more preferable.

And it is preferable that content of hydrogencarbonate is 5 mass% or more with respect to 100 mass% of binders, It is more preferable that it is 7 mass% or more, It is still more preferable that it is 10 mass% or more, It is especially preferable that it is 20 mass% or more. It is most preferable that it is 30 mass% or more, It is preferable that it is 85 mass% or less, It is more preferable that it is 70 mass% or less, It is still more preferable that it is 60 mass% or less, It is especially preferable that it is 50 mass% or less, 40 mass% It is most preferable that it is the following. When content of the hydrogencarbonate is 5 mass% or more with respect to 100 mass% of binders, the adhesiveness (fill strength) of a functional layer can be improved more. On the other hand, when content of a hydrogen carbonate is 85 mass% or less with respect to 100 mass% of binders, the slurry stability of a slurry composition and the rate characteristic of an electrochemical element can be improved.

<Solvent>

As a solvent contained in a binder composition, if it is a solvent which can melt | dissolve or disperse the above-mentioned binder and hydrogencarbonate, it will not specifically limit, Any water and an organic solvent can be used. As an organic solvent, for example, acetonitrile, N-methyl-2-pyrrolidone, tetrahydrofuran, acetone, acetylpyridine, cyclopentanone, dimethylformamide, dimethyl sulfoxide, methylformamide, methyl ethyl ketone , Furfural, ethylenediamine, dimethylbenzene (xylene), methylbenzene (toluene), cyclopentylmethyl ether, isopropyl alcohol and the like can be used.

In addition, these solvent can be used individually by 1 type or in mixture of multiple types by arbitrary mixing ratios.

<Other ingredients>

In addition to the binder, the hydrogen carbonate, and the solvent described above, the binder composition of the present invention optionally contains a polymer, a conductive material, a wetting agent, a viscosity modifier, and an electrolyte solution that does not have other specific functional groups different in composition and properties from the binder. You may contain the known additive which can be added to functional layers, such as an electrode mixture layer, a porous film layer, and an contact bonding layer, such as an additive. In addition, content of the additive mentioned above can be 5 mass parts or less, or 1 mass part or less per 100 mass parts of binders, for example.

Moreover, the binder composition of this invention may contain flame retardants, such as a phosphorus compound and a silicone type compound, from a viewpoint of the safety improvement of electrochemical elements, such as a secondary battery. In addition, the melamine compound may or may not be included. These other components may be used individually by 1 type, and may be used in combination of 2 or more type.

In addition, content of the flame retardant mentioned above can be 30 mass parts or less, or 15 mass parts or less per 100 mass parts of binders, for example.

<Preparation method of the binder composition>

Here, the method for preparing the binder composition is not particularly limited, but usually, a binder, a hydrogen carbonate, and other components that can be used as necessary are mixed in a solvent to prepare a binder composition. The mixing method is not particularly limited, but mixing is usually performed using a stirrer or a disperser that can be used.

(Slurry Composition for Electrochemical Device Functional Layer)

The slurry composition of this invention is a composition used for the formation use of a functional layer, contains the binder composition mentioned above, and optionally further contains functional particle and other components. That is, the slurry composition of this invention contains a binder, hydrogencarbonate, and a solvent normally, and also contains functional particle | grains and other components further. Moreover, the functional layer excellent in adhesiveness can be obtained by drying the slurry composition of this invention, for example on a base material. And when element elements, such as a battery member provided with the said functional layer, are used, the element characteristic (battery characteristic) excellent in electrochemical elements, such as a secondary battery, especially the outstanding rate characteristic and cycling characteristics can be exhibited.

<Binder composition>

As the binder composition, at least the binder composition of the present invention containing a binder and a hydrogen carbonate is used.

In addition, the compounding quantity of the binder composition in a slurry composition is not specifically limited. For example, when a slurry composition is a slurry composition for electrodes, the compounding quantity of a binder composition can be made into the quantity which is 0.5 mass part or more and 15 mass parts or less in 100 mass parts of electrode active material particle in conversion of solid content. For example, when a slurry composition is a slurry composition for porous film layers, the compounding quantity of a binder composition can be made into the quantity which becomes 0.5 mass part or more and 30 mass parts or less in conversion of solid content per 100 mass parts of nonelectroconductive particles. have. In addition, when a slurry composition is a slurry composition for electrochemical element adhesive layers, for example, it can be set as the quantity which is 0.5 mass part or more and 50 mass parts or less per 100 mass parts of organic particles.

<Functional particle>

Here, as functional particles for exhibiting a desired function in a functional layer, an electrode active material particle is mentioned, for example, when a functional layer is an electrode mixture layer, and nonelectroconductive particle when a functional layer is a porous film layer. Can be mentioned.

Electrode Active Material Particles

And as an electrode active material particle, it does not specifically limit, The particle | grains which consist of a known electrode active material used for electrochemical elements, such as a secondary battery, are mentioned. Specifically, for example, the electrode active material particles that can be used in the electrode mixture layer of the lithium ion secondary battery as an example of an electrochemical device such as a secondary battery are not particularly limited. Particles composed of the following electrode active materials are used. Can be used

Positive Electrode Active Material

As a positive electrode active material mix | blended with the positive electrode mixture layer of the positive electrode of a lithium ion secondary battery, For example, the compound containing a transition metal, for example, a transition metal oxide, a transition metal sulfide, a composite metal oxide of lithium and a transition metal, etc. Can be used. On the other hand, as a transition metal, Ti, V, Cr, Mn, Fe, Co, Ni, Cu, Mo etc. are mentioned, for example.

Specifically, the positive electrode active material is not particularly limited, and lithium-containing cobalt oxide (LiCoO ₂ ), lithium manganate (LiMn ₂ O ₄ ), lithium-containing nickel oxide (LiNiO ₂ ), and lithium containing Co-Ni-Mn Complex oxide, lithium-containing composite oxide of Ni-Mn-Al, lithium-containing composite oxide of Ni-Co-Al, olivine-type lithium iron phosphate (LiFePO ₄ ), olivine-type manganese phosphate (LiMnPO ₄ ), Li _{1 + x} Mn _2-x O ₄ spinel compounds of Li can be given over-expressed with (0 <X <2), such as _{Li [Ni 0.17 Li 0.2 Co 0.07} Mn 0.56] O 2, LiNi 0.5 Mn 1.5 O 4.

In addition, the positive electrode active material mentioned above may be used individually by 1 type, and may be used in combination of 2 or more type.

Negative Electrode Active Material

As a negative electrode active material mix | blended with the negative electrode mixture layer of the negative electrode of a lithium ion secondary battery, 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, a carbon-type negative electrode active material means the active material which uses carbon as a main skeleton which can insert lithium (it is also called "dope"). As the carbon-based negative electrode active material, specifically, coke, mesocarbon microbeads (MCMB), mesophase pitch-based carbon fiber, thermal decomposition vapor growth carbon fiber, phenol resin fired body, polyacrylonitrile-based carbon fiber, And carbonaceous materials such as pseudoisotropic carbon, furfuryl alcohol resin fired body (PFA) and hard carbon, and graphite materials such as natural graphite and artificial graphite.

In addition, a metal type negative electrode active material is an active material containing a metal, and usually contains the element which can insert lithium in a structure, and means the active material 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, a lithium metal or 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 and the like) and their oxides, sulfides, nitrides, silicides, carbides, phosphides, and the like. Moreover, oxides, such as lithium titanate, are mentioned.

In addition, the above-mentioned negative electrode active material may be used individually by 1 type, and may be used in combination of 2 or more type.

[Non-conductive Particles]

In addition, it is not specifically limited as nonelectroconductive particle mix | blended with a porous film layer, The known nonelectroconductive particle used for electrochemical elements, such as a secondary battery, is mentioned.

Specifically, although both inorganic fine particles and organic fine particles can be used as the nonelectroconductive particle, inorganic fine particles are usually used. Especially, as a material of nonelectroconductive particle, the material which exists stably under the use environment of electrochemical elements, such as a secondary battery, and is electrochemically stable is preferable. Preferred examples of the material of the non-conductive particles in this respect include aluminum oxide (alumina), hydrated aluminum oxide (boehmite), silicon oxide, magnesium oxide (magnesia), calcium oxide, titanium oxide (titania), BaTiO ₃ , ZrO Oxide particles such as alumina-silica composite oxide; Nitride particles such as aluminum nitride and boron nitride; Covalent crystal grains such as silicon and diamond; Poorly soluble ion crystal particles such as barium sulfate, calcium fluoride and barium fluoride; Clay fine particles such as talc and montmorillonite; Etc. can be mentioned. In addition, these particles may be subjected to elemental substitution, surface treatment, solid solution, or the like as necessary. In addition, when using organic fine particles as nonelectroconductive particle, it is preferable that swelling degree with respect to electrolyte solution is 1.2 times or less, and does not have melting | fusing point or glass transition temperature at 250 degrees C or less.

In addition, the nonelectroconductive particle mentioned above may be used individually by 1 type, and may be used in combination of 2 or more type.

<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 of this invention 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 method for preparing the slurry composition is not particularly limited.

For example, when a slurry composition is a slurry composition for electrodes, a slurry composition can be prepared by mixing a binder composition, electrode active material particle, and other components used as needed in presence of a solvent.

In addition, when a slurry composition is a slurry composition for porous film layers, a binder composition, a nonelectroconductive particle, and the other component used as needed can be mixed in presence of a solvent, and a slurry composition can be prepared.

And when a slurry composition is a slurry composition for adhesive layers, a binder composition may be used as it is, or it may be diluted with a solvent, and may be used as a slurry composition, The binder composition and the other components used as needed may be mixed in presence of a solvent, A slurry composition can also be prepared.

In addition, the solvent used at the time of preparation of a slurry composition includes the thing contained in the binder composition. In addition, the mixing method is not particularly limited, but mixing is carried out using a stirrer or a disperser which can be usually used.

<Functional layer for electrochemical device>

A functional layer for an electrochemical element (for example, a functional layer for a non-aqueous secondary battery) is a layer that is responsible for the function of receiving or reinforcing or bonding electrons in an electrochemical element (for example, a non-aqueous secondary battery). Examples of the functional layer include an electrode mixture layer which conducts electrons through an electrochemical reaction, a porous membrane layer that improves heat resistance and strength, and an adhesive layer that improves adhesion. And the functional layer mentioned above was formed from the slurry composition of this invention mentioned above, For example, after apply | coating the slurry composition mentioned above to the surface of a suitable base material, and forming a coating film, it can form by drying the formed coating film. have. That is, the functional layer mentioned above consists of the dry matter of the slurry composition mentioned above, and usually contains at least a binder and a hydrogen carbonate. In addition, since each component contained in the functional layer was contained in the said slurry composition, the suitable abundance ratio of those each component is the same as the suitable abundance ratio of each component in a slurry composition. In addition, when a binder is a polymer which has a crosslinkable functional group (for example, an epoxy group, an oxazoline group, etc.), the said polymer is bridge | crosslinked at the time of drying of a slurry composition, or at the time of heat processing optionally performed after drying, (The functional layer may contain the crosslinked material of the binder mentioned above).

Since the functional layer mentioned above is formed from the slurry composition of this invention containing the binder composition of this invention, it is excellent in adhesiveness, and it is the secondary battery etc. which have the element member (battery member) provided with the functional layer mentioned above. An excellent element characteristic (rate characteristic etc.) can be exhibited in an electrochemical element.

[materials]

Here, there is no restriction | limiting in the base material which apply | coats a slurry composition, For example, even if it forms a coating film of a slurry composition on the surface of a release base material, it dries and forms a functional layer, and peels a release base material from a functional layer. do. In this way, the functional layer peeled off from the release substrate can also be used as a self-supporting film to form element members (battery members) of electrochemical elements such as secondary batteries.

However, it is preferable to use an electrical power collector, a separator base material, or an electrode base material as a base material from a viewpoint of omitting the process of peeling a functional layer, and improving manufacturing efficiency of a battery member. Specifically, in preparing the electrode mixture layer, it is preferable to apply the slurry composition onto the current collector as the substrate. In addition, when preparing a porous film layer and an contact bonding layer, it is preferable to apply a slurry composition on a separator base material or an electrode base material.

Current collector

As the current collector, a material having electrical conductivity and 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. Especially, copper foil is especially preferable as an electrical power collector used for a negative electrode. Moreover, as an electrical power collector used for a positive electrode, aluminum foil is especially preferable. In addition, said material may be used individually by 1 type, and may be used combining two or more types by arbitrary ratios.

Separator base material

Although it does not specifically limit as a separator base material, Known separator base materials, such as an organic separator base material, are mentioned. The organic separator substrate is a porous member made of an organic material, and examples of the organic separator substrate include polyolefin resins such as polyethylene and polypropylene, microporous membranes and nonwoven fabrics containing aromatic polyamide resins, and the like. Polyethylene microporous membranes and nonwoven fabrics are preferred from the viewpoint of excellentness.

Electrode base material

Although it does not specifically limit as an electrode base material (positive electrode base material and negative electrode base material), The electrode base material in which the electrode mixture layer containing an electrode active material particle and a binder was formed on the electrical power collector mentioned above is mentioned.

The electrode active material particles and the binder included in the electrode mixture layer in the electrode base material are not particularly limited, and the electrode active material particles described in the section of “slurry composition for electrochemical element functional layers” and “binder composition for electrochemical element” The binder mentioned above can be used. In addition, the hydrogen carbonate may be contained in the electrode mixture layer in an electrode base material. That is, you may use the functional layer mentioned above as an electrode mixture layer in an electrode base material.

[Formation of Functional Layer]

The following method is mentioned as a method of forming a functional layer on base materials, such as an electrical power collector, a separator base material, and an electrode base material mentioned above.

1) The method of apply | coating the slurry composition of this invention to the surface of a base material (in the case of an electrode base material, the surface of an electrode mixture layer side, the same below), and then drying;

2) a method of drying the substrate in the slurry composition of the present invention and then drying it; And

3) The method of apply | coating the slurry composition of this invention on a release base material, drying to produce a functional layer, and transferring the obtained functional layer to the surface of a base material.

Among these, the method of said 1) is especially preferable at the point which is easy to control the layer thickness of a functional layer. The method of said 1) includes the process (coating process) of apply | coating a slurry composition on a base material in detail, and the process (drying process) of drying the slurry composition apply | coated on a base material to form a functional layer.

Application Process

And in a coating process, there is no restriction | limiting in particular as a method of apply | coating a slurry composition on a base material, For example, a doctor blade method, a reverse roll method, the direct roll method, the gravure method, the extrusion method, the brush coating method, etc. The method can be mentioned.

Drying process

In addition, in a drying process, it does not specifically limit as a method of drying the slurry composition on a base material, A well-known method can be used. As a drying method, drying by warm air, hot air, low humidity wind, vacuum drying, irradiation by infrared rays, an electron beam, etc. are mentioned, for example. The drying temperature is preferably less than 150 ° C, more preferably less than 130 ° C, in order to avoid the thermal decomposition and the sublimation of the hydrogen carbonate used.

On the other hand, when preparing the electrode mixture layer as a functional layer, it is preferable to pressurize an electrode mixture layer after a drying process using a metal mold | die press or a roll press.

<Element member (battery member) provided with a functional layer>

The element member (battery member (separator and electrode)) provided with the functional layer mentioned above may be provided with the functional layer mentioned above and components other than a base material, unless the effect of this invention is impaired remarkably. Such components are not particularly limited, and examples thereof include an electrode mixture layer, a porous membrane layer, and an adhesive layer, which do not correspond to the above-described functional layer.

In addition, the element member (battery member) may be provided with plural kinds of the functional layers described above. For example, an electrode is provided with the electrode mixture layer formed from the slurry composition for electrodes of this invention on an electrical power collector, and also the slurry composition for porous film layers and / or adhesive layer of this invention on the said electrode mixture layer. You may be provided with the porous film layer and / or the contact bonding layer formed. For example, a separator is provided with the porous film layer formed from the slurry composition for porous film layers on or in a separator base material, and also has the adhesive layer formed from the slurry composition for contact bonding layers of this invention on this porous film layer. You may be.

The battery member provided with the functional layer mentioned above can be adhere | attached favorably with the adjacent battery member, and can exhibit the outstanding element characteristic (for example, rate characteristic) to electrochemical elements, such as a secondary battery.

Electrochemical Devices

Electrochemical elements, such as a secondary battery, are equipped with the functional layer mentioned above. More specifically, electrochemical elements, such as a secondary battery, are equipped with a positive electrode, a negative electrode, a separator, and electrolyte solution, and the functional layer for electrochemical elements, such as a secondary battery, mentioned above is a positive electrode and a negative electrode which are element members (battery member). And a separator. And electrochemical elements, such as a secondary battery, can exhibit the outstanding element characteristic (for example, rate characteristic).

<Positive electrode, negative electrode and separator>

At least one of the positive electrode, the negative electrode, and the separator used for electrochemical elements, such as a secondary battery, is an element member (battery member) provided with the functional layer mentioned above. In addition, it does not specifically limit as a positive electrode, a negative electrode, and a separator which does not have the functional layer mentioned above, A known positive electrode, a negative electrode, and a separator 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, lithium salt is used in a lithium ion secondary battery, 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 , and CF ₃ SO ₃ Li are preferable because they dissolve easily in a solvent and exhibit high dissociation degrees. In addition, an electrolyte may be used individually by 1 type and may be used in combination of 2 or more type. 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 used in the electrolyte solution is not particularly limited as long as it can dissolve the supporting electrolyte. For example, in a lithium ion secondary battery, dimethyl carbonate (DMC), ethylene carbonate (EC), and diethyl carbonate (DEC) are used. Carbonates such as propylene carbonate (PC), butylene carbonate (BC), ethyl methyl carbonate (EMC) and vinylene carbonate (VC); 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. Among them, carbonates are preferable because the dielectric constant is high and the stable potential region is wide. Usually, the lower the viscosity of the solvent used, the higher the lithium ion conductivity is, and thus the lithium ion conductivity can be adjusted by the kind of solvent.

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

<Method for producing electrochemical device>

The above-described electrochemical elements such as secondary batteries are, for example, overlapping a positive electrode and a negative electrode through a separator, and winding them in a battery container by winding, folding, etc. as necessary, and injecting and sealing an electrolyte solution into the battery container. It can manufacture. On the other hand, at least one member of a positive electrode, a negative electrode, and a separator is made into the element member (battery member) provided with the functional layer mentioned above. The battery container may contain an expanded metal, an overcurrent prevention element such as a fuse or a PTC element, a lead plate, or the like, as necessary, to prevent pressure increase inside the battery and overcharge / discharge. The shape of the battery may be, for example, a coin type, a button type, a sheet type, a cylindrical shape, a square shape, or a flat type.

(Slurry Composition for Electrochemical Device Adhesion Layer)

The slurry composition for electrochemical device adhesion layers of this invention may contain the binder composition for electrochemical devices of this invention, arbitrary organic particle | grains, and does not contain an electrode active material particle and a nonelectroconductive particle, Even if it contains other components, do. In addition, an electrode active material particle and nonelectroconductive particle are as above-mentioned here.

<Organic Particles>

The said organic particle | grains are the water-insoluble polymer particles of the core / shell structure which may be a water-insoluble polymer particle which consists of (i) copolymer, or (ii) partial coating. However, the said organic particle does not contain the binder, nonelectroconductive particle, and electrode active material particle described in this specification.

As a "copolymer" in the said "(a) water-insoluble polymer particle which consists of a copolymer", For example, an acrylonitrile butadiene copolymer, a styrene butadiene copolymer, a (meth) acrylate copolymer, etc. are mentioned. Can be mentioned.

Although there is no restriction | limiting in particular as a volume average particle diameter of organic particle | grains, It is preferable that it is 200 nm or more, It is more preferable that it is 300 nm or more, It is especially preferable that it is 400 nm or more, Moreover, It is preferable that it is 1000 nm or less, It is preferable that it is 900 nm or less More preferably, it is especially preferable that it is 800 nm or less. When the volume average particle diameter of organic particle | grains is more than the said lower limit, resistance rise of a battery can be suppressed, and adhesiveness with an electrode can be improved by below the said upper limit.

It is preferable that organic particle | grains are larger in volume average particle diameter than binder, and are higher in glass transition temperature. The organic particles have a larger particle diameter than the binder and have a higher glass transition temperature, thereby exhibiting good adhesiveness with an electrode and suppressing a rise in resistance.

Although there is no restriction | limiting in particular as glass transition temperature of organic particle | grains, It is preferable that it is 20 degreeC or more, It is more preferable that it is 30 degreeC or more, It is especially preferable that it is 40 degreeC or more, In addition, It is preferable that it is 90 degrees C or less, It is 80 degrees C or less More preferably, it is especially preferable that it is 70 degrees C or less. When the glass transition temperature of organic particle | grains is more than the said lower limit, resistance rise of a battery can be suppressed, and adhesiveness with an electrode can be improved by below the said upper limit.

Although there is no restriction | limiting in particular as electrolyte solution swelling degree of organic particle | grains, It is preferable that it is 20 times or less, It is more preferable that it is 10 times or less, It is especially preferable that it is 5 times or less. When the electrolyte solution swelling degree of organic particle | grains is below the said upper limit, the resistance rise of a battery can be suppressed.

(Slurry Composition for Porous Membranes)

The slurry composition for porous films contains the binder composition for electrochemical elements of this invention, arbitrary nonelectroconductive particle, and another component. In addition, a nonelectroconductive particle is as above-mentioned here.

Although there is no restriction | limiting in particular as the volume average particle diameter of the binder in a slurry composition for porous films, It is preferable that it is 20 nm or more, It is more preferable that it is 30 nm or more, It is especially preferable that it is 40 nm or more, It is preferable that it is 300 nm or less, It is more preferable that it is 250 nm or less, It is especially preferable that it is 200 nm or less. When the volume average particle diameter of a binder and a hydrogen carbonate is more than the said lower limit, the air permeability of a porous film can be suppressed, and when it is below the said upper limit, favorable binding can be exhibited.

(Composite membrane)

The composite membrane of this invention introduce | transduces the slurry composition for porous film layers or the slurry composition for contact bonding layers which are the slurry compositions for functional layers of this invention in (i) apply | coating on a separator base material (lamination), or (ii) a separator base material. It is formed by doing (inside).

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, "%" and "part" which represent quantity are a mass reference | standard unless there is particular notice.

In the Example and the comparative example, the slurry stability of the slurry composition, the adhesiveness (fill strength) of a functional layer, the rate characteristic of a secondary battery, and cycling characteristics were evaluated by the following method.

<Slurry Stability of Slurry Composition>

The viscosity immediately after preparation of the produced slurry composition was defined as (eta) 0 (measured by a Brookfield viscometer, 25 degreeC, 60 rpm). At 25 ° C, the slurry viscosity after standing for 3 days is defined as η1. And as slurry stability, the viscosity change rate represented by (DELTA) = | (eta) 1- (eta) 0 | / (eta) 0x100 (%) was calculated | required and it evaluated by the following references | standards. The smaller the value of this viscosity change rate (DELTA) eta, the higher the stability of the slurry.

A: viscosity change rate is less than 20%

B: viscosity change rate is 20% or more but less than 40%

C: viscosity change rate is 40% or more but less than 60%

D: Viscosity change rate is 60% or more but less than 100%

E: viscosity change rate is 100% or more

<Adhesiveness (Peel Strength)>

<< Adhesion (fill strength) of the negative electrode mixture layer as a functional layer >>

The produced negative electrode for lithium ion secondary batteries was cut out in rectangular shape of length 100mm and width 10mm, and it was set as the test piece, the surface which has a negative electrode mixture layer facing down, and the surface of the negative electrode mixture layer of a test piece was prescribed | regulated to JIS Z1522. ) Was affixed on the test stand (SUS substrate) surface. Thereafter, one end of the current collector was pulled off at a pulling rate of 50 mm / min in the vertical direction to measure the stress (N / m) (the cellophane tape is fixed to the test bench). The same measurement was performed 3 times, the average value was calculated | required, this was made into peeling strength, and the following references | standards evaluated. As the value of the peel strength is larger, the negative electrode mixture layer and the current collector are firmly in contact with each other, indicating that the negative electrode mixture layer is excellent in adhesiveness.

A: Peel strength is 3.5 N / m or more

B: peel strength is 3.0 N / m or more and less than 3.5 N / m

C: Peel strength is 2.5 N / m or more but less than 3.0 N / m

D: Peel strength is 1.5 N / m or more and less than 2.5 N / m

E: peel strength is less than 1.5 N / m

<< Adhesion (Peel Strength) of the Positive Electrode Mixture Layer as a Functional Layer >>

The produced positive electrode for lithium ion secondary batteries is cut out in rectangular shape of length 100mm and width 10mm, and it is set as a test piece, the surface which has a positive electrode mixture layer facing down, and the surface of the positive electrode mixture layer of a test piece is prescribed | regulated by JIS Z1522. ) Was affixed on the test stand (SUS substrate) surface. Thereafter, one end of the current collector was pulled off at a pulling rate of 50 mm / min in the vertical direction to measure the stress (N / m) (the cellophane tape is fixed to the test bench). The same measurement was performed 3 times, the average value was calculated | required, this was made into peeling strength, and the following references | standards evaluated. As the value of the peel strength is larger, the positive electrode mixture layer and the current collector are firmly in contact with each other, indicating that the positive electrode mixture layer is excellent in adhesiveness.

A: Peel strength is 50.0 N / m or more

B: Peel Strength is more than 40.0 N / m but less than 50.0 N / m

C: Peel Strength is more than 30.0 N / m but less than 40.0 N / m

D: Peel Strength is more than 20.0 N / m but less than 30.0 N / m

E: peel strength is less than 20.0 N / m

<< adhesiveness (pill strength) of the porous film layer as a functional layer >>

The separator provided with the porous membrane layer was cut into a rectangle having a length of 100 mm and a width of 10 mm to form a test piece, and the surface having the porous membrane layer was faced down, and the surface of the porous membrane layer of the test piece was defined in cellophane tape (JIS Z1522). It was affixed on the test stand (substrate made from SUS) surface through the above). Thereafter, the stress (N / m) when one end of the separator substrate was pulled off at a pulling rate of 50 mm / min in the vertical direction was measured (on the other hand, the cellophane tape is fixed to the test bench). The same measurement was performed 3 times, the average value was calculated | required, this was made into peeling strength, and the following references | standards evaluated. The larger the value of the peel strength, the more strongly the porous membrane layer and the separator substrate adhere to each other, indicating that the porous membrane layer is excellent in adhesiveness.

A: Peel strength is 3.0 N / m or more

B: Peel Strength is 2.5 N / m or more but less than 3.0 N / m

C: Peel strength is 2.0 N / m or more and less than 2.5 N / m

D: Peel strength is more than 1.5 N / m but less than 2.0 N / m

E: peel strength is less than 1.5 N / m

<< adhesiveness (pill strength) of the contact bonding layer as a functional layer >>

The separator with the produced adhesive layer was cut into a rectangle of 100 mm in length and 10 mm in width to make a test piece, and the surface having the adhesive layer was faced down, and the surface of the adhesive layer of the test piece was tested using a cellophane tape (as defined in JIS Z1522). It was affixed on the surface of the substrate made of SUS. Thereafter, the stress (N / m) when one end of the separator substrate was pulled off at a pulling rate of 50 mm / min in the vertical direction was measured (on the other hand, the cellophane tape is fixed to the test bench). The same measurement was performed 3 times, the average value was calculated | required, this was made into peeling strength, and the following references | standards evaluated. As the value of the peel strength is larger, the adhesive layer and the separator substrate are firmly adhered to each other, indicating that the adhesive layer is excellent in adhesiveness.

A: Peel strength is 40.0 N / m or more

B: Peel Strength is more than 30.0 N / m but less than 40.0 N / m

C: Peel Strength is more than 20.0 N / m but less than 30.0 N / m

D: Peel Strength is more than 10.0 N / m but less than 20.0 N / m

E: peel strength is less than 10.0 N / m

<< Adhesiveness (Peel Strength) of the Composite Film >>

The produced composite membrane is cut out in rectangle of 100 mm in length and 10 mm in width, and it is set as a test piece, and when the column of "functional layer: arrangement" in Table 1-4 is "laminated", the surface which has a functional layer faces down. In addition, when the column of "functional layer: arrangement | positioning" in Table 1-4 is "inner", the surface of the functional layer of a test piece is placed on a cellophane tape (JIS Z1522) with any surface of a composite film facing down. It adhere | attached on the test stand (substrate made from SUS) surface through what was prescribed | regulated. Thereafter, the stress (N / m) when one end of the separator substrate was pulled off at a pulling rate of 50 mm / min in the vertical direction was measured (on the other hand, the cellophane tape is fixed to the test bench). The same measurement was performed 3 times, the average value was calculated | required, this was made into peeling strength, and the following references | standards evaluated. As the value of the peel strength is larger, the functional layer and the separator substrate are firmly adhered to each other, indicating that the composite film is excellent in adhesiveness.

A: Peel strength is 50.0 N / m or more

B: Peel Strength is more than 40.0 N / m but less than 50.0 N / m

C: Peel Strength is more than 30.0 N / m but less than 40.0 N / m

D: Peel Strength is more than 20.0 N / m but less than 30.0 N / m

E: peel strength is less than 20.0 N / m

<< Adhesion (fill strength) of the electrode mixture layer for electric double layer capacitor (EDLC) as a functional layer >>

The electrode for electric double layer capacitor which has the produced electrode mixture layer was cut out in rectangle of 100 mm in length, 10 mm in width, and it was set as a test piece, and the surface of an electrode mixture layer of a test piece was made into the surface with the electrode mixture layer down, and the cellophane tape ( It adhere | attached on the test stand (substrate made from SUS) surface through what is prescribed | regulated to JISZ1522. Thereafter, one end of the current collector was pulled off at a pulling rate of 50 mm / min in the vertical direction to measure the stress (N / m) (the cellophane tape is fixed to the test bench). The same measurement was performed 3 times, the average value was calculated | required, this was made into peeling strength, and the following references | standards evaluated. As the value of the peel strength is larger, the electrode mixture layer and the current collector are firmly adhered to each other, indicating that the electrode mixture layer is excellent in adhesiveness.

A: Peel strength is 15.0 N / m or more

B: Peel Strength is 12.0 N / m or more but less than 15.0 N / m

C: Peel strength is more than 9.0 N / m but less than 12.0 N / m

D: Peel strength is 5.0 N / m or more and less than 9.0 N / m

E: peel strength is less than 5.0 N / m

<< process adhesiveness >>

The produced positive electrode and the separator (both functional layers are provided on both sides) were cut out to 50 mm in length and 10 mm in width, respectively.

And the cut positive electrode and the separator were laminated | stacked and laminated | stacked. The obtained laminated piece was pressed at the press speed of 3 m / min using the roll press of temperature 70 degreeC, and the load of 10 kN / m, and the test piece was obtained.

On this test piece, the surface of the positive electrode collector side was faced down, and a cellophane tape (as defined in JIS Z1522) was affixed to the surface of the positive electrode collector side. On the other hand, the cellophane tape was fixed on a horizontal test bench. And the stress at the time of pulling one end of a separator upwardly and peeling off at the tensile speed of 50 mm / min was measured. The measurement was performed three times in total.

In addition, separately produced negative electrodes and separators were cut into lengths of 50 mm and widths of 10 mm, respectively. And the test piece was obtained like the case where the said positive electrode was used, and the stress was measured three times in total.

The average value of the total six stresses obtained by the measurement using the said positive electrode and the negative electrode was calculated | required as 2nd peel strength (N / m), and it evaluated by the following reference | standard as the process adhesiveness of the electrode and separator through a functional layer. The larger the second peel strength, the better the process adhesion.

A: 2nd peel strength is 10.0 N / m or more

B: 2nd peel strength is 7.0 N / m or more and less than 10.0 N / m

C: 2nd peel strength is 5.0 N / m or more and less than 7.0 N / m

D: 2nd peel strength is 2.0 N / m or more and less than 5.0 N / m

E: 2nd peel strength is less than 2.0 N / m

<< increase in air permeability >>

For the separator on which the separator base material and the functional layer were used for the production of the separator, a Gurley value (seconds / 100 ccAir) was used using a digital Oken type air permeability and smoothness tester (manufactured by Asahi Seiko, EYO-5-1M-R). ) Was measured. Specifically, the increase amount (DELTA) G (= G1-G0) of a Gurley value was calculated | required from Gurley value G0 of a "separator base material", and Gurley value G1 of the "separator" in which the functional layer was formed, and the following references | standards evaluated. The smaller the rate of increase ΔG of the Gurley value is, the more excellent the ion conductivity of the separator is.

A: The increase in Gurley value is less than 10 seconds / 100 ccAir.

B: The amount of increase in Gurley value is more than 10 second / 100 ccAir and less than 15 second / 100 ccAir.

C: The increase in the Gurley value is more than 15 seconds / 100 ccAir and less than 20 seconds / 100 ccAir.

D: The increase in Gurley value is 20 seconds / 100 ccAir or more and 30 seconds / 100 ccAir or less.

E: The increase in Gurley value is 30 seconds / 100 ccAir or more.

<Rate characteristic of the lithium ion secondary battery (LIB) as an electrochemical element>

The produced lithium ion secondary battery was left to stand at 25 degreeC for 5 hours after electrolyte solution injection. Next, it charged to the cell voltage of 3.65V by the constant current method of the temperature of 25 degreeC and 0.2C, and then, the aging process was performed at the temperature of 60 degreeC for 12 hours. And it discharged to the cell voltage 3.00V by the constant current method of the temperature of 25 degreeC and 0.2C. Thereafter, CC-CV charging (upper limit cell voltage 4.35 V) was performed at a constant current of 0.2 C, and CC discharge was performed up to cell voltage 3.00 V at a constant current of 0.2 C. The charging and discharging at 0.2 C was repeated three times.

Next, a constant current charge / discharge of 0.2 C was performed between the cell voltages 4.35-3.00V in the environment of the temperature of 25 degreeC, and the discharge capacity at this time was defined as C0. Then, CC-CV charge was carried out similarly with the constant current of 0.2C, and it discharged to 2.5V with the constant current of 0.5C in the environment of temperature -10 degreeC, and the discharge capacity at this time was defined as C1. And as a rate characteristic, the capacity | capacitance retention represented by (DELTA) C = (C1 / C0) x100 (%) was calculated | required and it evaluated by the following references | standards. The larger the value of the capacity retention ratio ΔC, the higher the discharge capacity at high current and low internal resistance under low temperature environment.

A: Capacity retention rate ΔC is 70% or more

B: Capacity retention ΔC is 65% or more but less than 70%

C: Capacity retention ΔC is 60% or more but less than 65%

D: Capacity retention ΔC is 55% or more but less than 60%

E: Capacity retention ΔC is less than 55%

<Rate Characteristics of Electric Double Layer Capacitors (EDLC) as Electrochemical Devices>

The produced electric double layer capacitor was left to stand at 25 degreeC for 5 hours after electrolyte solution injection. Next, it charged to 2.7V by the constant current constant voltage charging method of the temperature of 25 degreeC and 2.0 mA / cm <^2> . Then, it discharged to 0.0V at 25 degreeC and 2.0 mA / cm <^2> . This charging and discharging was repeated three times.

Next, constant current charge / discharge of 2.0 mA / cm ² was performed between the cell voltages of 2.7-0.0V in 25 degreeC environment, and the discharge capacity at this time was defined as C0. Thereafter, the battery was charged in a constant current constant voltage method of 2.0 mA / cm ² , and discharged to a constant current of 0.0 V at a constant current of 20.0 mA / cm ² under an environment of a temperature of −10 ° C., and the discharge capacity at this time was C1. Defined. And as a rate characteristic, the capacity | capacitance retention represented by (DELTA) C = (C1 / C0) x100 (%) was calculated | required and the following references | standards evaluated. The larger the value of the capacity retention ratio ΔC, the higher the discharge capacity at high current and low internal resistance under low temperature environment.

A: Capacity retention rate ΔC is 70% or more

B: Capacity retention ΔC is 65% or more but less than 70%

C: Capacity retention ΔC is 60% or more but less than 65%

D: Capacity retention ΔC is 55% or more but less than 60%

E: Capacity retention ΔC is less than 55%

<Cycle Characteristics of Lithium Ion Secondary Battery (LIB) as Electrochemical Device>

The produced lithium ion secondary battery was left still for 24 hours in 25 degreeC environment. Thereafter, at 25 ° C., the battery was charged up to 4.35 V (cut-off condition: 0.02 C) with a constant voltage constant current (CC-CV) method at a charge rate of 1 C, and up to 3.0 V with a constant current (CC) method at a discharge rate of 1 C. Operation of charging and discharging to discharge was performed and initial stage C0 was measured.

Moreover, operation of the same charge / discharge was repeated in 45 degreeC environment, and the capacity C1 after 300 cycles was measured. And capacity retention ratio (DELTA) C = (C1 / C0) x100 (%) was computed and evaluated based on the following reference | standard. The higher the value of the capacity retention rate, the smaller the decrease in discharge capacity, indicating that the cycle characteristics are excellent.

A: The 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 rate ΔC is less than 70%

<Cycle Characteristics of Electric Double Layer Capacitors (EDLC) as Electrochemical Devices>

The produced electric double layer capacitor was left still for 24 hours in 25 degreeC environment. Then, at 25 ℃, the constant-voltage constant-current (CC-CV) method to 2.7 V at a charge rate of 20.0 mA / cm ^2: a (cut-off conditions, 0.2 mA / cm ²⁾ discharge rate of the charge and, 20.0 mA / cm ² up to The charging / discharging to discharge to 0.0V by the constant current (CC) method was performed, and initial stage C0 was measured.

In addition, the same charging / discharging operation was repeated in 60 degreeC environment, and the capacity C1 after 1000 cycles was measured. And capacity retention ratio (DELTA) C = (C1 / C0) x100 (%) was computed and evaluated based on the following reference | standard. The higher the value of the capacity retention rate, the smaller the decrease in discharge capacity, indicating that the cycle characteristics are excellent.

A: 90% or more of capacity retention rate ΔC

B: Capacity retention ΔC is 85% or more but less than 90%

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

D: Capacity retention ΔC is 75% or more but less than 80%

E: capacity retention ΔC is less than 75%

(Example 1)

<Preparation of binder (polymer A)>

In a 5 MPa pressure vessel equipped with a stirrer, 32 parts of styrene as an aromatic vinyl monomer, 33 parts of 1,3-butadiene as an aliphatic conjugated diene monomer, 29 parts of acrylonitrile as a cyano group (nitrile group) -containing monomer, and a carboxyl group (carboxylic acid group) 5 parts of itaconic acid as a containing monomer, 1 part of 2-hydroxyethyl acrylate as a hydroxyl group containing monomer, 0.3 part of t-dodecyl mercaptan as a molecular weight modifier, 5 parts of sodium dodecylbenzenesulfonate as an emulsifier, ion exchange as a solvent 150 parts of water and 1 part of potassium persulfate as a polymerization initiator were thrown in, and after fully stirring, it heated to the temperature of 55 degreeC and started superposition | polymerization. At the time when the monomer consumption reached 95.0%, the reaction was stopped. A 5% sodium hydroxide aqueous solution was added to the aqueous dispersion containing the polymer thus obtained, and the pH was adjusted to 8. Thereafter, the unreacted monomer was removed by distillation under reduced pressure. Furthermore, after that, it cooled to the temperature of 30 degrees C or less, and obtained the aqueous dispersion containing the polymer A as a binder.

<Preparation of the binder composition for negative electrode mixture layers>

40 parts of sodium hydrogencarbonate as a hydrogencarbonate were mixed with respect to 100 parts (solid content equivalency) of the polymer A, and the binder composition was prepared.

<Preparation of the slurry composition for negative electrode mixture layers>

Into the planetary mixer, 48.75 parts of artificial graphite (theoretical capacity: 360 mAh / g) as the negative electrode active material, 48.75 parts of the natural graphite (theoretical capacity: 360 mAh / g), and 1 part of carboxymethyl cellulose as a solid content are added as a thickener. It was. Furthermore, it diluted with ion-exchange water so that solid content concentration might be 60%, and then knead | mixed for 60 minutes at 45 rpm of rotation speed. Subsequently, 1.5 parts of the binder composition for negative electrode mixture layers obtained above was added with solid content equivalent, and it knead | mixed for 40 minutes at the rotation speed of 40 rpm. And the slurry composition for negative electrode mixture layers was prepared by adding ion-exchange water so that a viscosity might be set to 3000 +/- 500 mPa * s (measured by Type-B viscometer, 25 degreeC, 60 rpm). Slurry stability was evaluated using this slurry composition for negative electrode mixture layers. The results are shown in Table 1-1.

<Manufacture of negative electrode>

The slurry composition for negative electrode mixture layers was applied to the surface of the copper foil (thickness 15 μm) which is a current collector by a comma coater so that the coating amount was 11 ± 0.5 mg / cm ² . Then, copper foil with which the slurry composition for negative electrode mixture layers was apply | coated was conveyed in the oven of temperature 80 degreeC for 2 minutes, and the inside of oven of temperature 110 degreeC over 2 minutes at the speed | rate of 500 mm / min over 2 minutes. The slurry composition of the phase was dried, and the negative electrode original fabric in which the negative electrode mixture layer was formed on the electrical power collector was obtained.

Thereafter, the negative electrode mixture layer side of the prepared negative electrode fabric was roll-pressed under conditions of a linear pressure of 11 t (ton) under an environment of a temperature of 25 ± 3 ° C. to obtain a negative electrode having a negative electrode mixture layer density of 1.60 g / cm ³ . Thereafter, the negative electrode was left to stand for one week in an environment having a temperature of 25 ± 3 ° C. and a relative humidity of 50 ± 5%. The peeling strength of the negative electrode mixture layer was evaluated using the negative electrode after standing. The results are shown in Table 1-1.

<Manufacture of positive electrode>

To the planetary mixer, 96 parts of Co-Ni-Mn lithium composite oxide-based active material (NMC111, LiNi _1/3 Co _1/3 Mn _1/3 O ₂ , average particle diameter 10 μm) as a positive electrode active material was used. 2 parts of acetylene black (manufactured by Denka Company Limited, trade name "HS-100"), and 2 parts of polyvinylidene fluoride (Kureha Chemical Co., Ltd., product name "KF-1100") as a binder were added. N-methyl-2-pyrrolidone (NMP) as a dispersion medium was added and mixed so that total solid content concentration might be 67%, and the slurry composition for positive electrode mixture layers was prepared.

Then, the obtained slurry composition for positive electrode mixture layers was apply | coated so that the application amount might be 20 +/- 0.5 mg / cm <^2> on aluminum foil of 20 micrometers thickness which is an electrical power collector by a comma coater.

Moreover, the slurry composition on aluminum foil is dried by conveying the inside of oven of temperature 90 degreeC for 4 minutes, and the inside of oven of temperature 120 degreeC over 4 minutes at the speed | rate of 300 mm / min, and it mixes positive electrode on an electrical power collector A positive electrode fabric having a layer formed thereon was obtained.

Then, the positive electrode mixture layer side of the produced positive electrode original fabric was roll-pressed on the conditions of linear pressure 14 t (ton) in the environment of the temperature of 25 +/- 3 degreeC, and the positive electrode mixture layer density was 3.20 g / cm <^3> . Thereafter, the positive electrode was left to stand for one week in an environment of a temperature of 25 ± 3 ° C. and a relative humidity of 50 ± 5%.

<Preparation of separator>

As the separator, Celgard 2500 made of polypropylene was used.

<Production of Lithium Ion Secondary Battery (LIB) as Electrochemical Device>

Using the said negative electrode, the positive electrode, and the separator, the wound cell (discharge capacity 520 mAh equivalent) was produced so that a negative electrode mixture layer and a positive electrode mixture layer might face through a separator, and it arrange | positioned in the aluminum packaging material. Then, in this aluminum packaging material, a mixed solvent of LiPF ₆ solution (solvent: ethylene carbonate (EC) / diethyl carbonate (DEC) = 3/7 (volume ratio) of 1.0 M) as electrolyte solution, and additive: vinylene carbonate 2 volume % (Solvent ratio)) was charged. In addition, in order to seal the opening of an aluminum packaging material, the aluminum packaging material was closed by heat-sealing with a temperature of 150 degreeC, and the lithium ion secondary battery was produced. Rate characteristics and cycle characteristics were evaluated using this lithium ion secondary battery. The results are shown in Table 1-1.

(Example 2)

When preparing the binder composition for the negative electrode mixture layer, the same procedure as in Example 1 was carried out except that NH ₄ HCO ₃ was used instead of NaHCO ₃ as the hydrogen carbonate salt, and the polymer A as the binder, the binder composition for the negative electrode mixture layer, and the negative electrode mixture layer were used. The slurry composition, the negative electrode, the positive electrode, the separator, and the secondary battery were produced. And it evaluated similarly to Example 1. The results are shown in Table 1-1.

(Example 3)

When preparing the binder composition for the negative electrode mixture layer, the same procedure as in Example 1 was carried out except that Ca (HCO ₃ ) ₂ was used instead of NaHCO ₃ as the hydrogen carbonate salt, and the polymer A as the binder, the binder composition for the negative electrode mixture layer, and the negative electrode were used. The slurry composition for negative electrode layers, the negative electrode, the positive electrode, the separator, and the secondary battery were manufactured. And it evaluated similarly to Example 1. The results are shown in Table 1-1.

(Example 4)

When preparing the binder composition for negative electrode mixture layers, it carried out similarly to Example 1 except having used the binder (polymer B) prepared by the method shown below instead of a binder (polymer A), and the binder composition for negative electrode mixture layers. , A slurry composition for negative electrode mixture layers, a negative electrode, a positive electrode, a separator, and a secondary battery were prepared. And it evaluated similarly to Example 1. The results are shown in Table 1-1.

<Preparation of binder (polymer B)>

In a 5 MPa pressure vessel equipped with a stirrer, 61 parts of styrene as an aromatic vinyl monomer, 33 parts of 1,3-butadiene as an aliphatic conjugated diene monomer, 5 parts of itaconic acid as a carboxyl group (carboxylic acid group) -containing monomer, and acrylic acid as a hydroxyl group-containing monomer 1 part of 2-hydroxyethyl, 0.3 part of t-dodecyl mercaptan as a molecular weight modifier, 5 parts of sodium dodecylbenzenesulfonate as an emulsifier, 150 parts of ion-exchanged water as a solvent, and 1 part of potassium persulfate as a polymerization initiator were added. After stirring sufficiently, the mixture was warmed to a temperature of 55 ° C to initiate polymerization. At the time when the monomer consumption reached 95.0%, the reaction was stopped. A 5% sodium hydroxide aqueous solution was added to the aqueous dispersion containing the polymer thus obtained, and the pH was adjusted to 8. Thereafter, the unreacted monomer was removed by distillation under reduced pressure. Furthermore, after that, it cooled to the temperature of 30 degrees C or less, and obtained the aqueous dispersion containing the polymer B as a binder.

(Example 5)

When preparing the binder composition for negative electrode mixture layers, it carried out similarly to Example 1 except having used the binder (polymer C) prepared by the method shown below instead of a binder (polymer A), and the binder composition for negative electrode mixture layers. , A slurry composition for negative electrode mixture layers, a negative electrode, a positive electrode, a separator, and a secondary battery were prepared. And it evaluated similarly to Example 1. The results are shown in Table 1-1.

<Preparation of binder (polymer C)>

In a 5 MPa pressure-resistant vessel equipped with a stirrer, 11 parts of styrene as an aromatic vinyl monomer, 33 parts of 1,3-butadiene as an aliphatic conjugated diene monomer, 50 parts of acrylonitrile as a cyano group (nitrile group) -containing monomer, and a carboxyl group (carboxylic acid group) 5 parts of itaconic acid as a containing monomer, 1 part of 2-hydroxyethyl acrylate as a hydroxyl group containing monomer, 0.3 part of t-dodecyl mercaptan as a molecular weight modifier, 5 parts of sodium dodecylbenzenesulfonate as an emulsifier, ion exchange as a solvent 150 parts of water and 1 part of potassium persulfate as a polymerization initiator were thrown in, and after fully stirring, it heated to the temperature of 55 degreeC and started superposition | polymerization. At the time when the monomer consumption reached 95.0%, the reaction was stopped. A 5% sodium hydroxide aqueous solution was added to the aqueous dispersion containing the polymer thus obtained, and the pH was adjusted to 8. Thereafter, the unreacted monomer was removed by distillation under reduced pressure. Furthermore, after that, it cooled to the temperature of 30 degrees C or less, and obtained the aqueous dispersion containing the polymer C as a binder.

(Example 6)

When preparing the binder composition for negative electrode mixture layers, it carried out similarly to Example 1 except having used the binder (polymer D) prepared by the method shown below instead of a binder (polymer A), and the binder composition for negative electrode mixture layers. , A slurry composition for negative electrode mixture layers, a negative electrode, a positive electrode, a separator, and a secondary battery were prepared. And it evaluated similarly to Example 1. The results are shown in Table 1-1.

<Preparation of binder (polymer D)>

In a 5 MPa pressure-resistant vessel equipped with a stirrer, 61 parts of styrene as an aromatic vinyl monomer, 38 parts of 1,3-butadiene as an aliphatic conjugated diene monomer, 1 part of 2-hydroxyethyl acrylate as a hydroxyl group-containing monomer, and t- as a molecular weight regulator 0.3 part of dodecyl mercaptan, 5 parts of sodium dodecylbenzenesulfonate as an emulsifier, 150 parts of ion-exchanged water as a solvent, and 1 part of potassium persulfate as a polymerization initiator were added, and after stirring sufficiently, the mixture was warmed to a temperature of 55 ° C and polymerization was carried out. Started. At the time when the monomer consumption reached 95.0%, the reaction was stopped. A 5% sodium hydroxide aqueous solution was added to the aqueous dispersion containing the polymer thus obtained, and the pH was adjusted to 8. Thereafter, the unreacted monomer was removed by distillation under reduced pressure. Furthermore, after that, it cooled to the temperature of 30 degrees C or less, and obtained the aqueous dispersion containing the polymer D as a binder.

(Example 7)

At the time of preparation of the binder composition for negative electrode mixture layers, it carries out except having prepared the slurry composition for negative electrode mixture layers as follows using the binder (polymer E) prepared by the method shown below instead of a binder (polymer A). In the same manner as in Example 1, a negative electrode, a positive electrode, a separator, and a secondary battery were manufactured. And it evaluated similarly to Example 1. The results are shown in Table 1-1.

<Preparation of binder (polymer E)>

720 g of ion-exchange water was thrown into the septum-mounted 1 L flask, it heated at the temperature of 40 degreeC, and the inside of the flask was replaced by nitrogen gas of 100 mL / min of flow volume. Next, 10 g of ion-exchanged water, 25 parts of acrylic acid as a carboxyl group (carboxylic acid group) -containing monomer, and 75 parts of acrylamide were mixed and injected into the flask with a syringe. Thereafter, 8 parts of a 2.5% aqueous solution of potassium persulfate as a polymerization initiator was added into the flask with a syringe. In addition, after 15 minutes, 22 parts of a 2.0% aqueous solution of tetramethylethylenediamine as a polymerization accelerator were added by syringe. After 4 hours, 4 parts of a 2.5% aqueous solution of potassium persulfate as a polymerization initiator was added into the flask, and 11 parts of a 2.0% aqueous solution of tetramethylethylenediamine as a polymerization accelerator were added, and the temperature was raised to 60 ° C to proceed with the polymerization reaction. I was. After 3 hours, the flask was opened in air to terminate the polymerization reaction, and the product was deodorized at a temperature of 80 ° C. to remove residual monomer. Then, the pH of the product was adjusted to 8 using the 10% aqueous solution of lithium hydroxide, and the aqueous dispersion containing the polymer E as a binder was obtained.

<Preparation of the binder composition for negative electrode mixture layers>

40 parts of sodium hydrogencarbonate as a hydrogencarbonate were mixed with respect to 100 parts (solid content equivalency) of the polymer E, and the binder composition was prepared.

<Preparation of the slurry composition for negative electrode mixture layers>

In the planetary mixer, 48.75 parts of artificial graphite (theoretical capacity: 360 mAh / g) as the negative electrode active material, 48.75 parts of the natural graphite (theoretical capacity: 360 mAh / g), and 2.5 parts of the binder composition for the negative electrode mixture layer in solid content Input. Furthermore, it diluted with ion-exchange water so that solid content concentration might be 60%, and then knead | mixed for 60 minutes at 45 rpm of rotation speed. And the slurry composition for negative electrode mixture layers was prepared by adding ion-exchange water so that a viscosity might be set to 3000 +/- 500 mPa * s (measured by Type-B viscometer, 25 degreeC, 60 rpm).

(Example 8)

<Preparation of binder (polymer F)>

In a reactor A equipped with a mechanical stirrer and a condenser, 85 parts of ion-exchanged water and 0.2 parts of linear alkylbenzenesulfonate were added to the reactor A under a nitrogen atmosphere, followed by heating to 55 ° C. while stirring, and 0.3 parts of potassium persulfate as a 5.0% aqueous solution. Was added to A. Subsequently, 90 parts of acrylonitrile as a cyano group (nitrile group) containing monomer and 2 parts of methacrylic acid as a carboxyl group (carboxylic acid group) containing monomer were put in the container B which is different from the above equipped with a mechanical stirrer in nitrogen atmosphere. 3 parts of dimethylaminoethyl methacrylate as the amino group-containing monomer, 5 parts of n-butyl acrylate (n-butylacrylate) as the (meth) acrylic acid ester monomer, and 0.6 parts of linear sodium alkylbenzenesulfonate, tertiary dodecyl 0.035 part of mercaptan, 0.4 part of polyoxyethylene lauryl ether, and 80 parts of ion-exchange water were added, and it stirred and emulsified and prepared the monomer liquid mixture. And in the state which stirred and emulsified this monomer liquid mixture, it added to Reactor A at constant speed over 5 hours, and made it react until the polymerization conversion ratio became 95%, and obtained the aqueous dispersion liquid of a copolymer. NMP was added to the aqueous dispersion of the obtained copolymer so that solid content concentration of a copolymer 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 of 8%) of the polymer F as a binder was obtained.

<Preparation of the binder composition for positive electrode mixture layers>

To 100 parts (solid content equivalent) of the NMP solution of the polymer F, 30 parts of sodium bicarbonate as a hydrogen carbonate was mixed to prepare a binder composition.

<Preparation of the slurry composition for positive electrode mixture layers>

₂ parts of acetylene black as a conductive material to 96 parts of Co-Ni-Mn lithium composite oxide-based active material (NMC111, LiNi _1/3 Co _1/3 Mn _1/3 O ₂ , average particle diameter 10 μm) as the positive electrode active material (Denka Company Limited, trade name "HS-100") and the binder composition for the positive electrode mixture layer were added 2 parts by solid content, diluted with NMP so that the total solid concentration might be 65%, and the disper Was stirred at 3000 rpm for 1 hour. And the slurry composition for positive electrode mixture layers was prepared by adding ion-exchange water so that a viscosity might become 3000 +/- 500 mPa * s (measured by a type-B viscometer, 25 degreeC, 60 rpm). Slurry stability was evaluated using this slurry composition for positive electrode mixture layers. The results are shown in Table 1-1.

<Manufacture of positive electrode>

A positive electrode original fabric and a positive electrode were produced in the same manner as in Example 1, except that the slurry composition for the positive electrode mixture layer obtained above was used. And the adhesiveness (fill strength) of the positive electrode mixture layer was evaluated using the obtained positive electrode. The results are shown in Table 1-1.

<Manufacture of negative electrode>

Into the planetary mixer, 48.75 parts of artificial graphite (theoretical capacity: 360 mAh / g) as the negative electrode active material, 48.75 parts of the natural graphite (theoretical capacity: 360 mAh / g), and 1 part of carboxymethyl cellulose as a thickener were added as solid content. It was. Furthermore, it diluted with ion-exchange water so that solid content concentration might be 60%, and then knead | mixed for 60 minutes at 45 rpm of rotation speed. Thereafter, 1.5 parts of Polymer A obtained in the same manner as in Example 1 was charged with a solid content equivalent, and kneaded for 40 minutes at a rotational speed of 40 rpm. And the slurry composition for negative electrode mixture layers was prepared by adding ion-exchange water so that a viscosity might be set to 3000 +/- 500 mPa * s (measured by Type-B viscometer, 25 degreeC, 60 rpm).

The slurry composition for negative electrode mixture layers was applied to the surface of a copper foil having a thickness of 15 μm, which is a current collector, by a comma coater such that the coating amount was 11 ± 0.5 mg / cm ² . Then, copper foil with which the slurry composition for negative electrode mixture layers was apply | coated was conveyed in the oven of temperature 80 degreeC for 2 minutes, and the inside of oven of temperature 110 degreeC over 2 minutes at the speed | rate of 500 mm / min over 2 minutes. The slurry composition of the phase was dried, and the negative electrode original fabric in which the negative electrode mixture layer was formed on the electrical power collector was obtained.

Thereafter, the negative electrode mixture layer side of the prepared negative electrode fabric was roll-pressed under conditions of a linear pressure of 11 t (ton) under an environment of a temperature of 25 ± 3 ° C. to obtain a negative electrode having a negative electrode mixture layer density of 1.60 g / cm ³ . Thereafter, the negative electrode was left to stand for one week in an environment having a temperature of 25 ± 3 ° C. and a relative humidity of 50 ± 5%.

<Manufacture of Separator and Secondary Battery>

Except having used the positive electrode and negative electrode obtained above, the separator was prepared like Example 1, and the secondary battery was produced. And rate characteristic and cycling characteristics were evaluated using the obtained lithium ion secondary battery. The results are shown in Table 1-1.

(Example 9)

At the time of preparation of the binder composition for positive electrode mixture layers, it carried out similarly to Example 8 except having used the binder (polymer G) prepared by the method shown below instead of a binder (polymer F), and the binder composition for positive electrode mixture layers. , A slurry composition for positive electrode mixture layers, a positive electrode, a negative electrode, a separator, and a secondary battery were prepared. And it evaluated similarly to Example 8. The results are shown in Table 1-1.

<Preparation of binder (polymer G)>

In a reactor A equipped with a mechanical stirrer and a condenser, 85 parts of ion-exchanged water and 0.2 parts of linear alkylbenzenesulfonate were added to the reactor A under a nitrogen atmosphere, followed by heating to 55 ° C. while stirring, and 0.3 parts of potassium persulfate as a 5.0% aqueous solution. Was added to A. Subsequently, 65 parts of acrylonitrile as a cyano group (nitrile group) containing monomer and 2 parts of methacrylic acid as a carboxyl group (carboxylic acid group) containing monomer in the container B separate from the above equipped with a mechanical stirrer in nitrogen atmosphere. 3 parts of dimethylaminoethyl methacrylate as an amino group containing monomer, 20 parts of 2-ethylhexyl acrylate (2-ethylhexyl acrylate) as a (meth) acrylic acid ester monomer, and n-butyl acrylate as a (meth) acrylic acid ester monomer ( 10 parts of n-butyl acrylate), and 0.6 parts of linear alkylbenzenesulfonate, 0.035 parts of tertiarydecyl mercaptan, 0.4 parts of polyoxyethylene lauryl ether, and 80 parts of ion-exchanged water were added, and this was stirred and emulsified. The monomer liquid mixture was prepared. And in the state which stirred and emulsified this monomer liquid mixture, it added to Reactor A at constant speed over 5 hours, and made it react until the polymerization conversion ratio became 95%, and obtained the aqueous dispersion liquid of a copolymer. NMP was added to the aqueous dispersion of the obtained copolymer so that solid content concentration of a copolymer 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 of 8%) of the polymer G as a binder was obtained.

(Example 10)

At the time of preparation of the binder composition for positive electrode mixture layers, it carried out similarly to Example 8 except having used the binder (polymer H) prepared by the method shown below instead of a binder (polymer F), and the binder composition for positive electrode mixture layers. , A slurry composition for positive electrode mixture layers, a positive electrode, a negative electrode, a separator, and a secondary battery were prepared. And it evaluated similarly to Example 8. The results are shown in Table 1-1.

<Preparation of binder (polymer H)>

In a reactor A equipped with a mechanical stirrer and a condenser, 85 parts of ion-exchanged water and 0.2 parts of linear alkylbenzenesulfonate were added to the reactor A under a nitrogen atmosphere, followed by heating to 55 ° C. while stirring, and 0.3 parts of potassium persulfate as a 5.0% aqueous solution. Was added to A. Subsequently, 30 parts of acrylonitrile as a cyano group (nitrile group) containing monomer and acrylamido-2-methylpropanesulfonic acid as a sulfonic acid group containing monomer are contained in the container B separate from the above equipped with a mechanical stirrer in nitrogen atmosphere. 2 parts, 3 parts of dimethylaminoethyl methacrylate as an amino group containing monomer, 55 parts of 2-ethylhexyl acrylate (2-ethylhexyl acrylate) as a (meth) acrylic acid ester monomer, and acrylic acid n- as a (meth) acrylic acid ester monomer 10 parts of butyl (n-butyl acrylate) and 0.6 parts of linear alkylbenzenesulfonate, 0.035 parts of tertiarydecyl mercaptan, 0.4 parts of polyoxyethylene lauryl ether, and 80 parts of ion-exchanged water were added, and this was stirred. It emulsified and prepared the monomer liquid mixture. And in the state which stirred and emulsified this monomer liquid mixture, it added to Reactor A at constant speed over 5 hours, and made it react until the polymerization conversion ratio became 95%, and obtained the aqueous dispersion liquid of a copolymer. NMP was added to the aqueous dispersion of the obtained copolymer so that solid content concentration of a copolymer 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 of 8%) of the polymer H as a binder was obtained.

(Example 11)

At the time of preparation of the binder composition for positive electrode mixture layers, it carried out similarly to Example 8 except having used the binder (polymer I) prepared by the method shown below instead of a binder (polymer F), and the binder composition for positive electrode mixture layers. , A slurry composition for positive electrode mixture layers, a positive electrode, a negative electrode, a separator, and a secondary battery were prepared. And it evaluated similarly to Example 8. The results are shown in Table 1-1.

<Preparation of binder (polymer I)>

In a reactor A equipped with a mechanical stirrer and a condenser, 85 parts of ion-exchanged water and 0.2 parts of linear alkylbenzenesulfonate were added to the reactor A under a nitrogen atmosphere, followed by heating to 55 ° C. while stirring, and 0.3 parts of potassium persulfate as a 5.0% aqueous solution. Was added to A. Subsequently, 53 parts of acrylonitrile as a cyano group (nitrile group) containing monomer, 15 parts of acrylic acid as a carboxyl group (carboxylic acid group) containing monomer in the container B which differs from the above equipped with a mechanical stirrer, and nitrogen atmosphere, and 32 parts of n-butyl acrylate (n-butyl acrylate) as a (meth) acrylic acid ester monomer, 0.6 parts of linear alkylbenzenesulfonates, 0.035 parts of tertiary dodecyl mercaptan, 0.4 parts of polyoxyethylene lauryl ether, and 80 parts of ion-exchanged water was added, and this was stirred and emulsified to prepare a monomer liquid mixture. And in the state which stirred and emulsified this monomer liquid mixture, it added to Reactor A at constant speed over 5 hours, and made it react until the polymerization conversion ratio became 95%, and obtained the aqueous dispersion liquid of a copolymer. NMP was added to the aqueous dispersion of the obtained copolymer so that solid content concentration of a copolymer might be 7%. The mixture was distilled under reduced pressure at 90 ° C to remove water and excess NMP to obtain an NMP solution (solid content concentration of 8%) of Polymer I as a binder.

(Example 12)

At the time of preparation of the binder composition for positive electrode mixture layers, it carried out similarly to Example 8 except having used the binder (polymer J) prepared by the method shown below instead of a binder (polymer F), and the binder composition for positive electrode mixture layers. , A slurry composition for positive electrode mixture layers, a positive electrode, a negative electrode, a separator, and a secondary battery were prepared. And it evaluated similarly to Example 8. The results are shown in Table 1-1.

<Preparation of binder (polymer J)>

In a reactor A equipped with a mechanical stirrer and a condenser, 85 parts of ion-exchanged water and 0.2 parts of linear alkylbenzenesulfonate were added to the reactor A under a nitrogen atmosphere, followed by heating to 55 ° C. while stirring, and 0.3 parts of potassium persulfate as a 5.0% aqueous solution. Was added to A. Subsequently, 99 parts of acrylonitrile as a cyano group (nitrile group) containing monomer, and methacrylic acid 1 as a carboxyl group (carboxylic acid group) containing monomer were put in the container B separate from the above equipped with a mechanical stirrer under nitrogen atmosphere. Part 0.6 part of linear alkylbenzenesulfonate, 0.035 part of tertiarydecyl mercaptan, 0.4 part of polyoxyethylene lauryl ether, and 80 parts of ion-exchanged water were added, and this was stirred and emulsified to prepare a monomer mixture. And in the state which stirred and emulsified this monomer liquid mixture, it added to Reactor A at constant speed over 5 hours, and made it react until the polymerization conversion ratio became 95%, and obtained the aqueous dispersion liquid of a copolymer. NMP was added to the aqueous dispersion of the obtained copolymer so that solid content concentration of a copolymer 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 of 8%) of the polymer J as a binder was obtained.

(Example 13)

At the time of preparation of the binder composition for positive electrode mixture layers, it carried out similarly to Example 8 except having used the binder (polymer K) prepared by the method shown below instead of a binder (polymer F), and the binder composition for positive electrode mixture layers. , A slurry composition for positive electrode mixture layers, a positive electrode, a negative electrode, a separator, and a secondary battery were prepared. And it evaluated similarly to Example 8. The results are shown in Table 1-1.

<Preparation of binder (polymer K)>

150 parts of ion-exchanged water and 0.2 part of sodium dodecylbenzenesulfonate were added to the separable flask, and the inside of the flask was replaced with nitrogen gas having a flow rate of 100 mL / min. On the other hand, in another container, 60 parts of ion-exchanged water, 0.8 parts of an ether sulfate type emulsifier as an emulsifier in terms of solid content, 20 parts of acrylonitrile as a cyano group (nitrile group) -containing monomer, and a carboxyl group (carboxylic acid group) contained 5 parts of methacrylic acid as a monomer, 10 parts of methyl methacrylate as a (meth) acrylic acid ester monomer, 40 parts of 2-ethylhexyl acrylate (2-ethylhexyl acrylate) as a (meth) acrylic acid ester monomer, and meta 25 parts of 2,2,2-trifluoroethyl krylic acid were mixed and the monomer emulsion containing the mixture of the said monomers was prepared. Thereafter, the flask was warmed, and 0.5 part of ammonium persulfate as a polymerization initiator was added when the temperature inside the flask reached 60 ° C. And when the internal temperature of the flask reached 70 degreeC, the above-mentioned adjusted monomer emulsion liquid was started to add to the flask, and the monomer emulsion liquid was slowly dripped over 3 hours, maintaining the flask internal temperature at 70 degreeC. Then, the internal temperature of the flask was heated up to 85 degreeC and the polymerization reaction was advanced. After 3 hours, the flask was opened in air to terminate the polymerization reaction to obtain an aqueous dispersion of the copolymer. NMP was added to the aqueous dispersion of the obtained copolymer so that solid content concentration of a copolymer might be 7%. The mixture was distilled under reduced pressure at 90 ° C to remove water and excess NMP to obtain an NMP solution (solid content concentration of 8%) of polymer K as a binder.

(Example 14)

At the time of preparation of the binder composition for the positive electrode mixture layer, the same amount as that of Example 10 was used except that the compounding amount of sodium bicarbonate was changed to 55 parts (the content of sodium bicarbonate relative to the binder was 55% by mass). Polymer H, the binder composition for the positive electrode mixture layer, the slurry composition for the positive electrode mixture layer, the positive electrode, the negative electrode, the separator, and the secondary battery were prepared. And it evaluated similarly to Example 10. The results are shown in Table 1-2.

(Example 15)

At the time of preparation of the binder composition for the positive electrode mixture layer, it was the same as in Example 10 except that the compounding quantity of sodium hydrogen carbonate was changed to 8 parts (content of sodium hydrogen carbonate relative to the binder was 8% by mass). Polymer H, the binder composition for the positive electrode mixture layer, the slurry composition for the positive electrode mixture layer, the positive electrode, the negative electrode, the separator, and the secondary battery were prepared. And it evaluated similarly to Example 10. The results are shown in Table 1-2.

(Example 16)

At the time of preparation of the binder composition for the positive electrode mixture layer, it was the same as in Example 10 except that the compounding quantity of sodium hydrogen carbonate was changed to 5 parts (content of sodium hydrogen carbonate relative to the binder 5 mass%). Polymer H, the binder composition for the positive electrode mixture layer, the slurry composition for the positive electrode mixture layer, the positive electrode, the negative electrode, the separator, and the secondary battery were prepared. And it evaluated similarly to Example 10. The results are shown in Table 1-2.

(Example 17)

At the time of preparation of the binder composition for the positive electrode mixture layer, except that the compounding amount of sodium hydrogen carbonate was changed to 30 parts (the content of sodium hydrogen carbonate to the binder is 30% by mass) and the melamine cyanurate as the melamine compound was changed to 20 parts. In the same manner as in Example 10, Polymer H as a binder, a binder composition for a positive electrode mixture layer, a slurry composition for a positive electrode mixture layer, a positive electrode, a negative electrode, a separator, and a secondary battery were prepared. And it evaluated similarly to Example 10. The results are shown in Table 1-2.

(Example 18)

<Preparation of binder (polymer L)>

To the reactor equipped with a stirrer, 70 parts of ion-exchanged water, 0.15 parts of sodium lauryl sulfate (product name "Emal 2F") as an emulsifier, and 0.5 parts of ammonium persulfate were respectively supplied, and the gas phase part was replaced with nitrogen gas. , The temperature was raised to 60 ° C.

On the other hand, 50 parts of ion-exchanged water, 0.5 parts of sodium dodecylbenzenesulfonate as an emulsifier, 35 parts of n-butyl acrylate (n-butylacrylate) as a (meth) acrylic acid ester monomer and 60 parts of methyl methacrylate, and 5 parts of methacrylic acid as a carboxylic acid group (carboxyl group) containing monomer were mixed, and the monomer composition was obtained. This monomer composition was continuously added to the reactor over 4 hours to conduct polymerization. During addition, reaction was performed at 60 degreeC. After completion of the addition, the mixture was further stirred at 70 ° C for 3 hours to complete the reaction, thereby obtaining an aqueous dispersion containing Polymer L as a binder.

<Preparation of the binder composition for porous film layers>

To 100 parts (solid content equivalent) of the aqueous dispersion of the polymer L, 35 parts of sodium bicarbonate as a hydrogen carbonate was mixed to prepare a binder composition.

<Preparation of the slurry composition for the functional layer (porous membrane layer) for non-aqueous secondary batteries>

100 parts of alumina (Sumitomo Chemical Co., Ltd. product name "AKP3000") as a non-conductive particle in solid content correspondence, 5 mass parts (solid content equivalent) of the said binder composition for porous film layers, 1.5 mass parts of polyacrylamide as a thickener, 0.8 mass part of polyacrylic acid as a dispersing agent and 0.2 mass part of emulgen 120 (made by Cao) as a wetting agent were added so that solid content concentration might be 40%, it mixed using a ball mill, and the functional layer for non-aqueous secondary batteries The slurry composition for (porous membrane layer) was obtained. Slurry stability was evaluated using this slurry composition for functional layers (porous membrane layer) for non-aqueous secondary batteries. The results are shown in Table 1-2.

<Production of Separator (Composite Membrane) with Functional Layers (Porous Membrane Layer) for Non-Aqueous Secondary Batteries on Both Sides>

On the organic separator base material (made of polypropylene, product name "Celgard 2500") as a base material, the slurry composition for the functional layer (porous membrane layer) for nonaqueous secondary batteries obtained above is obtained, and the said functional layer (porous membrane layer) for a non-aqueous secondary battery. The slurry composition for) was applied so as to have a thickness of 2 μm, and dried at 50 ° C. for 10 minutes to obtain a separator (composite membrane) having a functional layer (porous membrane layer) for nonaqueous secondary batteries on one side of the organic separator substrate. The adhesiveness of the non-aqueous secondary battery functional layer (porous membrane layer) was evaluated using the separator (composite membrane) which has a functional layer (porous membrane layer) for nonaqueous secondary batteries on this single side. The results are shown in Table 1-2. Moreover, the separator (composite membrane) which has the functional layer (porous membrane layer) for non-aqueous secondary batteries on both surfaces of the organic separator base material was obtained by performing the said application | coating and drying operation on both surfaces separately.

<Manufacture of negative electrode>

In the same manner as in Example 8, a negative electrode was produced.

<Manufacture of positive electrode>

In the same manner as in Example 1, a positive electrode was produced.

<Production of Secondary Battery>

Using a separator having a porous membrane layer on the negative electrode, the positive electrode, and both surfaces, a wound cell (equivalent to a discharge capacity of 520 mAh) was produced so as to face the negative electrode mixture layer and the positive electrode mixture layer through the separator, and placed in an aluminum packaging material. . The wound cell was pressed with an aluminum packaging material at a temperature of 70 ° C. and a pressure of 1.0 MPa for 8 seconds with a heated flat press to bond the separator and the electrodes (negative electrode and positive electrode).

Thereafter, a mixed solvent of a LiPF ₆ solution (solvent: ethylene carbonate (EC) / diethyl carbonate (DEC) = 3/7 (volume ratio)) having a concentration of 1.0 M in an aluminum packaging material, and an additive: 2% by volume of vinylene carbonate (Solvent ratio))). In addition, in order to seal the opening of an aluminum packaging material, the aluminum packaging material was closed by heat-sealing with a temperature of 150 degreeC, and the lithium ion secondary battery was produced. Rate characteristics and cycle characteristics were evaluated using this lithium ion secondary battery. The results are shown in Table 1-2.

(Example 19)

When preparing the binder composition for porous membrane layers, it carried out similarly to Example 18 except having used the binder (polymer M) prepared by the method shown below instead of the binder (polymer L), and the binder composition for porous membrane layers , Slurry composition for porous membrane layers, separator (composite membrane), negative electrode, positive electrode, and secondary battery were manufactured. And it evaluated similarly to Example 18. The results are shown in Table 1-2.

<Preparation of binder (polymer M)>

To the reactor equipped with a stirrer, 70 parts of ion-exchanged water, 0.15 parts of sodium lauryl sulfate (product name "Emal 2F") as an emulsifier, and 0.5 parts of ammonium persulfate were respectively supplied, and the gas phase part was replaced with nitrogen gas. , The temperature was raised to 60 ° C.

In another vessel, 50 parts of ion-exchanged water, 0.5 part of sodium dodecylbenzenesulfonate as an emulsifier, 30 parts of acrylonitrile as a cyano group (nitrile group) -containing monomer, and n-butyl acrylate as a (meth) acrylic acid ester monomer ( n-butyl acrylate) 28 parts, methyl methacrylate 30 parts, methacrylic acid as a carboxylic acid group (carboxyl group) containing monomer 10 parts, and allyl glycidyl ether as an epoxy group containing monomer were mixed, and the monomer composition was obtained. This monomer composition was continuously added to the reactor over 4 hours to conduct polymerization. During addition, reaction was performed at 60 degreeC. After completion of the addition, the mixture was further stirred at 70 ° C for 3 hours to terminate the reaction, thereby obtaining an aqueous dispersion containing Polymer M as a binder.

(Example 20)

When preparing the binder composition for the porous membrane layer, the same procedure as in Example 19 was carried out except that sodium hydrogen carbonate was used instead of sodium hydrogen carbonate, and the binder composition for the porous membrane layer, the slurry composition for the porous membrane layer, the separator (composite membrane), A negative electrode, a positive electrode, and a secondary battery were manufactured. And it evaluated similarly to Example 19. The results are shown in Table 1-2.

(Example 21)

<Preparation of binder composition for electric double layer capacitor>

To 100 parts (solid content equivalent) of the aqueous dispersion of Polymer A, 35 parts of sodium bicarbonate as a hydrogen carbonate was mixed to prepare a binder composition.

<Preparation of slurry composition for electric double layer capacitor electrode>

To the planetary mixer, 92 parts of activated carbon as an electrode active material (steam revitalization activated carbon using coconut shells, Kuraray Chemical Co., Ltd., YP-50F, specific surface area: 1600 m ² / g), and Ketjen Black as a conductive material 2 parts of Lion Corporation, ECP) and carboxymethyl cellulose as a thickener were charged in 3.0 parts by solid content, and it diluted with ion-exchange water so that solid content concentration might be 38%. Thereafter, 3.0 parts of the binder composition for an electric double layer capacitor obtained above was charged with a solid content equivalent, and kneaded for 40 minutes at a rotational speed of 40 rpm. Thereafter, the mixture was kneaded at a rotational speed of 40 rpm for 60 minutes to obtain a paste slurry. Furthermore, ion-exchange water was added so that a viscosity might become 5000 +/- 500 mPa * s (measured by a B viscometer, 60 rpm), and the slurry composition for electric double layer capacitor electrodes was prepared. Slurry stability was evaluated using this slurry composition for electric double layer capacitor electrodes. The results are shown in Table 1-2.

<Production of Electrode for Electric Double Layer Capacitor>

The slurry composition for electric double layer capacitors was apply | coated so that the coating amount might be 8.0 mg / cm <^2> on the surface of 20 micrometers thickness aluminum foil which is an electrical power collector by the comma coater. On the other hand, this application | coating was performed so that the location which a slurry composition may not apply to may be left in order to ensure the part in which the electrode mixture layer is not formed on the aluminum foil after drying. Aluminum foil by which this slurry composition for electrical double layer capacitor electrodes was apply | coated was conveyed in the oven of temperature 80 degreeC for 4 minutes, and the oven of temperature 110 degreeC over 4 minutes at the speed | rate of 0.3 m / min, for 4 minutes. The slurry composition on the phase was dried. Then, the slurry composition was apply | coated similarly to the back surface side of aluminum foil, and it dried, and obtained the electrode original fabric.

And the obtained electrode original fabric was pressed so that the density might be set to 0.59 g / cm <^3> by the roll press machine, and the double-sided electrode was obtained by vacuum-drying at 120 degreeC for 24 hours. The adhesiveness (fill strength) of an electrode mixture layer and an electrical power collector was evaluated using this double sided electrode. The results are shown in Table 1-2.

Fabrication of Electric Double Layer Capacitors

The double-sided electrode produced as described above was cut out so that the portion where the electrode mixture layer was not formed remained 2 cm x 2 cm, and the portion where the electrode mixture layer was formed was 5 cm x 5 cm (at this time). The portion where the electrode mixture layer is not formed is formed so as to extend one side of the square of the portion where the electrode mixture layer is formed. Moreover, the cellulose separator (made by Nippon Koshido Co., Ltd., TF4035) was cut out so that it might be 5.3 cm x 5.3 cm. In this way, 9 cut-out electrodes (4 positive electrodes and 5 negative electrodes) and 10 separators were arrange | positioned in the same direction so that the part in which the electrode mixture layer of a positive electrode collector and a negative electrode collector is not formed may not overlap each other, And the positive electrode and the negative electrode were alternately arrange | positioned, and the separator was arrange | positioned so that it may be located between a positive electrode and a negative electrode, and all were laminated | stacked. Moreover, the four sides of the uppermost layer and the lowermost layer were tape fixed, and the laminated body was obtained. At this time, a separator is arrange | positioned in the uppermost layer and the lowest layer (outermost layer) of the obtained laminated body, and the negative electrode contact | connects both inside a laminated body in the separator of an uppermost layer and a lowermost layer. Subsequently, the electrode laminated body was produced by ultrasonically welding the tab material which consists of aluminum 7 cm x 1 cm x 0.02 cm in thickness to the part in which the electrode mixture layer of each of the top electrodes was not formed.

After placing the electrode laminate inside the deep-drawing exterior film and fusion of three sides, an electrolyte solution (composition: (C ₂ H ₅ ) ₄ NBF ₄ solution (solvent is propylene carbonate) with a concentration of 1.0 M, Kishida Chemical Co., Ltd.) (Preparation) was vacuum impregnated, and the remaining one side was fused under reduced pressure to prepare an electric double layer capacitor. Rate characteristics and cycle characteristics were evaluated using this electric double layer capacitor. The results are shown in Table 1-2.

(Comparative Example 1)

In preparing the binder composition for the negative electrode mixture layer, in place of the binder (polymer A), the binder (polymer H) prepared in Example 10 is used, except that sodium hydrogencarbonate as the hydrogen carbonate is not blended. In the same manner as that, a binder composition for a negative electrode mixture layer, a slurry composition for a negative electrode mixture layer, a negative electrode, a positive electrode, a separator, and a secondary battery were prepared. And it evaluated similarly to Example 1. The results are shown in Table 1-2.

(Comparative Example 2)

When preparing the binder composition for the negative electrode mixture layer, instead of the binder (polymer A), a binder (polymer N) shown below was used, and the compounding quantity of sodium hydrogencarbonate was 35 parts (content of sodium hydrogen carbonate relative to the binder). In the same manner as in Example 1, except that was changed to 35 mass%), a negative electrode mixture layer binder composition, a negative electrode mixture layer slurry composition, a negative electrode, a positive electrode, a separator, and a secondary battery. And it evaluated similarly to Example 1. The results are shown in Table 1-2.

<Preparation of binder (polymer N)>

Polyvinylidene fluoride (polymer N, Kureha Chemical make, brand name "KF-1100") as a binder was dissolved in NMP, and the NMP solution (solid content concentration: 8%) of polymer N as a binder was prepared.

(Example 22)

<Preparation of Organic Particles A>

In the formation of the core portion, 37 parts of 2-ethylhexyl acrylate (2-ethylhexyl acrylate) (2EHA) as a (meth) acrylic acid ester monomer and 55 parts of styrene (ST) as an aromatic vinyl monomer were placed in a 5 MPa pressure vessel equipped with a stirrer. , 2.9 parts of methacrylic acid (MAA) as an acid group-containing monomer, 1 part of sodium dodecylbenzenesulfonate as an emulsifier, 150 parts of ion-exchanged water, and 0.5 part of potassium persulfate as a polymerization initiator were added, and the mixture was sufficiently stirred and then heated to 60 ° C. Polymerization was initiated. The polymerization was continued until the polymerization conversion ratio reached 96%, thereby obtaining an aqueous dispersion containing the particulate polymer X constituting the core portion. Subsequently, when the polymerization conversion ratio reached 96%, in order to form a shell portion, 5 parts of styrene (ST) as an aromatic vinyl monomer and 0.1 part of methacrylic acid (MAA) as an acid group-containing monomer were continuously added and heated to 70 ° C. The polymerization was continued, and when the conversion ratio reached 96%, the mixture was cooled to stop the reaction to obtain an aqueous dispersion containing organic particles A. The obtained organic particle A had the core-shell structure which the outer surface of the core part which consists of polymer X partially covered with the shell part which consists of polymer Y.

And the electrolyte solution swelling degree, volume average particle diameter, and glass transition temperature of the obtained organic particle A were measured. The results are shown in Table 1-3.

Glass transition temperature (Tg)

The aqueous dispersion containing the organic particles A was dried at a temperature of 25 ° C. for 48 hours to obtain a powdery sample to obtain a measurement sample.

10 mg of measurement samples are weighed in an aluminum pan, and the temperature increase rate is 20 ° C / min in a measurement temperature range of -100 ° C to 200 ° C with a differential thermal analysis measurement device (EXEX DSC6220 manufactured by SAI Nano Technology Co., Ltd.). Then, measurement was performed under the conditions specified in JIS Z8703 to obtain a differential scanning calorimetry (DSC) curve. Meanwhile, an empty aluminum pan was used as a reference. In this temperature raising process, the temperature at which the differential signal (DDSC) shows a peak was determined as the glass transition temperature (° C). On the other hand, since a plurality of peaks were measured, the temperature represented by the peak with large displacement was taken as the glass transition temperature of the organic particles A.

Electrolyte swelling degree of organic particle A

An aqueous dispersion containing organic particles A was placed in a polytetrafluoroethylene chalet. The aqueous dispersion which entered the chalet was dried for 48 hours at the temperature of 25 degreeC, and the powdery sample was obtained. A test piece was obtained by pressing about 0.2 g of the sample at a temperature of 200 ° C. and a pressure of 5 MPa for 2 minutes. The weight of the obtained test piece was measured and set to W0.

Next, the obtained test piece was immersed for 72 hours in electrolyte solution of temperature 60 degreeC. Here, as an electrolyte solution, it is a density | concentration as a supporting electrolyte in the mixed solvent (volume mixing ratio: EC / DEC / VC = 68.5 / 30 / 1.5) of ethylene carbonate (EC), diethyl carbonate (DEC), and vinylene carbonate (VC). A solution containing 1 M LiPF ₆ was used.

The test piece after immersion was taken out from the electrolyte solution, and the electrolyte solution on the surface of the test piece was wiped off. The weight of the test piece after the said immersion was measured, and it was set as W1. Using measured W0 and W1, electrolyte solution swelling degree S (mass%) was computed as S = (W1 / W0) * 100.

Volume average particle size

The volume average particle diameter of the organic particle A was measured by the laser diffraction method. Specifically, the aqueous dispersion (prepared to 0.1 mass% of solid content concentration) containing the prepared organic particle | grain A was used as the sample. And in the particle size distribution (volume basis) measured using the laser diffraction type particle size distribution measuring apparatus (manufactured by Beckman Coulter, product name "LS-13 320"), the cumulative volume calculated from the small diameter side is 50%. Particle diameter D50 was taken as the volume average particle diameter.

<Preparation of the slurry composition for non-aqueous secondary battery functional layer (adhesive layer)>

35 parts of sodium hydrogencarbonate (NaHCO ₃ ) as a hydrogen carbonate, 1000 parts of said organic particles A in solid content, and emuls 120 as a wetting agent with respect to 65 parts (solid content equivalent) of the polymer M as a binder. 1 part) was mixed in a stirring vessel to obtain a mixture.

The obtained mixture was diluted with ion-exchange water, and the slurry composition (solid content concentration: 10%) for slurry-like non-aqueous secondary battery functional layers (adhesive layer) was obtained.

And the slurry stability of the obtained slurry composition for functional layers (adhesive layer) for non-aqueous secondary batteries was evaluated. The results are shown in Table 1-3.

In addition, the particle diameter and Tg of the polymer M were measured by the method similar to the particle diameter and Tg of the organic particle A. FIG.

<Production of Separator (Composite Membrane) with Functional Layer (Adhesion Layer) for Non-Aqueous Secondary Battery on Both Sides>

A separator base material (manufactured by Celgard, trade name "Celgard 2500", thickness: 25 µm) made of polypropylene was prepared. The slurry composition for non-aqueous secondary battery functional layers (adhesive layer) obtained above was apply | coated to the surface of the prepared separator base material, and it dried for 3 minutes at 50 degreeC. The same operation was performed also on the other surface of the separator base material, and the separator (thickness of each functional layer (adhesive layer): 1 micrometer each) provided with the functional layer (adhesive layer) for nonaqueous secondary batteries on both surfaces was obtained.

And the peeling strength of the obtained functional layer (adhesive layer) for non-aqueous secondary batteries, and the process adhesiveness of the obtained separator (composite film) were evaluated. The results are shown in Table 1-3. In addition, the negative electrode and the positive electrode produced as follows were used for evaluation of process adhesiveness.

<Production of negative electrode>

In a 5 MPa pressure vessel equipped with a stirrer, 33 parts of 1,3-butadiene as aliphatic conjugated diene monomer, 3.5 parts of itaconic acid as carboxylic acid group-containing monomer, 63.5 parts of styrene as aromatic vinyl monomer, and 0.4 parts of sodium dodecylbenzenesulfonate as emulsifier , 150 parts of ion-exchanged water, and 0.5 part of potassium persulfate as a polymerization initiator were added thereto, and after sufficiently stirring, the mixture was heated to 50 ° C to initiate polymerization. When the polymerization conversion ratio reached 96%, the mixture was cooled to stop the polymerization reaction, thereby obtaining a mixture containing a particulate binder (styrene-butadiene copolymer). To the mixture, 5% aqueous sodium hydroxide solution was added to adjust pH to 8, and then unreacted monomer was removed by distillation under reduced pressure. Then, the mixture was cooled to 30 degrees C or less, and the aqueous dispersion containing the binder for negative electrodes was obtained.

A mixture containing 100 parts of artificial graphite (average particle size: 15.6 μm) and 2 parts of an aqueous solution of carboxymethylcellulose sodium salt as a thickener (manufactured by Nippon Paper Co., Ltd., trade name "MAC350HC") in solids equivalent to 1 part with ion exchange water. After adjusting to solid content concentration 68%, it mixed at 25 degreeC for 60 minutes. Furthermore, after adjusting to 62% of solid content concentration by ion-exchange water, it mixed again at 25 degreeC for 15 minutes, and obtained the liquid mixture. To the obtained liquid mixture, 1.5 parts of solid content equivalent amount and ion-exchange water were added to the aqueous dispersion liquid containing the binder for negative electrodes mentioned above, it adjusted so that it might become final solid content concentration 52%, and it mixed again for 10 minutes. The liquid mixture was defoamed under reduced pressure to obtain a slurry composition for negative electrodes having good fluidity.

The slurry composition for nonaqueous secondary battery negative electrodes obtained above was apply | coated to copper foil (thickness: 20 micrometers) as an electrical power collector so that the film thickness after drying might be about 150 micrometers using a comma coater, and it dried. The said drying was performed by conveying the inside of 60 degreeC oven over 2 minutes for the apply | coated copper foil at a speed | rate of 0.5 m / min. Then, the negative electrode original fabric before press was obtained by heat-processing at 120 degreeC for 2 minutes. The negative electrode original fabric before the said press was rolled by the roll press, and the negative electrode (thickness of a negative electrode mixture layer: 80 micrometers) after press was obtained.

On the other hand, the single-sided negative electrode which apply | coated the slurry composition to the single side | surface, and the double-sided negative electrode which apply | coated the slurry composition to both surfaces are produced, the single-sided negative electrode is used for evaluation of process adhesiveness, and it is used for preparation of the non-aqueous secondary battery which mentions a double-sided negative electrode later. It was.

<Formation of Positive Electrode>

100 parts of LiCoO ₂ (volume average particle diameter: 12 μm) as a positive electrode active material, ₂ parts of acetylene black (manufactured by Denka Company Limited, product name "HS-100") as a conductive material, and polyfluoride as a binder for a positive electrode Two parts were mixed with N-methylpyrrolidone as a solvent by the vinylidene (Kureha Co. make, product name "# 7208") solid content equivalent, and the mixed liquid which adjusted the total solid content concentration to 70% was obtained. The slurry mixture for non-aqueous secondary battery positive electrodes was obtained by mixing the obtained liquid mixture using a planetary mixer.

The slurry composition for nonaqueous secondary battery positive electrodes obtained above was apply | coated to the aluminum foil (thickness 20 micrometers) as an electrical power collector so that the film thickness after drying might be about 150 micrometers using a comma coater, and it dried. The said drying was performed by conveying the inside of 60 degreeC oven over 2 minutes for aluminum foil at a speed | rate of 0.5 m / min. Then, the positive electrode original fabric before press was obtained by heat-processing at 120 degreeC for 2 minutes. The positive electrode original fabric before the said press was rolled by the roll press, and the positive electrode (thickness of the positive electrode mixture layer: 80 micrometers) after press was obtained.

On the other hand, the single-sided positive electrode which apply | coated the slurry composition to the single side | surface, and the double-sided positive electrode which apply | coated the slurry composition to both sides are produced, the single-sided positive electrode is used for evaluation of process adhesiveness, and it is used for preparation of the non-aqueous secondary battery which mentions a double-sided positive electrode later. It was.

<Production of Lithium Ion Secondary Battery (LIB) as Electrochemical Device>

10 sheets of 5 cm x 5 cm after the obtained double-sided positive electrode obtained above, and 20 sheets of 5.5 cm x 5.5 cm of the separator (composite film) provided with the functional layer (adhesive layer) on both surfaces obtained above are 20 sheets 11 sheets of double-sided negative electrodes after one press were cut out. These were laminated | stacked in order of negative electrode / separator / positive electrode /, and the pre laminated body was obtained by pressing for 90 second 2 MPa 5 seconds. The resultant pre-laminate is further laminated in the order of pre-laminate / separator / pre-laminate, and then pressed again at 90 ° C. 2 MPa for 5 seconds to give a laminate (pre-laminate 1 / separator / pre-laminate 2 / separator). / Pre lamination 3 / separator / pre lamination 4 / separator / pre lamination 5 / separator / pre lamination 6 / separator / pre lamination 7 / separator / pre lamination 8 / separator / pre lamination 9 / separator / A pre laminate 10) was obtained.

Subsequently, this laminated body was wrapped in the aluminum packaging exterior as an exterior of a battery, and electrolyte solution was injected so that air might not remain. Here, as electrolyte solution, it is concentration as a supporting electrolyte in the mixed solvent (volume mixing ratio: EC / DEC / VC = 68.5 / 30 / 1.5) of ethylene carbonate (EC), diethyl carbonate (DEC), and vinylene carbonate (VC). A solution containing 1 M LiPF ₆ was used. Then, at 150 ° C, the opening of the aluminum packaging enclosure was heat-sealed at 150 ° C to seal and close the aluminum packaging exterior, thereby manufacturing a wound lithium ion secondary battery having a capacity of 800 mAh. The rate characteristic (low temperature output characteristic) and cycling characteristics of the obtained wound type lithium ion secondary battery were evaluated. The results are shown in Table 1-3. And it confirmed that the manufactured lithium ion secondary battery operated | worked favorably.

(Example 23)

At the time of preparation of the slurry composition for a non-aqueous secondary battery functional layer (adhesive layer), it carried out similarly to Example 22 except having changed the organic particle A into the organic particle | grains B manufactured as follows, and a non-aqueous secondary battery functional layer (adhesive layer) ), A separator (composite membrane), a negative electrode, a positive electrode, and a secondary battery were prepared. And it evaluated similarly to Example 22. The results are shown in Table 1-3.

<< Preparation of Organic Particles B >>

In the formation of the core portion, 23 parts of 2-ethylhexyl acrylate (2-ethylhexyl acrylate) (2EHA) as a (meth) acrylic acid ester monomer and 36.3 parts of styrene (ST) as an aromatic vinyl monomer in a 5 MPa pressure-resistant container equipped with a stirrer. 2 parts of methacrylic acid (MAA) as an acid group-containing monomer, 8.5 parts of acrylonitrile (AN) as a cyano group-containing monomer, 0.2 parts of ethylene glycol dimethacrylate (EDMA) as a crosslinkable monomer, dodecylbenzenesulfonic acid as an emulsifier 1 part of sodium, 150 parts of ion-exchanged water, and 0.5 part of potassium persulfate as a polymerization initiator were added, and after sufficiently stirring, the mixture was heated to 60 ° C to initiate polymerization. The polymerization was continued until the polymerization conversion ratio reached 96%, thereby obtaining an aqueous dispersion containing the particulate polymer X constituting the core portion. Then, at the time when the polymerization conversion ratio reached 96%, in order to form a shell portion, 29.5 parts of styrene (ST) as an aromatic vinyl monomer and 0.5 part of methacrylic acid (MAA) as an acid group-containing monomer were continuously added and heated to 70 ° C. The polymerization was continued, and when the conversion ratio reached 96%, the mixture was cooled to stop the reaction to obtain an aqueous dispersion containing organic particles B. The obtained organic particle B had the core-shell structure which the outer surface of the core part which consists of polymer X partially covered with the shell part which consists of polymer Y.

And the electrolyte solution swelling degree, volume average particle diameter, and glass transition temperature of the obtained organic particle B were measured similarly to organic particle A. FIG. The results are shown in Table 1-3.

(Example 24)

At the time of preparation of the slurry composition for a non-aqueous secondary battery functional layer (adhesive layer), it carried out similarly to Example 22 except having changed the organic particle A into the organic particle C manufactured as follows, and a non-aqueous secondary battery functional layer (adhesive layer) ), A separator (composite membrane), a negative electrode, a positive electrode, and a secondary battery were prepared. And it evaluated similarly to Example 22. The results are shown in Table 1-3.

<< Preparation of Organic Particles C >>

In the formation of the core portion, 38.5 parts of methyl methacrylate (MMA) as a (meth) acrylic acid ester monomer, 28.6 parts of butyl acrylate (BA), and 0.1 part of allyl methacrylate (AMA) in a 5 MPa pressure vessel equipped with a stirrer; 2.8 parts of methacrylic acid (MAA) as an acid group-containing monomer, 1 part of sodium dodecylbenzenesulfonate as an emulsifier, 150 parts of ion-exchanged water, and 0.5 part of potassium persulfate as a polymerization initiator were added, followed by sufficient stirring, followed by heating to 60 ° C. The polymerization was initiated. The polymerization was continued until the polymerization conversion ratio reached 96%, thereby obtaining an aqueous dispersion containing the particulate polymer X constituting the core portion. Then, at the time when the polymerization conversion ratio reached 96%, in order to form a shell portion, 29.5 parts of styrene (ST) as an aromatic vinyl monomer and 0.5 part of methacrylic acid (MAA) as an acid group-containing monomer were continuously added and heated to 70 ° C. The polymerization was continued, and when the conversion ratio reached 96%, the mixture was cooled to stop the reaction to obtain an aqueous dispersion containing organic particles C. The obtained organic particle C had the core-shell structure which the outer surface of the core part which consists of polymer X partially covered with the shell part which consists of polymer Y.

And the electrolyte solution swelling degree, volume average particle diameter, and glass transition temperature of the obtained organic particle C were measured similarly to organic particle A. FIG. The results are shown in Table 1-3.

(Comparative Example 3)

A non-aqueous secondary battery functional layer (adhesive layer) was prepared in the same manner as in Example 22 except that sodium hydrogencarbonate (NaHCO ₃ ) as a hydrogen carbonate was not used when preparing the slurry composition for a non-aqueous secondary battery functional layer (adhesive layer). ), A separator (composite membrane), a negative electrode, a positive electrode, and a secondary battery were prepared. And it evaluated similarly to Example 22. The results are shown in Table 1-3.

(Comparative Example 4)

A non-aqueous secondary battery functional layer (adhesive layer) was prepared in the same manner as in Example 23 except that sodium hydrogencarbonate (NaHCO ₃ ) as a hydrogen carbonate was not used when preparing the slurry composition for a non-aqueous secondary battery functional layer (adhesive layer). ), A separator (composite membrane), a negative electrode, a positive electrode, and a secondary battery were prepared. And it evaluated similarly to Example 23. The results are shown in Table 1-3.

(Comparative Example 5)

A non-aqueous secondary battery functional layer (adhesive layer) was prepared in the same manner as in Example 24 except that sodium hydrogencarbonate (NaHCO ₃ ) as a hydrogen carbonate was not used when preparing the slurry composition for a non-aqueous secondary battery functional layer (adhesive layer). ), A separator (composite membrane), a negative electrode, a positive electrode, and a secondary battery were prepared. And it evaluated similarly to Example 24. The results are shown in Table 1-3.

(Example 25)

<Preparation of the slurry composition for separators (composite membrane) provided with the functional layer (adhesive layer) for non-aqueous secondary batteries>

60 parts of polymer O (particle size 190 nm) as a binder prepared as follows, 40 parts of sodium hydrogencarbonate (1) (NaHCO ₃ (1), particle size 190 nm) as a hydrogen carbonate, and an emulsifier 120 (Kao as a wetting agent) 5 parts and 565 parts of ion-exchange water as a liquid medium were stirred for 30 minutes with a 3-one motor, and the slurry composition for separators (composite membrane) of 500 g in total amount was produced.

And the slurry stability of the obtained slurry composition for separators (composite membrane) was evaluated. The results are shown in Table 1-4.

In addition, the particle diameter of the polymer O and sodium hydrogencarbonate (1) was measured by the method similar to the particle diameter of the organic particle A mentioned above.

<Preparation of binder (polymer O)>

To the reactor equipped with a stirrer, 70 parts of ion-exchanged water, 0.15 parts of sodium lauryl sulfate (product name "Emal 2F") as an emulsifier, and 0.5 parts of ammonium persulfate were respectively supplied, and the gas phase part was replaced with nitrogen gas. , The temperature was raised to 60 ° C.

On the other hand, in another vessel, 50 parts of ion-exchanged water, 0.5 part of sodium dodecylbenzenesulfonate as an emulsifier, 35 parts of n-butyl acrylate (n-butylacrylate) as a (meth) acrylic acid ester monomer and 45 parts of methyl methacrylate , 14 parts of acrylonitrile as a cyano group (nitrile group) -containing monomer, 5 parts of methacrylic acid as a carboxyl group (carboxylic acid group) -containing monomer, and 1 part of allylglycidyl ether as an epoxy group-containing monomer unit were mixed to obtain a monomer composition. This monomer composition was continuously added to the reactor over 4 hours to conduct polymerization. During addition, reaction was performed at 60 degreeC. After completion of the addition, the mixture was further stirred at 70 ° C for 3 hours to complete the reaction, thereby obtaining an aqueous dispersion containing Polymer O as a binder.

<Manufacture of a separator (composite film) provided with the functional layer (adhesive layer) for nonaqueous secondary batteries>

A separator base material (manufactured by Celgard, trade name "Celgard 2500", thickness: 25 µm) made of polypropylene was prepared. The separator (the thickness of a functional layer: 2 micrometers) which apply | coats the slurry composition for separators (composite film) obtained above to the surface of the prepared separator base material, it dries at 50 degreeC for 3 minutes, and has a functional layer (adhesive layer) on one side. )

And the rise value of adhesiveness (fill strength) and air permeability of the obtained separator (composite film) were evaluated. On the other hand, the impregnation into the inside means that the composition for a composite film exists to the inside of the thickness direction of a separator base material, For example, it can confirm by cutting a separator in thickness direction and observing with an electron microscope. When a specific element exists in a composite composition, or when a specific structure exists, it can also confirm by glow discharge emission spectrometry, the EPMA analysis by Os staining, etc. Therefore, the obtained composite film is cross-sectional processed using a cross section polisher (manufactured by JEOL Corporation), the cross section is observed with FE-SEM (manufactured by Hitachi High-Technologies Corporation, S4700), and is the functional layer laminated on the separator substrate? It was checked whether it was impregnated inside. The results are shown in Table 1-4.

<Manufacture of positive electrode>

100 parts of LiCoO ₂ (volume average particle diameter (D50): 12 μm) as a positive electrode active material, ₂ parts of acetylene black (manufactured by Denka Company Limited, HS-100) as a conductive material, and a binder for the positive electrode mixture layer PVDF (polyvinylidene fluoride, manufactured by Kureha Co., Ltd., # 7208) was mixed with 2 parts of solid equivalents, and NMP (N-methylpyrrolidone) in an amount such that the total solid concentration was 70%. These were mixed by the planetary mixer and the slurry composition for positive electrodes was obtained.

The obtained slurry composition for positive electrodes was apply | coated and dried so that the film thickness after drying might be about 150 micrometers on the aluminum foil of 20 micrometers thickness which is an electrical power collector by a comma coater. This drying was performed by conveying the inside of 60 degreeC oven over 2 minutes for aluminum foil at a speed | rate of 0.5 m / min. Then, the positive electrode original fabric was rolled by the roll press, and the positive electrode whose thickness of a positive electrode mixture layer is 95 micrometers was obtained.

<Manufacture of negative electrode>

In a 5 MPa pressure vessel equipped with a stirrer, 33.5 parts of 1,3-butadiene, 3.5 parts of itaconic acid, 62 parts of styrene, 1 part of 2-hydroxyethyl acrylate, 0.4 part of sodium dodecylbenzenesulfonate as an emulsifier, 150 parts of ion-exchanged water And 0.5 part of potassium peroxo disulfate was added as a polymerization initiator, after fully stirring, it heated to 50 degreeC and started superposition | polymerization. When the polymerization conversion ratio reached 96%, the mixture was cooled and the reaction was stopped to obtain a mixture containing the binder for negative electrode mixture layer (SBR). 5% sodium hydroxide aqueous solution was added to the mixture containing the said negative electrode mixture layer binder, and it adjusted to pH 8, and the unreacted monomer was removed by heat-pressure distillation. Then, it cooled to 30 degrees C or less, and obtained the aqueous dispersion containing the binder for desired negative electrode mixture layers.

Solid content concentration of the mixture of 100 parts of artificial graphite (volume average particle diameter (D50): 15.6 micrometer) as a negative electrode active material, and the 2% aqueous solution of the sodium salt of carboxymethylcellulose as a thickener (made by Nippon Paper Co., Ltd., MAC350HC) by solid content is equivalent to 1 part. Was adjusted to 68% with ion-exchanged water and then mixed at 25 ° C. for 60 minutes. Again adjusted to 62% solids concentration with ion-exchanged water, and mixed at 25 ℃ for 15 minutes. The above negative electrode mixture layer binder (SBR) was added in an amount corresponding to 1.5 parts by solid content and ion-exchanged water, and adjusted to a final solid content concentration of 52%, followed by mixing for 10 minutes. This was degassed under reduced pressure to prepare a slurry composition for negative electrode having good fluidity.

The obtained slurry composition for negative electrodes was apply | coated so that the film thickness after drying might be about 150 micrometers on copper foil of 20 micrometers thickness which is an electrical power collector by a comma coater, and it dried. This drying was performed by conveying the inside of 60 degreeC oven over 2 minutes for copper foil at a speed | rate of 0.5 m / min. Then, the negative electrode original fabric was rolled by the roll press, and the negative electrode whose thickness of a negative electrode active material layer is 100 micrometers was obtained.

<Production of Lithium Ion Secondary Battery>

As the exterior of the battery, an aluminum packaging exterior was prepared. The produced positive electrode was cut out to the square of 4.6 cm x 4.6 cm, and the rectangular positive electrode was obtained. Furthermore, the produced separator (composite membrane) was cut out to the square of 5.2 cm x 5.2 cm, and the rectangular separator (composite membrane) was obtained. Furthermore, the produced negative electrode was cut out to square of 5 cm x 5 cm, and the rectangular negative electrode was obtained. The rectangular positive electrode was arrange | positioned in a packaging exterior so that the surface of the electrical power collector side may be in contact with an aluminum packaging exterior. And the rectangular separator (composite film) was arrange | positioned so that the rectangular positive electrode might contact on the surface of the rectangular positive electrode on the positive electrode mixture layer side. Moreover, the rectangular negative electrode was arrange | positioned on the separator (composite film) so that the surface of the negative electrode mixture layer side may face the separator (composite film). Next, the electrolyte solution (solvent (volume ratio): ethylene carbonate (EC) / ethyl methyl carbonate (EMC) / vinylene carbonate (VC) = 68.5 / 30 / 1.5, electrolyte: LiPF _{6 with a} concentration of 1 M) so that no air remains. Injected. Further, a 150 ° C. heat seal was used to close the aluminum packaging exterior, thereby producing a lithium ion secondary battery.

Rate characteristics and cycle characteristics were evaluated for this lithium ion secondary battery. The results are shown in Table 1-4.

(Example 26)

At the time of preparation of the slurry composition for the separator (composite membrane), 40 parts of "sodium hydrogen carbonate (1) as hydrogencarbonate (NaHCO ₃ (1), particle diameter 190 nm)" was referred to as "sodium hydrogen carbonate (1) as hydrogencarbonate (1) (NaHCO ₃ (1), 30 parts of particle diameters 190 nm), and 10 parts (equivalent to solid content) of alumina (Sumitomo Chemical Co., Ltd. product name "AKP30", particle diameter 300 nm) as nonelectroconductive particle ", it changed similarly to Example 25. Thus, a slurry composition for a separator (composite membrane), a separator (composite membrane), a negative electrode, a positive electrode, and a secondary battery were manufactured. And it evaluated similarly to Example 25. The results are shown in Table 1-4. In addition, the particle diameter of the nonelectroconductive particle was measured by the method similar to the particle diameter of the organic particle A mentioned above.

(Example 27)

At the time of preparation of the slurry composition for the separator (composite membrane), 40 parts of "sodium hydrogen carbonate (1) (NaHCO ₃ (1), particle size 190 nm) as a hydrogen carbonate salt" were referred to as "sodium hydrogen carbonate (2) (NaHCO) as a hydrogen carbonate salt". ₃ (2), particle size 50 nm) 40 parts "," Polymer O (particle size 190 nm) as a binder "is changed to" Polymer O (particle size 50 nm) as a binder ", and" Separator (composite film) ), And the slurry composition for a separator (composite film), a negative electrode, a positive electrode, and a secondary battery were produced like Example 25 except having performed as follows. And it evaluated similarly to Example 25. The results are shown in Table 1-4.

<Production of Separator (Composite Film)>

After immersing for 2 minutes in the slurry composition for separators (composite membrane) which prepared the separator base material (thickness: 12 micrometers, air permeability: 100 sec / 100 ccAir) made from polyethylene, it is taken out from the slurry composition, and the extra separator of the surface ( The slurry composition for composite membranes) was scraped off. Then, it dried for 1 minute in 50 degreeC oven, and manufactured the separator (composite film).

(Example 28)

At the time of preparation of the slurry composition for the separator (composite membrane), 40 parts of "sodium hydrogen carbonate (1) (NaHCO ₃ (1), particle size 190 nm) as a hydrogen carbonate salt" were referred to as "sodium hydrogen carbonate (2) (NaHCO) as a hydrogen carbonate salt". ₃ (2), particle size 50 nm) 40 parts ", and the same as in Example 25, except that" Polymer O (particle size 190 nm) "as a binder was changed to" Polymer O (particle size 50 nm) as a binder ". The slurry composition for a separator (composite film), the negative electrode, the positive electrode, and the secondary battery were produced. And it evaluated similarly to Example 25. The results are shown in Table 1-4.

(Example 29)

Separator (composite membrane) in the preparation of the slurry composition, "as the hydrogen carbonate of sodium hydrogen carbonate (2) (NaHCO ₃ (2)) 40 parts" a (NaHCO ₃ "as the hydrogen carbonates sodium hydrogen carbonate (2) (2) ) 40 parts) and 10 parts and alumina as a non-conductive particle (Nippon Aerosil, product name "AEROXIDE Alu65", particle size 25 nm) 30 parts (solid content equivalent) "except for changing to a separator similarly to Example 27, The slurry composition, the negative electrode, the positive electrode, and the secondary battery for (composite film) were manufactured. And it evaluated similarly to Example 27. The results are shown in Table 1-4.

(Example 30)

At the time of preparation of the slurry composition for the separator (composite film), 40 parts of "sodium bicarbonate (1) (NaHCO ₃ (1), particle size 190 nm) as a hydrogen carbonate""were referred to as" potassium hydrogen carbonate (1) (KHCO) as a hydrogen carbonate " ₃ (1), particle size 190 nm) 40 parts ", and the slurry composition for separators (composite film), the separator (composite film), the negative electrode, the positive electrode, and the secondary battery were produced like Example 25. . And it evaluated similarly to Example 25. The results are shown in Table 1-4.

(Example 31)

At the time of preparation of the slurry composition for the separator (composite membrane), 40 parts of "sodium hydrogen carbonate (2) (NaHCO ₃ (2), particle size 50 nm) as a hydrogen carbonate salt" were referred to as "potassium hydrogen carbonate (2) (KHCO) as a hydrogen carbonate salt". ₃ (2), particle size 50 nm) 40 parts "was prepared in the same manner as in Example 27 to prepare a slurry composition for a separator (composite membrane), a separator (composite membrane), a negative electrode, a positive electrode, and a secondary battery. . And it evaluated similarly to Example 27. The results are shown in Table 1-4.

(Comparative Example 6)

The separator for the the preparation of the (composite film), a slurry composition, except that do not use as the hydrogen carbonates sodium hydrogen carbonate _{(1) (NaHCO 3 (1} )), in the same manner as in Example 25, the separator (composite film) The slurry composition, the separator (composite film), the negative electrode, the positive electrode, and the secondary battery were manufactured. And it evaluated similarly to Example 25. The results are shown in Table 1-4.

(Comparative Example 7)

The separator for the the preparation of the (composite film), a slurry composition, except that do not use as the hydrogen carbonates sodium hydrogen carbonate _{(2) (NaHCO 3 (2} )), in the same manner as in Example 27, the separator (composite film) The slurry composition, the separator (composite film), the negative electrode, the positive electrode, and the secondary battery were manufactured. And it evaluated similarly to Example 27. The results are shown in Table 1-4.

Table 1-1

TABLE 1-2

Table 1-3

Table 1-4

From Table 1-1 and Table 1-2, in Examples 1-21 using the binder composition containing a specific binder and a hydrogen carbonate, the rate characteristic of a secondary battery, exhibiting the outstanding adhesiveness (fill strength) to a functional layer, And it turns out that a cycle characteristic can be improved.

On the other hand, from Table 1-2, in Comparative Example 1 using a binder composition containing a specific binder but not containing a hydrogen carbonate, the rate characteristics of the secondary battery while exhibiting excellent adhesion (fill strength) to the functional layer and It can be seen that the cycle characteristics cannot be improved. Moreover, from Table 1-2, in the comparative example 2 using the binder composition which contains a hydrogen carbonate but does not contain a specific binder, the rate characteristic of a secondary battery, and exhibiting the outstanding adhesiveness (fill strength) to a functional layer, It can be seen that the cycle characteristics cannot be improved.

From Tables 1-3, in Examples 22 to 24 using a binder composition containing a specific binder, a specific hydrogen carbonate, and specific organic particles, excellent adhesion to the adhesive layer (fill strength, It can be seen that the rate characteristics and cycle characteristics of the secondary battery can be improved while exhibiting process adhesion).

From Tables 1-4, in Examples 25 to 31 using a binder composition containing a specific binder and a specific hydrogen carbonate salt, excellent adhesion (fill strength) to the composite membrane was exhibited while exhibiting slurry stability in the slurry composition, It can be seen that the composite membrane can exhibit an excellent air permeability and also improve the rate characteristics and cycle characteristics of the secondary battery.

[Industry availability]

According to the present invention, a functional layer (electrode mixture layer, porous membrane layer, adhesive layer) or (composite membrane) capable of improving the rate characteristics and cycle characteristics of an electrochemical device (for example, a secondary battery) while excellent in binding property ) Can be provided a binder composition for an electrochemical device.

Moreover, according to this invention, the functional layer (electrode mixture layer) which has the outstanding adhesiveness (fill strength, process adhesiveness), and can improve the rate characteristic and cycling characteristics of an electrochemical element (for example, a secondary battery). , Porous membrane layer, adhesive layer) or (composite membrane) can be provided a slurry composition for an electrochemical device functional layer.

The present invention also provides a (composite film) having excellent adhesion (fill strength, process adhesion) and capable of improving rate characteristics and cycle characteristics of an electrochemical device (for example, a secondary battery). Can be.

Claims (9)

Including a binder and hydrogen carbonate,
The binder composition for electrochemical elements which the said binder is a polymer which has a functional group selected from the group which consists of a carboxyl group, a hydroxyl group, a cyano group, an amino group, an epoxy group, an oxazoline group, an isocyanate group, and a sulfonic acid group. The method of claim 1,
The binder composition for electrochemical elements whose content of the said hydrogen carbonate is 5 mass% or more and 85 mass% or less with respect to the said binder. The method according to claim 1 or 2,
The binder comprises at least one of a carboxyl group and a cyano group,
The sum total of content of the carboxyl group in the said binder and content of the cyano group in the said binder is 0.1 mmol or more and 50 mmol or less per 1 g of said binders. The method according to any one of claims 1 to 3,
The binder contains a cyano group,
The binder composition for electrochemical elements whose content of the cyano group in the said binder is 1 mmol or more and 40 mmol or less per 1 g of said binders. The slurry composition for electrochemical element functional layers containing the binder composition for electrochemical elements as described in any one of Claims 1-4. The method of claim 5,
Slurry composition for electrochemical element functional layers containing an electrode active material further. Including the binder composition for electrochemical elements as described in any one of Claims 1-4,
The slurry composition for electrochemical element adhesive layers which does not contain an electrode active material and nonelectroconductive particle. The method of claim 5,
A slurry composition for an electrochemical device functional layer, further comprising non-conductive particles. The composite film which laminated | stacked the separator composition of Claim 5 or 8 on the separator base material, or was introduce | transduced in the separator base material.