JP5928712B2 - Binder composition for lithium ion secondary battery electrode, slurry for lithium ion secondary battery electrode, method for producing lithium ion secondary battery electrode, and method for producing lithium ion secondary battery - Google Patents

Description

  The present invention relates to an electrode binder composition, an electrode slurry containing the binder composition and an electrode active material, an electrode prepared by applying and drying the slurry on a current collector, and an electricity storage device including the electrode About.

  In recent years, a power storage device having a high voltage and a high energy density has been required as a power source for driving electronic equipment. In particular, lithium ion batteries and lithium ion capacitors are expected as power storage devices having high voltage and high energy density.

  The electrode used for such an electricity storage device is usually produced by applying and drying a mixture of an electrode active material and polymer particles functioning as a binder onto the surface of the current collector. The properties required for the polymer particles include the ability to bind electrode active materials and the ability to bind the electrode active material and the current collector, the abrasion resistance in the process of winding the electrode, and subsequent cutting. Examples thereof include powder-off resistance in which fine powder of the electrode active material is not generated from the applied electrode composition layer (hereinafter also simply referred to as “electrode active material layer”). When the polymer particles satisfy these various required characteristics, the degree of freedom in designing the structure of the electricity storage device, such as the method of folding the obtained electrode and setting the winding radius, is increased, and the miniaturization of the device is achieved. Can do. In addition, as for the bonding ability between the electrode active materials and the adhesion ability between the electrode active material layer and the current collector, and the powder fall resistance, it has been empirically revealed that the performance is almost proportional. . Therefore, in the present specification, hereinafter, the term “adhesiveness” may be used in a comprehensive manner.

  As a binder for electrodes, when producing a positive electrode, it is advantageous to use a fluorine-containing organic polymer which is slightly inferior in adhesiveness such as polyvinylidene fluoride but excellent in oxidation resistance. On the other hand, when producing a negative electrode, it is advantageous to use a (meth) acrylic acid polymer which is slightly inferior in oxidation resistance but excellent in adhesion.

  Various techniques for improving characteristics such as oxidation resistance and adhesion of the polymer used in the electrode binder as described above have been studied and proposed. For example, Patent Document 1 proposes a technique for making both the oxidation resistance and adhesion of a negative electrode binder compatible by using polyvinylidene fluoride and a rubber-based polymer in combination. Patent Document 2 discloses a technique for improving adhesion by dissolving polyvinylidene fluoride in a specific organic solvent, applying it onto the current collector surface, and then removing the solvent at a low temperature. Has been proposed. Further, Patent Document 3 proposes a technique for improving adhesion by applying a binder for an electrode having a side chain having a fluorine atom to a main chain made of a vinylidene fluoride copolymer. ing.

  Furthermore, a technique for improving the above characteristics by controlling the binder composition (see Patent Document 4) and a technique for improving the above characteristics using a binder having an epoxy group or a hydroxyl group (see Patent Documents 5 and 6) are proposed. Has been.

  On the other hand, in order to use the binder composition in an actual production line, it is necessary to store the electrode binder composition for a long period of time in a warehouse or the like, in addition to the above characteristics. Even in such long-term storage, it is necessary that the binder composition for an electrode does not deteriorate due to, for example, precipitation of the polymer. As techniques for improving such storage stability, Patent Documents 7 and 8 disclose a method using an isothiazoline compound.

JP 2011-3529 A JP 2010-55847 A JP 2002-42819 A JP 2000-299109 A JP 2010-205722 A JP 2010-3703 A International Publication No. 2012/002451 Pamphlet JP 2012-9775 A

  However, according to the technique of Patent Document 1 in which a fluorine-containing organic polymer and a rubber polymer are used in combination, although the adhesion is improved, the oxidation resistance of the organic polymer is greatly impaired. However, there is a problem that the charge / discharge characteristics are irreversibly deteriorated by repeated charge / discharge. On the other hand, according to the techniques of Patent Documents 2 and 3 using only a fluorine-containing organic polymer as an electrode binder, the level of adhesion is still insufficient.

  In addition, in the binder composition as in Patent Documents 4 and 5, although the adhesion is improved, the binder itself attached to the electrode active material becomes a resistance component of the electrode, and it is difficult to maintain good charge / discharge characteristics for a long time. there were.

  Further, Patent Documents 7 and 8 evaluate the antiseptic property of the binder composition containing the isothiazoline-based compound, and as a result, it has been clarified that the storage stability is effective. However, Patent Documents 7 and 8 merely evaluate the superiority and inferiority of the electricity storage device produced by using the binder composition immediately after preparation, and are most important for practical use for long-term storage. No study has been made on the characteristics of the electricity storage device produced using the binder composition after the treatment. That is, Patent Documents 7 and 8 are merely evaluated with respect to the storage stability of the polymer particle dispersion, and it is possible to produce an electricity storage device exhibiting good characteristics using the composition after long-term storage. The long term storage stability as an “electrode” binder composition remains unclear.

  Accordingly, some aspects of the present invention provide an electrode having excellent storage stability over a long period of time by solving the above-described problems, and excellent adhesion and charge / discharge characteristics even when stored for a long period of time. The binder composition for electrodes which can manufacture is provided.

  SUMMARY An advantage of some aspects of the invention is to solve at least a part of the problems described above, and the invention can be implemented as the following aspects or application examples.

[Application Example 1]
One aspect of the binder composition for electrodes according to the present invention is:
A binder composition for producing an electrode used in an electricity storage device,
A polymer (A), an isothiazoline-based compound (B), and a liquid medium (C),
The polymer (A) is
A repeating unit (Ma) derived from a fluorine-containing ethylene monomer;
A repeating unit (Mb) derived from an unsaturated carboxylic acid ester;
It is the fluorine-containing polymer particle which has this.

[Application Example 2]
In the binder composition for electrodes of Application Example 1,
When differential scanning calorimetry (DSC) is performed on the fluorine-containing polymer particles in accordance with JIS K7121, only one endothermic peak in the temperature range of −50 to + 250 ° C. can be observed.

[Application Example 3]
In the binder composition for electrodes of Application Example 2,
The endothermic peak can be observed in a temperature range of −30 to + 30 ° C.

[Application Example 4]
In the electrode binder composition of any one of Application Examples 1 to 3,
The concentration of the compound (B) in the binder composition may be 50 to 1,500 ppm.

（式（１）中、Ｒ^１は水素原子または炭化水素基を表し、Ｒ^２およびＲ^３はそれぞれ水素原子、ハロゲン原子または炭化水素基を表す。）

（式（２）中、Ｒ^４は水素原子または炭化水素基を表し、Ｒ^５はそれぞれ独立に水素原子または有機基を表す。ｎは０〜４の整数を表す。） [Application Example 5]
In the electrode binder composition of any one of Application Examples 1 to 4,
The compound (B) may be at least one selected from the group consisting of a compound represented by the following general formula (1) and a compound represented by the following general formula (2).

(In formula (1), R ¹ represents a hydrogen atom or a hydrocarbon group, and R ² and R ³ each represent a hydrogen atom, a halogen atom or a hydrocarbon group.)

(In formula (2), R ⁴ represents a hydrogen atom or a hydrocarbon group, R ⁵ each independently represents a hydrogen atom or an organic group, and n represents an integer of 0 to ^4. )

[Application Example 6]
In the electrode binder composition of any one of Application Examples 1 to 5,
The number average particle diameter of the fluorine-containing polymer particles may be 50 to 400 nm.

[Application Example 7]
One aspect of the slurry for electrodes according to the present invention is:
It contains the binder composition for electrodes of any one example of the application example 1 thru | or the application example 6, and an electrode active material, It is characterized by the above-mentioned.

[Application Example 8]
One aspect of the electrode according to the present invention is:
It is characterized by comprising: a current collector; and a layer formed by applying and drying the electrode slurry of Application Example 7 on the surface of the current collector.

[Application Example 9]
One aspect of the electricity storage device according to the present invention is:
The electrode of Application Example 8 is provided.

  According to the binder composition for an electrode according to the present invention, an electrode having excellent storage stability over a long period of time and excellent adhesion and charge / discharge characteristics even when stored for a long period of time can be produced. An electricity storage device including an electrode manufactured using the binder composition for an electrode according to the present invention has extremely good charge / discharge rate characteristics, which is one of electrical characteristics.

4 is a DSC chart of polymer particles obtained in Example 3. FIG.

  Hereinafter, preferred embodiments according to the present invention will be described in detail. It should be understood that the present invention is not limited only to the embodiments described below, and includes various modified examples that are implemented without departing from the scope of the present invention. In the present specification, “(meth) acrylic acid” is a concept encompassing both “acrylic acid” and “methacrylic acid”. Further, “˜ (meth) acrylate” is a concept encompassing both “˜acrylate” and “˜methacrylate”.

1. Electrode Binder Composition The electrode binder composition according to the present embodiment is a binder composition for producing an electrode used in an electricity storage device, and comprises a polymer (A) and an isothiazoline compound (B). And a liquid medium (C). Hereinafter, each component contained in the binder composition for electrodes which concerns on this Embodiment is demonstrated in detail.

1.1. Polymer (A)
The polymer (A) contained in the electrode binder composition according to the present embodiment is preferably in a latex form dispersed as particles in the liquid medium (C). It is preferable that the electrode binder composition is in a latex form, because the stability of the electrode slurry prepared by mixing with the electrode active material becomes good and the applicability of the electrode slurry to the current collector becomes good. . Hereinafter, the polymer (A) dispersed as particles in the liquid medium (C) is referred to as “polymer particles (A)”.

  As the polymer particles (A), commercially available latexes may be used. When the electrode binder composition according to the present embodiment is used for producing a positive electrode, the polymer particles (A) are preferably fluorine-containing polymer particles described below.

  The fluorine-containing polymer particles have a repeating unit (Ma) derived from a fluorine-containing ethylene monomer and a repeating unit (Mb) derived from an unsaturated carboxylic acid ester. The fluorine-containing polymer particles include a polymer (Aa) having a repeating unit (Ma) derived from a fluorine-containing ethylene monomer and a polymer having a repeating unit (Mb) derived from an unsaturated carboxylic acid ester. It is preferable that the polymer alloy particles have (Ab).

  “Polymer alloy” is a “generic name for multi-component polymers obtained by mixing or chemical bonding of two or more components” according to the definition in “Iwanami Physical and Chemical Dictionary 5th edition. Iwanami Shoten”. “Polymer blends physically mixed with different polymers, block and graft copolymers in which different polymer components are covalently bonded, polymer complexes in which different polymers are associated by intermolecular forces, and different polymers entangled with each other IPN (Interpenetrating Polymer Network) etc. ". However, the polymer alloy particles that can be contained in the electrode binder composition of the present invention are those called IPN (interpenetrating polymer network) among “polymer alloys in which different types of polymer components are not bonded by covalent bonds”. It is the particle which consists of.

  When the fluorine-containing polymer particles are polymer alloy particles, the polymer (Aa) having a repeating unit (Ma) derived from the fluorine-containing ethylene monomer has a main segment of crystalline resin aggregated, It is considered that the chain is given a pseudo-crosslinking point such as C—H... F—C. For this reason, when a polymer (Aa) is used alone as a binder resin, its oxidation resistance is good, but adhesion and flexibility are insufficient. On the other hand, the polymer (Ab) having a repeating unit (Mb) derived from an unsaturated carboxylic acid ester is excellent in adhesion and flexibility but has low oxidation resistance. When it is used for the above, good charge / discharge characteristics cannot be obtained because it undergoes oxidative decomposition and alteration due to repeated charge / discharge.

  However, by using polymer alloy particles having a polymer (Aa) and a polymer (Ab), oxidation resistance and adhesion can be expressed at the same time, and a positive electrode exhibiting better charge / discharge characteristics can be obtained. Can be manufactured. In addition, when a polymer alloy particle has a polymer (Aa) and a polymer (Ab), oxidation resistance can also be improved further.

  Hereinafter, each repeating unit constituting the fluorine-containing polymer particle will be described.

（一般式（３）中、Ｒ^６は水素原子またはメチル基であり、Ｒ^７はフッ素原子を含有する炭素数１〜１８の炭化水素基である。） 1.1.1. Repeating units derived from fluorine-containing ethylene monomers (Ma)
As described above, the fluorine-containing polymer particles used in the present embodiment have a repeating unit (Ma) derived from a fluorine-containing ethylene monomer. Examples of the fluorine-containing ethylene monomer include olefin compounds having fluorine atoms and (meth) acrylate compounds having fluorine atoms. Examples of the olefin compound having a fluorine atom include vinylidene fluoride, tetrafluoroethylene, hexafluoropropylene, ethylene trifluoride chloride, and perfluoroalkyl vinyl ether. As the (meth) acrylate compound having a fluorine atom, for example, a compound represented by the following general formula (3), (meth) acrylic acid 3 [4 [1-trifluoromethyl-2,2-bis [bis (trifluoro) Methyl) fluoromethyl] ethynyloxy] benzooxy] 2-hydroxypropyl and the like.

(In General Formula (3), R ⁶ is a hydrogen atom or a methyl group, and R ⁷ is a C 1-18 hydrocarbon group containing a fluorine atom.)

Examples of R ⁷ in the general formula (3) include a fluorinated alkyl group having 1 to 12 carbon atoms, a fluorinated aryl group having 6 to 16 carbon atoms, and a fluorinated aralkyl group having 7 to 18 carbon atoms. Of these, a fluorinated alkyl group having 1 to 12 carbon atoms is preferable. Preferable specific examples of R ^{7 in} the general formula (3) include, for example, 2,2,2-trifluoroethyl group, 2,2,3,3,3-pentafluoropropyl group, 1,1,1, 3,3,3-hexafluoropropan-2-yl group, β- (perfluorooctyl) ethyl group, 2,2,3,3-tetrafluoropropyl group, 2,2,3,4,4,4- Hexafluorobutyl group, 1H, 1H, 5H-octafluoropentyl group, 1H, 1H, 9H-perfluoro-1-nonyl group, 1H, 1H, 11H-perfluoroundecyl group, perfluorooctyl group and the like can be mentioned. .

  Of these, the fluorine-containing ethylene monomer is preferably an olefin compound having a fluorine atom, and more preferably at least one selected from the group consisting of vinylidene fluoride, tetrafluoroethylene and hexafluoropropylene. preferable. Said fluorine-containing ethylene-type monomer may be used individually by 1 type, and 2 or more types may be mixed and used for it.

  In general, a fluorinated polymer component having a repeating unit (Ma) derived from a fluorine-containing ethylene-based monomer is considered to have good oxidation resistance and has been conventionally used in a positive electrode binder composition. Although there was a thing, such a fluorinated polymer component was inferior to adhesiveness. Therefore, in the prior art, studies have been made to improve the adhesion of the fluorinated polymer by various modifications. However, for example, an attempt to improve adhesion by introducing a functional group into a polymer chain requires precise control of the polymer synthesis conditions, and it has been difficult to achieve the object.

  In the present invention, by using fluorine-containing polymer particles having a repeating unit (Ma) derived from a fluorine-containing ethylene monomer and a repeating unit (Mb) derived from an unsaturated carboxylic acid ester. It is possible to develop adhesion without deteriorating oxidation resistance. Further, the fluorine-containing polymer particles have a polymer (Aa) having a repeating unit (Ma) derived from a fluorine-containing ethylene-based monomer, and a polymer having a repeating unit (Mb) derived from an unsaturated carboxylic acid ester. By using it as a polymer alloy particle having a combination (Ab), adhesion can be expressed more effectively without degrading oxidation resistance.

  When the fluorine-containing polymer particles are polymer alloy particles, the polymer (Aa) may have only a repeating unit (Ma) derived from the fluorine-containing ethylene monomer, and the fluorine-containing ethylene single particles You may have the repeating unit derived from the copolymerizable unsaturated monomer other than the repeating unit (Ma) derived from a monomer. Examples of such other unsaturated monomers include alkyl esters of unsaturated carboxylic acids, cycloalkyl esters of unsaturated carboxylic acids, hydrophilic monomers, crosslinkable monomers, α-olefins, and hydroxyl groups. Compounds (excluding those corresponding to the aforementioned hydrophilic monomers and crosslinkable monomers; the same shall apply hereinafter) and the like, and one or more selected from these may be used. it can.

  Examples of the alkyl ester of the unsaturated carboxylic acid include methyl (meth) acrylate, ethyl (meth) acrylate, n-propyl (meth) acrylate, i-propyl (meth) acrylate, and (meth) acrylic acid n. -Butyl, i-butyl (meth) acrylate, n-amyl (meth) acrylate, i-amyl (meth) acrylate, hexyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, (meth) acryl N-octyl acid, nonyl (meth) acrylate, decyl (meth) acrylate, and the like. Examples of the unsaturated carboxylic acid cycloalkyl ester include cyclohexyl (meth) acrylate, and the like. One or more selected from among them can be used.

Examples of the hydrophilic monomer include unsaturated carboxylic acids, hydroxyalkyl esters of unsaturated carboxylic acids, polyhydric alcohol esters of unsaturated carboxylic acids, α, β-unsaturated nitrile compounds, and compounds having a hydroxyl group. be able to. Examples of the unsaturated carboxylic acid include (meth) acrylic acid, crotonic acid, maleic acid, fumaric acid, itaconic acid and the like;
Examples of the hydroxyalkyl ester of the unsaturated carboxylic acid include hydroxymethyl (meth) acrylate and hydroxyethyl (meth) acrylate;
Examples of the polyhydric alcohol ester of the unsaturated carboxylic acid include (meth) acrylic acid ethylene glycol;
Examples of the crosslinkable monomer include ethylene glycol di (meth) acrylate, propylene glycol di (meth) acrylate, trimethylolpropane tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, and hexa (meth). Dipentaerythritol acrylate, etc .;
Examples of the α, β-unsaturated nitrile compound include acrylonitrile, methacrylonitrile, α-chloroacrylonitrile, α-ethylacrylonitrile, vinylidene cyanide and the like;
Examples of the compound having a hydroxyl group include p-hydroxystyrene, and one or more selected from these compounds can be used.

  Since the polymer (Aa) has the structural unit derived from the unsaturated carboxylic acid among the above, the dispersion stability of the electrode slurry used when producing the electrode active material layer is improved. And a homogeneous electrode active material layer in which the fluorine-containing polymer particles are not unevenly distributed locally can be produced. As a result, it becomes an electrode active material layer that is homogeneous in strength and electricality, and the electrode active material layer is locally peeled off from the current collector, or the electrode active material and binder are unevenly distributed to locally concentrate the potential. It is preferable at the point which can suppress electrode deterioration by doing effectively.

  The content ratio of the repeating unit (Ma) derived from the fluorine-containing ethylene-based monomer in the polymer (Aa) is preferably 80% by mass or more, more preferably based on the total mass of the polymer (Aa). 90% by mass or more.

  When a polymer (Aa) contains the repeating unit derived from vinylidene fluoride, the content rate becomes like this. Preferably it is 50-99 mass%, More preferably, it is 80-98 mass%. When a polymer (Aa) contains the repeating unit derived from ethylene tetrafluoride, the content rate becomes like this. Preferably it is 1-50 mass%, More preferably, it is 2-20 mass%. When a polymer (Aa) contains the repeating unit derived from a hexafluoropropylene, the content rate becomes like this. Preferably it is 1-50 mass%, More preferably, it is 2-20 mass%.

  The polymer (Aa) can be easily produced by emulsion polymerization of the above fluorine-containing ethylene monomer and optionally another unsaturated monomer according to a known method.

1.1.2. Repeating units derived from unsaturated carboxylic acid esters (Mb)
As described above, the fluorine-containing polymer particles used in the present embodiment have a repeating unit (Mb) derived from an unsaturated carboxylic acid ester. In general, a polymer having a repeating unit (Mb) derived from an unsaturated carboxylic acid ester is considered to have good adhesion but poor oxidation resistance and has been conventionally used for a positive electrode. Was not. However, the present invention uses fluorine-containing polymer particles having a repeating unit (Ma) derived from a fluorine-containing ethylene monomer and a repeating unit (Mb) derived from an unsaturated carboxylic acid ester. Thus, it has succeeded in developing sufficient oxidation resistance while maintaining good adhesion.

  The unsaturated carboxylic acid ester is preferably a (meth) acrylate compound. Specific examples of such (meth) acrylate compounds include, for example, methyl (meth) acrylate, ethyl (meth) acrylate, n-propyl (meth) acrylate, i-propyl (meth) acrylate, (meth) N-butyl acrylate, i-butyl (meth) acrylate, n-amyl (meth) acrylate, i-amyl (meth) acrylate, hexyl (meth) acrylate, cyclohexyl (meth) acrylate, (meth) 2-ethylhexyl acrylate, n-octyl (meth) acrylate, nonyl (meth) acrylate, decyl (meth) acrylate, hydroxymethyl (meth) acrylate, hydroxyethyl (meth) acrylate, (meth) acrylic acid Ethylene glycol, ethylene glycol di (meth) acrylate, propylene glycol di (meth) acrylate , Trimethylolpropane tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, dipentaerythritol hexa (meth) acrylate, allyl (meth) acrylate, ethylene di (meth) acrylate, etc. It can be one or more selected from these. Of these, one or more selected from methyl (meth) acrylate, ethyl (meth) acrylate and 2-ethylhexyl (meth) acrylate is preferable, and methyl (meth) acrylate is particularly preferable. preferable.

  When the fluorine-containing polymer particles are polymer alloy particles, the polymer (Ab) may be a polymer having only a repeating unit (Mb) derived from an unsaturated carboxylic acid ester, or an unsaturated carboxylic acid ester. In addition to the repeating unit derived from (Mb), it may have a structural unit derived from another copolymerizable unsaturated monomer.

  The content ratio of the repeating unit (Mb) derived from the unsaturated carboxylic acid ester in the polymer (Ab) is preferably 65% by mass or more, more preferably 75% by mass with respect to the total mass of the polymer (Ab). % Or more.

  Examples of the other unsaturated monomer include α, β-unsaturated nitrile compounds such as acrylonitrile, methacrylonitrile, α-chloroacrylonitrile, α-ethylacrylonitrile, vinylidene cyanide; acrylic acid, methacrylic acid, croton Unsaturated carboxylic acids such as acid, maleic acid, fumaric acid and itaconic acid; 1,3-butadiene, 2-methyl-1,3-butadiene, 2,3-dimethyl-1,3-butadiene, 2-chloro-1 Conjugated diene compounds such as 1,3-butadiene; aromatic vinyl compounds such as styrene, α-methylstyrene, p-methylstyrene, vinyltoluene, chlorostyrene, divinylbenzene, and other unsaturated monomers. , One or more selected from these.

1.1.3. Preparation of fluorinated polymer particles As long as the fluorinated polymer particles have the above-described configuration, the synthesis method is not particularly limited. For example, a known emulsion polymerization step or a combination thereof is appropriately combined. Can be easily synthesized.

For example, first, a polymer (Aa) having a repeating unit (Ma) derived from a fluorine-containing ethylene monomer is synthesized by a known method. Next, a monomer for constituting the polymer (Ab) is added to the polymer (Aa), and the monomer is sufficiently absorbed into the stitch structure of the polymer particles containing the polymer (Aa). Thereafter, the fluorine-containing polymer particles can be easily produced by a method of synthesizing the polymer (Ab) by polymerizing monomers absorbed in the stitch structure of the polymer (Aa). When polymer alloy particles are produced by such a method, it is essential that the polymer (Aa) sufficiently absorb the monomer of the polymer (Ab). When the absorption temperature is too low or when the absorption time is too short, only a part of the core-shell particle or the surface layer becomes a particle having an IPN type structure, and the fluorine-containing polymer particle in the present invention may not be obtained. Many. However, if the absorption temperature is too high, the pressure of the polymerization system becomes too high, which is disadvantageous in terms of reaction system handling and reaction control, and even if the absorption time is excessively long, further advantageous results are not obtained. .

  From the above viewpoint, the absorption temperature is preferably 30 to 100 ° C., more preferably 40 to 80 ° C .; the absorption time is preferably 1 to 12 hours, and preferably 2 to 8 hours. It is more preferable. At this time, it is preferable to lengthen the absorption time when the absorption temperature is low, and a short absorption time is sufficient when the absorption temperature is high. The conditions are such that the value obtained by multiplying the absorption temperature (° C.) and the absorption time (h) is generally in the range of 120 to 300 (° C. · h), preferably 150 to 250 (° C. · h).

  The operation of absorbing the monomer of the polymer (Ab) in the stitch structure of the polymer (Aa) is preferably performed in a known solvent used for emulsion polymerization, for example, in water.

  The content of the polymer (Aa) in the fluorinated polymer particles is preferably 1 to 60 parts by mass and more preferably 5 to 55 parts by mass in 100 parts by mass of the fluorinated polymer particles. Preferably, it is 10-50 mass parts, More preferably, it is 20-40 mass parts. When the fluorine-containing polymer particles contain the polymer (Aa) in the above range, the balance between oxidation resistance and adhesion becomes better.

  Production of the fluorine-containing polymer particles of the present invention, that is, polymerization of the polymer (Aa) or polymerization of the polymer (Ab) performed after the monomer is absorbed in the obtained polymer (Aa), or these Both of them can be carried out in the presence of a known emulsifier (surfactant), a polymerization initiator, a molecular weight modifier and the like.

  Specific examples of emulsifiers include, for example, sulfate esters of higher alcohols, alkylbenzene sulfonates, alkyl diphenyl ether disulfonates, aliphatic sulfonates, aliphatic carboxylates, dehydroabietic acid salts, naphthalene sulfonic acid / formalin condensates. Anionic surfactants such as sulfate salts of nonionic surfactants; nonionic surfactants such as alkyl esters of polyethylene glycol, alkyl phenyl ethers of polyethylene glycol, and alkyl ethers of polyethylene glycol; perfluorobutyl sulfonic acid Fluorosurfactants such as salts, perfluoroalkyl group-containing phosphate esters, perfluoroalkyl group-containing carboxylates, perfluoroalkylethylene oxide adducts, etc. It is possible to use one or more selected from among these.

  Specific examples of the polymerization initiator include water-soluble polymerization initiators such as lithium persulfate, potassium persulfate, sodium persulfate, and ammonium persulfate; cumene hydroperoxide, benzoyl peroxide, t-butyl hydroperoxide, and acetyl peroxide. Oil-soluble polymerization initiators such as oxide, diisopropylbenzene hydroperoxide, 1,1,3,3-tetramethylbutyl hydroperoxide, azobisisobutyronitrile, 1,1′-azobis (cyclohexanecarbonitrile), etc. It can be appropriately selected and used. Of these, potassium persulfate, sodium persulfate, cumene hydroperoxide or t-butyl hydroperoxide is particularly preferably used. The use ratio of the polymerization initiator is not particularly limited, but is appropriately set in consideration of the monomer composition, the pH of the polymerization reaction system, a combination of other additives, and the like.

Specific examples of the molecular weight regulator include alkyl mercaptans such as n-hexyl mercaptan, n-octyl mercaptan, t-octyl mercaptan, n-dodecyl mercaptan, t-dodecyl mercaptan, n-stearyl mercaptan; dimethylxanthogen disulfide, diisopropyl Xanthogen compounds such as xanthogen disulfide; thiuram compounds such as terpinolene, tetramethylthiuram disulfide, tetraethylthiuram disulfide, tetramethylthiuram monosulfide; phenols such as 2,6-di-t-butyl-4-methylphenol and styrenated phenol Compounds; allyl compounds such as allyl alcohol; halogenated hydrocarbon compounds such as dichloromethane, dibromomethane, and carbon tetrabromide; In addition to vinyl ether compounds such as ziroxystyrene, α-benzyloxyacrylonitrile, α-benzyloxyacrylamide, etc., triphenylethane, pentaphenylethane, acrolein, methacrolein, thioglycolic acid, thiomalic acid, 2-ethylhexylthioglycolate, (alpha) -methylstyrene dimer etc. can be mentioned and 1 or more types selected from these can be used.

1.1.4. Physical properties of polymer particles (A) 1.1.4.1. Tetrahydrofuran (THF) Insoluble Content The THF insoluble content of the polymer particles (A) is preferably 80% or more, and more preferably 90% or more. The THF-insoluble content is estimated to be approximately proportional to the amount of insoluble content in the electrolytic solution used in the electricity storage device. For this reason, if the THF-insoluble content is in the above range, it is presumed that it is favorable because an electricity storage device is produced and elution of the polymer (A) into the electrolytic solution can be suppressed even when charging and discharging are repeated for a long period of time. it can.

1.1.4.2. Transition temperature When the polymer particles (A) are fluorine-containing polymer particles, the endothermic peak is 1 in the temperature range of −50 to 250 ° C. when measured by differential scanning calorimetry (DSC) according to JIS K7121. It is preferable that it has only one. The temperature of this endothermic peak is more preferably in the range of -30 to + 30 ° C. When the temperature of only one endothermic peak of the fluorine-containing polymer particles is in the range of −30 to + 30 ° C., the particles have better flexibility and adhesion to the electrode active material layer. It is preferable in that it can be imparted and, therefore, the adhesion can be further improved.

  In the case where the polymer (Aa) is present alone, it generally has an endothermic peak (melting temperature) at -50 to 250 ° C. The polymer (Ab) generally has an endothermic peak (glass transition temperature) different from that of the polymer (Aa). For this reason, when the polymer (Aa) and the polymer (Ab) in the particles are present in phase separation as in, for example, a core-shell structure, two endothermic peaks should be observed at −50 to 250 ° C. It is. However, when there is only one endothermic peak at −50 to 250 ° C., it indicates that the polymer (Aa) and the polymer (Ab) exist without phase separation, and the particles Can be presumed to be polymer alloy particles.

1.1.4.3. Number average particle diameter The number average particle diameter of the polymer particles (A) is preferably in the range of 50 to 400 nm, and more preferably in the range of 100 to 250 nm. When the number average particle diameter of the polymer particles (A) is in the above range, the polymer particles (A) can be sufficiently adsorbed on the surface of the electrode active material. The particles (A) can also follow and move. As a result, it is possible to suppress only one of the two particles from migrating alone, thereby suppressing deterioration of electrical characteristics.

The number average particle diameter of the polymer particles (A) is the accumulation of the number of particles when the particle size distribution is measured using a particle size distribution measuring apparatus based on the light scattering method and the particles are accumulated from small particles. This is the value of the particle diameter (D50) at which the frequency is 50%. Examples of such a particle size distribution measuring apparatus include Coulter LS230, LS100, LS13320 (above, manufactured by Beckman Coulter. Inc), FPAR-1000 (manufactured by Otsuka Electronics Co., Ltd.), and the like. These particle size distribution measuring devices are not intended to evaluate only the primary particles of the polymer particles, but can also evaluate the secondary particles formed by aggregation of the primary particles. Therefore, the particle size distribution measured by these particle size distribution measuring devices can be used as an indicator of the dispersion state of the polymer particles contained in the electrode slurry. The number average particle size of the polymer particles (A) is also measured by a method of centrifuging the electrode slurry and precipitating the electrode active material, and then measuring the supernatant with the above particle size distribution measuring apparatus. be able to.

1.2. Isothiazoline compounds (B)
The binder composition for electrodes according to the present embodiment contains an isothiazoline compound (B). By adding the isothiazoline compound (B) to the electrode binder composition, the isothiazoline compound (B) acts as a preservative, and when the electrode binder composition is stored, bacteria, sputum, etc. grow. Thus, the generation of foreign matters can be suppressed. Furthermore, since deterioration of the binder is suppressed during charging / discharging of the electricity storage device, it is possible to suppress a decrease in charge / discharge characteristics of the electricity storage device.

  The manifestation mechanism of the effect of suppressing the deterioration of the binder during charging / discharging of the electricity storage device is not clear, but is considered as follows. Since the affinity between the isothiazoline compound (B) and the polymer particles is good, the isothiazoline compound (B) is adsorbed by the polymer functioning as a binder even when the electrode active material layer is immersed in the electrolytic solution. It is considered that the electrode active material layer is hardly eluted into the electrolyte solution. By holding the isothiazoline-based compound (B) in the polymer, the deterioration of the polymer functioning as a binder due to the electrolytic solution is suppressed and the alteration of the electrolytic solution itself is also suppressed. As a result, the charge / discharge characteristics are not deteriorated. It is guessed.

  In general, when a new component is added to a dispersion of polymer particles such as latex, the new component triggers and aggregation tends to occur. However, since the isothiazoline-based compound (B) has little influence on the dispersibility of the polymer particles, the generation of aggregates can be suppressed. Therefore, since there is no component that triggers when the electrode binder composition of the present invention and the electrode active material are mixed to produce an electrode slurry, the aggregation of the polymer particles and the electrode active material can be suppressed. it can. Therefore, an electrode in which a homogeneous electrode active material layer is formed on the surface of the current collector can be manufactured, and it is estimated that the charge / discharge characteristics of the electricity storage device are improved.

  Furthermore, it is considered that the fluidity of the electrode slurry can be improved by adding the isothiazoline compound (B) to the electrode binder composition. As a result of improving the fluidity of the electrode slurry, it is possible to form an electrode active material layer with a more uniform thickness, and even when charging / discharging at a high rate, a uniform voltage is applied to the entire surface of the electrode active material layer. Therefore, it is considered that stable charge / discharge characteristics can be expressed.

  The concentration of the isothiazoline-based compound (B) in the electrode binder composition is preferably 50 to 1,500 ppm, more preferably 50 to 1,200 ppm, and particularly preferably 50 to 1,000 ppm. preferable. When the concentration of the isothiazoline-based compound (B) in the electrode binder composition is in the above range, the storage stability of the electrode binder composition over a long period of time is improved, and an electrode slurry produced using the slurry. An electricity storage device including an electrode produced by further applying a sucrose to a current collector exhibits good charge / discharge characteristics.

In addition, when the concentration of the component (B) is less than the above range, the above-described effects cannot be sufficiently exhibited, and a power storage device that exhibits good charge / discharge characteristics particularly when stored for a long period of time is manufactured. There are cases where it is not possible. When the concentration of the component (B) exceeds the above range, a large amount of the component (B) is adsorbed on the surface of the polymer particles, the binding force of the polymer particles is reduced, and the current collector and the electrode active material layer Adhesiveness may deteriorate.

  The isothiazoline-based compound (B) contained in the electrode binder composition according to the present embodiment is not particularly limited as long as it is a compound having an isothiazoline skeleton, but is specifically represented by the following general formula (1). And compounds represented by the following general formula (2).

上記式（１）中、Ｒ^１は水素原子または炭化水素基であり、Ｒ^２、Ｒ^３はそれぞれ水素原子、ハロゲン原子または炭化水素基を表す。Ｒ^１、Ｒ^２、Ｒ^３が炭化水素基である場合、直鎖あるいは分岐鎖のような鎖状の炭素骨格を有していてもよく、環状の炭素骨格を有していてもよい。また、炭化水素基の炭素数は１〜１２であることが好ましく、１〜１０であることがより好ましく、１〜８であることが特に好ましい。このような炭化水素基の具体例としては、メチル基、エチル基、プロピル基、イソプロピル基、ブチル基、ヘキシル基、シクロヘキシル基、オクチル基、２−エチルヘキシル基等が挙げられる。

In said formula (1), R < ¹ > is a hydrogen atom or a hydrocarbon group, R < ² >, R < ³ > represents a hydrogen atom, a halogen atom, or a hydrocarbon group, respectively. When R ¹ , R ² and R ³ are hydrocarbon groups, they may have a linear or branched carbon skeleton, or may have a cyclic carbon skeleton. Moreover, it is preferable that carbon number of a hydrocarbon group is 1-12, it is more preferable that it is 1-10, and it is especially preferable that it is 1-8. Specific examples of such a hydrocarbon group include a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, a hexyl group, a cyclohexyl group, an octyl group, and a 2-ethylhexyl group.

上記式（２）中、Ｒ^４は水素原子または炭化水素基であり、Ｒ^５はそれぞれ独立に水素原子または有機基を表す。Ｒ^４が炭化水素基である場合、上記式（１）で説明した炭化水素基と同様の炭化水素基であることができる。また、Ｒ^５が有機基である場合、この有機基にはアルキル基やシクロアルキル基である脂肪族基や芳香族基が含まれるが、脂肪族基であることが好ましい。アルキル基の炭素数は１〜１２であることが好ましく、１〜１０であることがより好ましく、１〜８であることが特に好ましい。これらのアルキル基およびシクロアルキル基は、ハロゲン原子、アルコキシル基、ジアルキルアミノ基、アシル基、アルコキシカルボニル基等の置換基を有していてもよい。前記脂肪族基の具体例としては、メチル基、エチル基、プロピル基、イソプロピル基、ブチル基、ヘキシル基、シクロヘキシル基、オクチル基、２−エチルヘキシル基等が挙げられる。上記式（２）中、ｎは０〜４の整数を表す。

In the above formula (2), R ⁴ is a hydrogen atom or a hydrocarbon group, R ⁵ each independently represent a hydrogen atom or an organic group. When R ⁴ is a hydrocarbon group, it can be a hydrocarbon group similar to the hydrocarbon group described in the above formula (1). When R ⁵ is an organic group, the organic group includes an aliphatic group or an aromatic group that is an alkyl group or a cycloalkyl group, and is preferably an aliphatic group. The alkyl group preferably has 1 to 12 carbon atoms, more preferably 1 to 10 carbon atoms, and particularly preferably 1 to 8 carbon atoms. These alkyl groups and cycloalkyl groups may have a substituent such as a halogen atom, an alkoxyl group, a dialkylamino group, an acyl group, or an alkoxycarbonyl group. Specific examples of the aliphatic group include a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, a hexyl group, a cyclohexyl group, an octyl group, and a 2-ethylhexyl group. In said formula (2), n represents the integer of 0-4.

Specific examples of the component (B) contained in the electrode binder composition according to the present embodiment include 1,2-benzisothiazolin-3-one, OLE_LINK12-methyl-4,5-trimethylene-4-isothiazoline- 3-one OLE_LINK1, 2-methyl-4-isothiazolin-3-one, 5-chloro-2-methyl-4-isothiazolin-3-one, Nn-butyl-1,2-benzisothiazolin-3-one, 2-n-octyl-4-isothiazoline-3-
ON, 4,5-dichloro-2-n-octyl-4-isothiazolin-3-one, and the like, and one or more of these can be used. Among these, 2-methyl-4-isothiazolin-3-one, 2-n-octyl-4-isothiazolin-3-one, 5-chloro-2-methyl-4-isothiazolin-3-one, 1,2- It is preferably at least one selected from the group consisting of benzisothiazolin-3-one.

1.3. Liquid medium (C)
The binder composition for electrodes according to the present embodiment contains a liquid medium (C). The liquid medium (C) is preferably an aqueous medium containing water. The aqueous medium can contain a non-aqueous medium other than water. Examples of the non-aqueous medium include amide compounds, hydrocarbons, alcohols, ketones, esters, amine compounds, lactones, sulfoxides, sulfone compounds, and the like. Use one or more selected from these. Can do. When the liquid medium (C) contains water and a non-aqueous medium other than water, 90% by mass or more is preferably water, and 98% by mass or more is water in 100% by mass of the total amount of the liquid medium (C). More preferably. In the electrode binder composition according to the present embodiment, the use of an aqueous medium as the liquid medium (C) reduces the degree of adverse effects on the environment and increases the safety for handling workers.

  The content ratio of the non-aqueous medium contained in the aqueous medium is preferably 10 parts by mass or less, more preferably 5 parts by mass or less, and substantially no content with respect to 100 parts by mass of the aqueous medium. Is particularly preferred. Here, “substantially does not contain” means that a non-aqueous medium is not intentionally added as a liquid medium, and is inevitably mixed when preparing a binder composition for electrodes. May be included.

1.4. Other Additives The electrode binder composition according to the present embodiment may contain additives other than the components (A), (B), and (C) described above as necessary. An example of such an additive is a thickener. By including a thickener, the electrode binder composition according to the present embodiment can further improve its applicability, charge / discharge characteristics of the obtained electricity storage device, and the like.

  Examples of such thickeners include cellulose compounds such as carboxymethyl cellulose, methyl cellulose, and hydroxypropyl cellulose; ammonium salts or alkali metal salts of the above cellulose compounds; poly (meth) acrylic acid, modified poly (meth) acrylic acid, and the like. Polycarboxylic acids of the above; alkali metal salts of the above polycarboxylic acids; polyvinyl alcohol (co) polymers such as polyvinyl alcohol, modified polyvinyl alcohol, ethylene-vinyl alcohol copolymers; (meth) acrylic acid, maleic acid and fumaric acid And water-soluble polymers such as saponified products of copolymers of unsaturated carboxylic acids and vinyl esters. Among these, particularly preferred thickeners include alkali metal salts of carboxymethyl cellulose and alkali metal salts of poly (meth) acrylic acid.

  Examples of commercially available thickeners include alkali metal salts of carboxymethyl cellulose such as CMC1120, CMC1150, CMC2200, CMC2280, and CMC2450 (above, manufactured by Daicel Chemical Industries, Ltd.).

  When the binder composition for electrodes which concerns on this Embodiment contains a thickener, it is preferable that the usage-amount of a thickener is 5 mass% or less with respect to the total solid content of the binder composition for electrodes. More preferably, it is 0.1-3 mass%.

2. Electrode slurry As described above, the electrode slurry according to the present embodiment can be produced using the electrode binder composition described above. The electrode slurry is a dispersion used to form an electrode active material layer on the current collector surface after being applied to the current collector surface and then dried. The electrode slurry according to the present embodiment contains the above-described electrode binder composition, an electrode active material, and water. Hereinafter, each component contained in the electrode slurry according to the present embodiment will be described in detail. However, since the electrode binder composition is as described above, the description thereof is omitted.

2.1. Electrode active material There is no restriction | limiting in particular as a material which comprises the electrode active material contained in the slurry for electrodes which concerns on this Embodiment, A suitable material can be suitably selected with the kind of the electrical storage device made into the objective.

  For example, when producing the positive electrode of a lithium ion secondary battery, it is preferable that it is a lithium atom containing oxide. “Oxide” in the present specification is a concept that means a compound or salt composed of oxygen and an element having an electronegativity lower than that of oxygen. In addition to metal oxide, metal phosphate, nitrate , Halogen oxo acid salts, sulfonic acid salts and the like.

Examples of the lithium atom-containing oxide include a composite metal oxide represented by the following general formula (4a) or (4b), and a lithium atom-containing oxide represented by the following general formula (5) and having an olivine crystal structure. It is preferable to use at least one selected from the group consisting of these.
Li _{1 + x} M ¹ _y M ² _z O ₂ (4a)
Li _{1 + x} M ¹ _y M ² _z O ₄ (4b)
(In Formulas (4a) and (4b), M ¹ is at least one metal atom selected from the group consisting of Co, Ni and Mn; M ² is at least one selected from the group consisting of Al and Sn) Is a metal atom of the species; O is an oxygen atom; x, y and z are in the range of 0.10 ≧ x ≧ 0, 4.00 ≧ y ≧ 0.85 and 2.00 ≧ z ≧ 0, respectively Is the number of
Li _1-x M ³ _x (XO ₄ ) (5)
(In the formula (5), ^{M 3} is a metal selected Mg, Ti, V, Nb, Ta, Cr, Mn, Fe, Co, Ni, Cu, Zn, Al, Ga, from the group consisting of Ge and Sn X is at least one selected from the group consisting of Si, S, P and V; x is a number and satisfies the relationship 0 <x <1.)

In addition, the value of x in the general formula (5) is selected so that the valence of the general formula (5) as a whole becomes zero according to the valences of M ³ and X, respectively.

Examples of the composite metal oxide represented by the general formula (4a) or (4b) include LiCoO ₂ , LiNiO ₂ , LiNi _y Co _1-y O ₂ (y = 0.01 to 0.99), LiMnO _2. , LiMn ₂ O ₄ , LiCo _x Mn _y Ni _z O ₂ (x + y + z = 1) and the like, and one or more selected from these can be used. Among these, LiCoO ₂ , LiMn ₂ O ₄ , LiNiO _2, and LiNi _0.33 Mn _0.33 Co _0.33 O ₂ have a high electrode potential and high efficiency, and therefore have a high voltage and high energy density. Can be obtained. Li _{1 + x} M ¹ _y M ² _z O ₂ is particularly preferable in that the Li diffusion rate in the solid is high and the charge / discharge rate is excellent.

The lithium atom-containing oxide represented by the general formula (5) and having an olivine crystal structure has different electrode potentials depending on the type of the metal element M ³ . Therefore, the battery voltage can be arbitrarily set by selecting the type of the metal element M. As typical examples of the lithium atom-containing oxide having an olivine crystal structure, LiFePO ₄ , LiCoPO ₄ , Li _0.
90 Ti _0.05 Nb _0.05 Fe _0.30 Co _0.30 Mn _0.30 PO _{4 and the} like. Among these, LiFePO ₄ is particularly preferable because it is easy to obtain an iron compound as a raw material and is inexpensive. Moreover, since the compound which substituted Fe ion in said compound by Co ion, Ni ion, or Mn ion also has the same crystal structure as said each compound, it has the same effect as an electrode active material.

  On the other hand, when producing a negative electrode of a lithium ion secondary battery, for example, carbon can be used as the electrode active material (negative electrode active material). Specific examples of carbon include carbon materials obtained by firing organic polymer compounds such as phenol resin, polyacrylonitrile, and cellulose; carbon materials obtained by firing coke and pitch; artificial graphite; natural graphite and the like Can be mentioned.

  In the case of producing an electric double layer capacitor electrode, as the electrode active material, for example, activated carbon, activated carbon fiber, silica, alumina or the like can be used. Moreover, when producing a lithium ion capacitor electrode, carbon materials such as graphite, non-graphitizable carbon, hard carbon, coke, polyacene organic semiconductor (PAS), or the like can be used.

  The number average particle diameter (Db) of the electrode active material is preferably in the range of 0.4 to 10 μm and more preferably in the range of 0.5 to 7 μm for the positive electrode. In a negative electrode, it is preferable to set it as the range of 3-30 micrometers, and it is more preferable to set it as the range of 5-25 micrometers. When the number average particle diameter (Db) of the electrode active material is within the above range, the diffusion distance of lithium in the electrode active material is shortened, so that the resistance associated with lithium desorption / insertion during charge / discharge can be reduced. As a result, the charge / discharge characteristics are further improved. Furthermore, when the slurry for electrodes contains the below-mentioned conductivity imparting agent, the number average particle diameter (Db) of the electrode active material is within the above range, so that the contact area between the electrode active material and the conductivity imparting agent is sufficient. As a result, the electronic conductivity of the electrode is improved, and the electrode resistance is further reduced.

  Here, the number average particle diameter (Db) of the electrode active material is the number of particles when the particle size distribution is measured using a particle size distribution measuring apparatus based on the laser diffraction method and the particles are accumulated from small particles. This is the value of the particle diameter (D50) at which the cumulative frequency is 50%. Examples of such a laser diffraction particle size distribution measuring apparatus include HORIBA LA-300 series, HORIBA LA-920 series (manufactured by Horiba, Ltd.) and the like. This particle size distribution measuring apparatus is not intended to evaluate only the primary particles of the electrode active material, but also evaluates the secondary particles formed by aggregation of the primary particles. Therefore, the number average particle diameter (Db) obtained by this particle size distribution measuring apparatus can be used as an indicator of the dispersion state of the electrode active material contained in the electrode slurry. The average particle diameter (Db) of the electrode active material is measured by centrifuging the electrode slurry to settle the electrode active material, then removing the supernatant and measuring the precipitated electrode active material by the above method. Can also be measured.

2.2. Other Components The electrode slurry can contain components other than the components described above as necessary. Examples of such components include a conductivity-imparting agent, a non-aqueous medium, and a thickener.

2.2.1. Conductivity-imparting agent Specific examples of the above-mentioned conductivity-imparting agent include carbon in a lithium ion secondary battery; in a nickel-hydrogen secondary battery, cobalt oxide at the positive electrode: nickel powder, cobalt oxide, titanium oxide, carbon at the negative electrode Etc. are used respectively. In both the batteries, examples of carbon include graphite, activated carbon, acetylene black, furnace black, graphite, carbon fiber, and fullerene. Among these, acetylene black or furnace black can be preferably used. The use ratio of the conductivity-imparting agent is preferably 20 parts by mass or less, more preferably 1 to 15 parts by mass, and particularly preferably 2 to 10 parts by mass with respect to 100 parts by mass of the electrode active material.

2.2.2. Non-aqueous medium The electrode slurry may contain a non-aqueous medium having a standard boiling point of 80 to 350 ° C. from the viewpoint of improving the applicability. Specific examples of such a non-aqueous medium include amide compounds such as N-methylpyrrolidone, dimethylformamide and N, N-dimethylacetamide; hydrocarbons such as toluene, xylene, n-dodecane and tetralin; 2-ethyl- Alcohols such as 1-hexanol, 1-nonanol and lauryl alcohol; ketones such as methyl ethyl ketone, cyclohexanone, phorone, acetophenone and isophorone; esters such as benzyl acetate, isopentyl butyrate, methyl lactate, ethyl lactate and butyl lactate; o-toluidine, m -Amine compounds such as toluidine and p-toluidine; lactones such as γ-butyrolactone and δ-butyrolactone; sulfoxide and sulfone compounds such as dimethyl sulfoxide and sulfolane. One or more selected from can be used. Among these, it is preferable to use N-methylpyrrolidone from the viewpoints of stability of polymer particles, workability when applying an electrode slurry, and the like.

2.2.3. Thickener The said electrode slurry can contain a thickener from a viewpoint of improving the coating property. Specific examples of the thickener include various compounds described in “1.4. Other additives”.

  When the electrode slurry contains a thickener, the use ratio of the thickener is preferably 20% by mass or less, more preferably 0.1 to 15% by mass with respect to the total solid content of the electrode slurry. %, Particularly preferably 0.5 to 10% by mass.

2.3. Method for Producing Electrode Slurry The electrode slurry according to the present embodiment is produced by mixing the above-mentioned electrode binder composition, electrode active material, water, and additives used as necessary. can do. These can be mixed by stirring by a known method. For example, a stirrer, a defoaming machine, a bead mill, a high-pressure homogenizer, or the like can be used.

The preparation of the electrode slurry (mixing operation of each component) is preferably performed at least part of the process under reduced pressure. Thereby, it can prevent that a big bubble arises in the electrode active material layer obtained. The degree of pressure reduction is preferably about 5.0 × 10 ^{4 to} 5.0 × 10 ⁵ Pa as an absolute pressure.

  As mixing and stirring for producing the electrode slurry, it is necessary to select a mixer capable of stirring to such an extent that no aggregates of the electrode active material remain in the slurry and a sufficient dispersion condition as necessary. The degree of dispersion can be measured with a particle gauge, but it is preferable to mix and disperse so that aggregates larger than at least 100 μm are eliminated. Examples of the mixer that meets such conditions include a ball mill, a sand mill, a pigment disperser, a crusher, an ultrasonic disperser, a homogenizer, a planetary mixer, and a Hobart mixer.

2.4. Characteristics of electrode slurry The ratio (Da / Db) of the number average particle diameter (Da) of the polymer particles (A) contained in the above-mentioned electrode binder composition to the number average particle diameter (Db) of the electrode active material is In the positive electrode, it is preferably in the range of 0.01 to 1.0, more preferably in the range of 0.05 to 0.5. In a negative electrode, it is preferable to exist in the range of 0.002-0.13, and it is more preferable to exist in the range of 0.003-0.1. The technical meaning of this is as follows.

  It has been confirmed that at least one of the polymer particles (A) and the electrode active material migrates in the step of drying the formed coating film after applying the electrode slurry to the surface of the current collector. That is, the particles move along the thickness direction of the coating film by receiving the action of surface tension. More specifically, at least one of the polymer particles (A) and the electrode active material is the side of the coating film surface opposite to the surface in contact with the current collector, that is, the gas-solid interface side where water evaporates. Move to. When such migration occurs, the distribution of the polymer particles (A) and the electrode active material becomes non-uniform in the thickness direction of the coating film, causing problems such as deterioration of electrode characteristics and loss of adhesion. For example, polymer particles (A) functioning as a binder bleed (transfer) to the gas-solid interface side of the electrode active material layer, and the amount of polymer particles (A) at the interface between the current collector and the electrode active material layer When the amount is relatively small, sufficient electrical characteristics cannot be obtained due to the inhibition of the electrolyte penetration into the electrode active material layer, and the binding property between the current collector and the electrode active material layer is insufficient. Will peel off. Furthermore, when the polymer particles (A) bleed, the smoothness of the electrode active material layer surface is impaired.

  However, when the ratio of the number average particle diameter of both particles (Da / Db) is in the above range, the occurrence of the problems as described above can be suppressed, and both good electrical characteristics and binding properties are compatible. The electrode can be easily manufactured. When the ratio (Da / Db) is less than the above range, the powder fall resistance may be insufficient. On the other hand, when the ratio (Da / Db) exceeds the above range, the binding property between the current collector and the electrode active material layer may be insufficient.

  The electrode slurry according to the present embodiment preferably has a solid content concentration (a ratio of the total mass of components other than the solvent in the slurry to the total mass of the slurry) of 20 to 80% by mass, 30 More preferably, it is -75 mass%.

  In the electrode slurry according to the present embodiment, the spinnability is preferably 30 to 80%, more preferably 33 to 79%, and particularly preferably 35 to 78%. If the spinnability is less than the above range, the leveling property is insufficient when the electrode slurry is applied onto the current collector, so that it may be difficult to obtain uniformity of the electrode thickness. If such an electrode having a non-uniform thickness is used, an in-plane distribution of charge / discharge reaction occurs, making it difficult to achieve stable battery performance. On the other hand, if the spinnability exceeds the above range, dripping tends to occur when the electrode slurry is applied onto the current collector, and it is difficult to obtain a stable quality electrode. Therefore, if the spinnability is within the above range, the occurrence of these problems can be suppressed, and it becomes easy to produce an electrode that achieves both good electrical characteristics and adhesion.

  The “threadability” in the present specification is measured as follows.

First, a Zaan cup (made by Dazai Equipment Co., Ltd., Zaan Bisco City Cup No. 5) having an opening with a diameter of 5.2 mm at the bottom is prepared. With this opening closed, 40 g of electrode slurry is poured into the Zahn cup. Thereafter, when the opening is opened, the electrode slurry flows out from the opening. Here, when T ₀ when opening the _opening, the T _A when the thread of the electrode slurry is _completed, when the outflow of the electrode slurry is completed the T _B, "hauls herein The “threadability” can be obtained from the following formula (6).
Spinnability (%) = ((T _A −T ₀ ) / (T _B −T ₀ )) × 100 (6)

3. Electrode The electrode according to the present embodiment includes a current collector and a layer formed by applying and drying the aforementioned electrode slurry on the surface of the current collector. Such an electrode is manufactured by applying the above-mentioned electrode slurry to the surface of an appropriate current collector such as a metal foil to form a coating film, and then drying the coating film to form an electrode active material layer. can do. The electrode produced in this manner is formed by binding an electrode active material layer containing the polymer (A) and the electrode active material described above, and an optional component added as necessary, on a current collector. Is. Such an electrode has excellent binding properties between the current collector and the electrode active material layer, and also has good charge / discharge rate characteristics, which is one of electrical characteristics. Therefore, such an electrode is suitable as an electrode for an electricity storage device.

  The current collector is not particularly limited as long as it is made of a conductive material. In a lithium ion secondary battery, a current collector made of metal such as iron, copper, aluminum, nickel, and stainless steel is used. In particular, when aluminum is used for the positive electrode and copper is used for the negative electrode, the above-mentioned electrode binder is used. The effect of the slurry for an electrode manufactured using is best exhibited. As the current collector in the nickel metal hydride secondary battery, a punching metal, an expanded metal, a wire mesh, a foam metal, a mesh metal fiber sintered body, a metal plated resin plate, or the like is used. The shape and thickness of the current collector are not particularly limited, but it is preferable that the current collector has a sheet shape with a thickness of about 0.001 to 0.5 mm.

  There is no particular limitation on the method of applying the electrode slurry to the current collector. The coating can be performed by an appropriate method such as a doctor blade method, a dip method, a reverse roll method, a direct roll method, a gravure method, an extrusion method, a dipping method, or a brush coating method. The coating amount of the electrode slurry is not particularly limited, but the thickness of the electrode active material layer formed after removing the liquid medium (which is a concept including both water and a non-aqueous medium that is optionally used) is not limited. The amount is preferably 0.005 to 5 mm, and more preferably 0.01 to 2 mm. When the thickness of the electrode active material layer is within the above range, the electrode active material layer can be effectively infiltrated with the electrolytic solution. As a result, the metal ions accompanying the charge / discharge between the electrode active material in the electrode active material layer and the electrolytic solution are easily exchanged, which is preferable because the electrode resistance can be further reduced. In addition, since the thickness of the electrode active material layer is within the above range, the electrode active material layer does not peel from the current collector even when the electrode is processed by folding or winding. Is preferable in that an electrode for an electricity storage device having good flexibility and high flexibility can be obtained.

  There is no particular limitation on the drying method from the coated film after coating (method for removing water and optionally used non-aqueous medium), for example, drying with hot air, hot air or low-humidity air; vacuum drying; (far) infrared , Drying by irradiation with an electron beam or the like. The drying speed is appropriately set so that the liquid medium can be removed as quickly as possible within a speed range in which the electrode active material layer does not crack due to stress concentration or the electrode active material layer does not peel from the current collector. Can be set.

  Furthermore, it is preferable to increase the density of the electrode active material layer by pressing the dried current collector and to adjust the porosity to the range shown below. Examples of the pressing method include a die press and a roll press. The pressing conditions should be appropriately set depending on the type of press equipment used and the desired values of the porosity and density of the electrode active material layer. This condition can be easily set by a few preliminary experiments by those skilled in the art. For example, in the case of a roll press, the linear pressure of the roll press machine is 0.1 to 10 (t / cm), preferably 0. At a pressure of 5 to 5 (t / cm), for example, at a roll temperature of 20 to 100 ° C., the current collector feed speed (roll rotation speed) after drying is 1 to 80 m / min, preferably 5 to 50 m / min. It can be performed in min.

Density of the electrode active material layer after pressing is preferably to 1.5~5.0g / cm ^3, more preferably to 1.5~4.0g / cm ^3, 1.6~3. Particularly preferred is 8 g / cm ³ . When the electrode active material is a composite metal oxide represented by the above general formula (4a) or (4b), the density of the electrode active material layer is preferably 2.0 to 4.0 g / cm ^3. 3.0 to 3.5 g / cm ³ is more preferable. When the electrode active material is a compound represented by the above general formula (5) and having an olivine type crystal structure, the density of the electrode active material layer may be 1.5 to 2.5 g / cm ^3. It is preferably 1.6 to 2.4 g / cm ³ , more preferably 1.7 to 2.2 g / cm ^3, and even more preferably 1.8 to 2.1 g / cm ^3. Particularly preferred. When the density of the electrode active material layer is in the above range, the binding property between the current collector and the electrode active material layer is improved, and an electrode having excellent powdering properties and electrical characteristics is obtained. Will be. If the density of the electrode active material layer is less than the above range, the polymer (A) in the electrode active material layer does not sufficiently function as a binder, and the electrode active material layer is agglomerated and peeled off, resulting in a decrease in powder fallability. To do. Moreover, when the density of an electrode active material layer exceeds the said range, the binder function of the polymer (A) in an electrode active material layer is too strong, and adhesion | attachment between electrode active materials will become too strong. As a result, the electrode active material layer cannot follow the flexibility of the current collector, and the interface between the current collector and the electrode active material layer may peel off, which is not preferable. The “density of the electrode active material layer” in the present invention is a value indicating the bulk density of the electrode active material layer, and can be known from the following measurement method. That is, in an electrode having an electrode active material layer having an area C (cm ² ) and a thickness D (μm) on one side of the current collector, the mass of the current collector is A (g) and the mass of the electrode for the electricity storage device is B In the case of (g), the density of the electrode active material layer is defined by the following formula (7).
Density of electrode active material layer (g / cm ³ ) = (B (g) −A (g)) / (C (cm ² ) × D (μm) × 10 ⁻⁴ ) (7)

The porosity of the electrode active material layer after pressing is preferably 10 to 50%, more preferably 15 to 45%, and particularly preferably 20 to 40%. When the porosity of the electrode active material layer is in the above range, the binding property between the current collector and the electrode active material layer is good, and an electrode having excellent powdering properties and electrical characteristics is obtained. It is done. Moreover, when the porosity of the electrode active material layer is within the above range, the electrolyte solution can be sufficiently infiltrated into the electrode active material layer, and the surface of the electrode active material and the electrolyte solution can be sufficiently in contact with each other. As a result, transfer of the lithium ion of the electrode active material and the electrolytic solution becomes easy, and good charge / discharge characteristics can be achieved. In the present invention, the “porosity of the electrode active material layer” means the volume of the pores (the volume occupied by the solid content (electrode active material, conductivity-imparting agent, binder, etc.) from the volume of the electrode active material layer) Is the ratio of the total volume of the electrode active material layer. That is, in an electrode having an electrode active material layer having an area C (cm ² ) and a thickness D (μm) on one side of the current collector, the mass of the electrode active material layer was measured by B (g), a mercury intrusion method. When the pore volume is V (cm ³ / g), it is a value defined by the following formula (8).
Porosity (%) of electrode active material layer = ((V [cm ³ / g] × B [g]) / (C [cm ² ] × D [μm] × 10 ⁻⁴ )) × 100 (8)

  The pore volume can be measured, for example, by a mercury intrusion method using a mercury porosimeter. As the mercury porosimeter, for example, the product name “PoreMaster” manufactured by Quantachrome, the product name “Autopore IV” manufactured by Shimadzu Corporation can be used.

4). Power Storage Device The power storage device according to the present embodiment includes the above-described electrode, and further contains an electrolytic solution, and can be manufactured according to a conventional method using components such as a separator. As a specific manufacturing method, for example, a negative electrode and a positive electrode are overlapped via a separator, and this is wound into a battery container according to a battery shape, put into a battery container, an electrolyte is injected into the battery container, and sealing is performed. The method of doing is mentioned. The shape of the battery can be an appropriate shape such as a coin shape, a button shape, a sheet shape, a cylindrical shape, a square shape, or a flat shape.

  The electrolyte may be liquid or gel, and an electrolyte that effectively expresses the function as a battery may be selected from known electrolytes used for the electricity storage device according to the type of the electrode active material. The electrolytic solution can be a solution in which an electrolyte is dissolved in a suitable solvent.

As the electrolyte, in the lithium ion secondary battery, any conventionally known lithium salt can be used, and specific examples thereof include, for example, LiClO ₄ , LiBF ₄ , LiPF ₆ , LiCF ₃ CO ₂ , LiAsF. ₆ , LiSbF ₆ , LiB ₁₀ Cl ₁₀ , LiAlCl ₄ , LiCl, LiBr, LiB (C ₂ H ₅ ) ₄ , LiCF ₃ SO ₃ , LiCH ₃ SO ₃ , LiC ₄ F ₉ SO ₃ , Li (CF ₃ SO ₂ ) ₂ N, lithium of lower fatty acid carboxylate etc. can be illustrated. In a nickel metal hydride secondary battery, for example, an aqueous potassium hydroxide solution having a conventionally known concentration of 5 mol / liter or more can be used.

  The solvent for dissolving the electrolyte is not particularly limited. Specific examples thereof include carbonate compounds such as propylene carbonate, ethylene carbonate, butylene carbonate, dimethyl carbonate, methyl ethyl carbonate, and diethyl carbonate; Lactone compounds such as butyl lactone; ether compounds such as trimethoxymethane, 1,2-dimethoxyethane, diethyl ether, 2-ethoxyethane, tetrahydrofuran, 2-methyltetrahydrofuran; sulfoxide compounds such as dimethyl sulfoxide, etc. One or more selected from these can be used. The concentration of the electrolyte in the electrolytic solution is preferably 0.5 to 3.0 mol / L, more preferably 0.7 to 2.0 mol / L.

5. EXAMPLES Hereinafter, the present invention will be specifically described based on examples, but the present invention is not limited to these examples. “Part” and “%” in Examples and Comparative Examples are based on mass unless otherwise specified.

5.1. Example 1
5.1.1. Preparation of polymer particles (A) The inside of an autoclave having an internal volume of about 6L equipped with an electromagnetic stirrer was sufficiently purged with nitrogen, and then charged with 2.5L of deoxygenated pure water and 25g of ammonium perfluorodecanoate as an emulsifier. The temperature was raised to 60 ° C. while stirring at 350 rpm. Next, a mixed gas composed of 70% of the monomer vinylidene fluoride (VDF (registered trademark)) and 30% propylene hexafluoride (HFP) was charged until the internal pressure reached 20 kg / cm ² . 25 g of Freon 113 solution containing 20% of diisopropyl peroxydicarbonate as a polymerization initiator was injected using nitrogen gas to initiate polymerization. During the polymerization, a mixed gas composed of 60.2% VDF and 39.8% HFP was sequentially injected so that the internal pressure was maintained at 20 kg / cm ² to maintain the pressure at 20 kg / cm ² . Further, since the polymerization rate decreased as the polymerization progressed, the same amount of the same polymerization initiator solution as that described above was injected using nitrogen gas after 3 hours, and the reaction was continued for 3 hours. Thereafter, the reaction liquid was cooled and the stirring was stopped at the same time, and after the unreacted monomer was released, the reaction was stopped to obtain an aqueous dispersion containing 40% of the fine particles of the polymer (Aa). The obtained polymer (Aa) was analyzed by ¹⁹ F-NMR. As a result, the mass composition ratio of each monomer was VDF / HFP = 21/4.

After fully replacing the inside of a 7 L separable flask with nitrogen, 1,600 g of an aqueous dispersion containing fine particles of the polymer (Aa) obtained in the above step (25 parts by mass in terms of polymer (Aa)) ), An emulsifier “ADEKA rear soap SR1025” (trade name, manufactured by ADEKA Corporation) 0.5 part by mass, methyl methacrylate (MMA) 30 parts by mass, 2-ethylhexyl acrylate (EHA) 40 parts by mass and methacrylic acid (MAA) 5 parts by mass and 130 parts by mass of water were sequentially added, and the mixture was stirred at 70 ° C. for 3 hours to allow the polymer (Aa) to absorb the monomer. Next, 20 mL of a tetrahydrofuran solution containing 0.5 part by mass of azobisisobutyronitrile, which is an oil-soluble polymerization initiator, is added, heated to 75 ° C., reacted for 3 hours, and further reacted at 85 ° C. for 2 hours. went. Then, after cooling, the reaction was stopped, and the aqueous dispersion containing 40% of polymer particles (A) was obtained by adjusting the pH to 7 with a 2.5N aqueous sodium hydroxide solution.

About 10 g of the obtained aqueous dispersion was weighed into a Teflon (registered trademark) petri dish having a diameter of 8 cm and dried at 120 ° C. for 1 hour to form a film. 1 g of the obtained membrane (polymer) was immersed in 400 mL of tetrahydrofuran (THF) and shaken at 50 ° C. for 3 hours. Next, the THF phase was filtered through a 300-mesh wire mesh to separate the insoluble matter, and the weight (Y (g)) of the residue obtained by evaporating and removing the dissolved THF was measured. When the THF-insoluble content was determined by 9), the THF-insoluble content of the polymer particles was 85%.
THF insoluble matter (%) = ((1-Y) / 1) × 100 (9)

  Further, when the obtained fine particles were measured by a differential scanning calorimeter (DSC), only one single glass transition temperature Tg was observed at -5 ° C. Despite the use of two types of polymers, the obtained polymer particles (A) show only one Tg, so it can be assumed that the polymer particles (A) are polymer alloy particles.

5.1.2. Preparation of Electrode Binder Composition An aqueous suspension containing 1% 2-methyl-4-isothiazolin-3-one was added to 1,000 g of the aqueous dispersion containing the polymer particles (A) obtained above. An electrode binder composition was prepared by charging 31 g and stirring at 300 rpm. In the following examples and comparative examples, when the component (B) was water-insoluble, a dispersion in a state of being dispersed in an aqueous solution by ultrasonic waves was added to prepare a binder composition for an electrode.

  About the obtained binder composition for electrodes, a particle size distribution is measured using a particle size distribution measuring apparatus (model "FPAR-1000" manufactured by Otsuka Electronics Co., Ltd.) having a dynamic light scattering method as a measurement principle. From which the number average particle size was 330 nm.

  In addition, content of the component (B) in the binder composition for electrodes can also be confirmed by analyzing the binder composition for electrodes in the following procedures. That is, 2.0 g of the obtained electrode binder composition is weighed, and an aqueous aluminum sulfate solution is added to cause aggregation. Next, the agglomerated polymer component is filtered, and a high-performance liquid chromatography apparatus (column: manufactured by Waters, μBondasphere 5μ C18-100Å (inner diameter: 3.9 mm, length: 150 mm), mobile phase: using distilled water. Trifluoroacetic acid was added to 2 L of the prepared 0.01 M ammonium acetate, pH was adjusted to 4.0, 500 mL of acetonitrile for high performance liquid chromatography was added and mixed, flow rate: 0.6 mL / min) As a result, it was confirmed that the content of 2-methyl-4-isothiazolin-3-one was 300 ppm.

5.1.3. Storage Stability Evaluation of Electrode Binder Composition Generally, electrode binder compositions are generally stored in large quantities for use in factories that produce electricity storage devices. And the binder composition for electrodes stored in large quantities is consumed sequentially as needed. When bacteria and the like propagate during storage of the electrode binder composition, the electrode slurry produced using this electrode binder composition tends to agglomerate, which improves crack resistance and charge / discharge characteristics of the electricity storage device. Since it may worsen, it is not preferable.

In addition, the storage environment of the electrode binder composition cannot be strictly controlled from the viewpoint of cost, and is therefore often exposed to an environment near 0 ° C. due to a change in temperature. For this reason, in the following evaluation of the freezing temperature, freezing at 0 ° C. is not acceptable, and the freezing temperature is required to be −0.5 ° C. or lower. Therefore, when the freezing temperature is −0.5 ° C. or lower, it can be determined that the stability of the electrode binder composition is high and good.

  Furthermore, the storage of the electrode binder composition may extend over a long period (approximately several months to several years). For this reason, even if it is a case where the binder composition for electrodes stored for a long period of time is used, performance, such as a charge / discharge characteristic of the electrode obtained, needs to become constant. Therefore, the electrode produced using the binder composition after long-term storage in “5.1.6. Production and evaluation of electricity storage device” described below is inferior to the electrode produced using the binder composition immediately after preparation. In the case where no charge / discharge characteristics are exhibited, it can be determined that the long-term storage stability is good.

<Septic test>
To 100 g of the electrode binder composition prepared above, 5 g of the bacterial solution was added and stored at 35 ° C. for 2 weeks. Thereafter, 5 g of the bacterial solution was further added and stored at 35 ° C. for 2 months. The number of bacteria of this binder composition for electrodes was determined by using the commercially available “EASICULT TTC” (Orion
After culturing in a thermostat at 28 ° C. for 48 hours using Diagnostica (Finland), the density of the generated colonies of the bacteria was determined by comparison with a control table. In addition, to the aqueous dispersion containing 40% of the polymer particles (A) prepared in the section of “5.1.1. Preparation of polymer particles (A)”, commonas acidovorans was added as an indicator bacterium to rot, aqueous dispersion number of bacteria became ¹⁰⁷ cells / ml was used as a bacterial solution.

Here, the electrode binder composition having excellent storage stability has a small number of bacteria. The number of bacteria is preferably 0 / ml. However, when manufacturing an electrode, it is acceptable if the number of bacteria is up to 10 ⁴ / ml, and more stable if the number of bacteria is less than 10 ³ / ml. Thus, a good electrode can be manufactured. However, if the number of bacteria exceeds 10 ⁴ / ml, foreign matter generated by the bacteria increases, and it becomes impossible to produce a homogeneous electrode, and the productivity of the electrode decreases. Therefore, up to 10 ⁴ cells / ml as the threshold of the number of bacteria is considered to be a good range. The evaluation criteria are as follows, and the evaluation results are also shown in Table 1.
○: The number of bacteria is less than 10 ³ / ml Δ: The number of bacteria is 10 ³ / ml or more and less than 10 ⁴ / ml ×: The number of bacteria is 10 ⁴ / ml or more

<Evaluation of freezing temperature>
The electrode binder composition prepared above was filled in 1000 g in a polybin, and then stored in a freezer at −10 ° C., and the temperature at which freezing started (freezing temperature) was measured. As a result, the freezing temperature of the electrode binder composition was -0.6 ° C. The results of freezing temperature evaluation are also shown in Table 1.

5.1.4. Preparation and Evaluation of Electrode Slurry Biaxial Planetary Mixer (product name “TK Hibismix 2P-03” manufactured by PRIMIX Corporation) and thickener (product name “CMC1120”, manufactured by Daicel Chemical Industries, Ltd.) 1 mass Part (solid content conversion), electrode active material having a particle diameter (D50 value) of 0.5 μm obtained by grinding a commercially available lithium iron phosphate (LiFePO ₄ ) in an agate mortar and classifying with a sieve 100 parts by mass, 5 parts by mass of acetylene black and 68 parts by mass of water were added and stirred at 60 rpm for 1 hour. Subsequently, the electrode binder composition obtained in the above "5.1.2. Preparation of electrode binder composition" is added so that the polymer particles contained in the composition are 1 part by mass, The mixture was further stirred for 1 hour to obtain a paste. Water was added to the obtained paste to adjust the solid content concentration to 50%, and then the mixture was stirred at 200 rpm for 2 minutes using a stirring defoamer (trade name “Awatori Nertaro” manufactured by Shinky Co., Ltd.). , 800 rpm for 5 minutes,
Furthermore, slurry for electrodes was prepared by stirring and mixing at 1,800 rpm for 1.5 minutes under vacuum (about 5.0 × 10 ³ Pa).

<Measurement of spinnability>
The spinnability of the obtained electrode slurry was measured as follows.

First, a Zaan cup (made by Dazai Equipment Co., Ltd., Zaan Biscocity Cup No. 5) having an opening with a diameter of 5.2 mm at the bottom of the container was prepared. With the opening of the Zahn cup closed, 40 g of the electrode slurry prepared above was poured. When the opening was opened, the slurry flowed out. In this case, the time instant of opening the opening and T _0, the time continued to flow out so as to draw the yarn when the slurry flows measured visually, the time was T _A. Moreover, to continue the measurement from no longer attracted yarn was measured time T _B until no flow out electrode slurry. The measured values T ₀ , T _A and T _B were substituted into the following formula (6) to determine the spinnability.
Spinnability (%) = ((T _A −T ₀ ) / (T _B −T ₀ )) × 100 (6)

  It can be judged good when the spinnability of the electrode slurry is 30 to 80%. Table 1 also shows the measurement results of the spinnability.

5.1.5. Production and Evaluation of Electrode On the surface of a current collector made of an aluminum foil having a thickness of 30 μm, the electrode slurry prepared above was uniformly applied by a doctor blade method so that the film thickness after drying was 100 μm, and 120 ° C. For 20 minutes. Then, the electrode (positive electrode) was obtained by press-processing with a roll press so that the density of a film | membrane (electrode active material layer) might become the value of Table 1.

<Measurement of peel strength>
A test piece having a width of 2 cm and a length of 12 cm was cut out from the obtained electrode, and the surface of the test piece on the electrode active material layer side was attached to an aluminum plate using a double-sided tape. On the other hand, a 18 mm wide tape (manufactured by Nichiban Co., Ltd., trade name “Cello Tape (registered trademark)”, prescribed in JIS Z1522) was attached to the surface of the current collector of the test piece. The force (mN / 2 cm) when this 18 mm wide tape was peeled 2 cm in the 90 ° direction at a speed of 50 mm / min was measured 6 times, and the average value was calculated as the adhesion strength (peel strength, mN / 2 cm). Note that the greater the peel strength value, the higher the adhesion strength between the current collector and the electrode active material layer, and it can be evaluated that the electrode active material layer is less likely to peel from the current collector. When it is 20 mN / 2 cm or more, it can be judged to be good. The measurement results of peel strength are also shown in Table 1.

<Measurement of crack rate>
The obtained electrode was cut into an electrode plate having a width of 2 cm and a length of 10 cm, and the positive electrode plate was repeatedly bent at 100 times along a round bar having a diameter of 2 mm in the width direction. The size of the crack along the round bar was visually observed and measured, and the crack rate was measured. The crack rate was defined by the following formula (10).
Crack rate (%) = (length with crack [mm] ÷ total length of electrode plate [mm]) × 100 (10)

  Here, the electrode plate excellent in flexibility and adhesion has a low crack rate. The crack rate is preferably 0%. However, when the electrode plate group is manufactured by spirally winding through a separator, the crack rate is allowed up to 20%. However, if the crack rate is greater than 20%, the electrodes are easily cut off, making it impossible to manufacture the electrode plate group, and the productivity of the electrode plate group decreases. From this, it is considered that a good range is up to 20% as the threshold of the crack rate. The measurement results of the crack rate are also shown in Table 1.

5.1.6. Manufacturing and evaluation of electricity storage devices <Manufacture of counter electrode (negative electrode)>
A biaxial planetary mixer (product name “TK Hibismix 2P-03” manufactured by PRIMIX Corporation), 4 parts by mass of polyvinylidene fluoride (PVDF) (in terms of solid content), and 100 parts by mass of graphite as a negative electrode active material (solid) Minute conversion), 80 parts by mass of N-methylpyrrolidone (NMP) was added, and the mixture was stirred at 60 rpm for 1 hour. Then, after adding 20 parts by mass of NMP, using a stirring defoaming machine (product name “Awatori Netaro” manufactured by Shinky Co., Ltd.) for 2 minutes at 200 rpm, then for 5 minutes at 1,800 rpm, further vacuum A slurry for the counter electrode (negative electrode) was prepared by stirring and mixing at 1,800 rpm for 1.5 minutes below.

The counter electrode (negative electrode) slurry prepared above was uniformly applied to the surface of the current collector made of copper foil by the doctor blade method so that the film thickness after drying was 150 μm, and dried at 120 ° C. for 20 minutes. . Then, the counter electrode (negative electrode) was obtained by pressing using a roll-press machine so that the density of a film | membrane may be 1.5 g / cm < ³ >.

<Assembly of lithium-ion battery cells>
A bipolar coin cell (manufactured by Hosen Co., Ltd.) manufactured by punching and molding the electrode (negative electrode) produced in the above to a diameter of 15.95 mm in a glove box substituted with Ar so that the dew point is −80 ° C. or lower. The name “HS flat cell”). Next, a separator made of a polypropylene porous film punched to a diameter of 24 mm (product name “Celguard # 2400” manufactured by Celgard Co., Ltd.) was placed, and after injecting 500 μL of electrolyte so that air did not enter, A lithium ion battery cell (power storage device) was assembled by placing the positive electrode manufactured in the above-described method by punching and molding the positive electrode to a diameter of 16.16 mm, and sealing the outer body of the bipolar coin cell with a screw. The electrolytic solution used here is a solution obtained by dissolving LiPF ₆ at a concentration of 1 mol / L in a solvent of ethylene carbonate / ethyl methyl carbonate = 1/1 (mass ratio).

<Evaluation of charge / discharge rate characteristics>
About the electrical storage device manufactured above, charging is started at a constant current (0.2 C), and when the voltage reaches 4.2 V, charging is continued at a constant voltage (4.2 V). The charge capacity at 0.2C was measured with the time when the temperature reached 0.01C being regarded as completion of charge (cutoff). Next, discharge was started at a constant current (0.2 C), and when the voltage reached 2.7 V, the discharge was completed (cut off), and the discharge capacity at 0.2 C was measured.

  Next, charging is started at a constant current (3C) for the same cell, and when the voltage reaches 4.2V, charging is continued at a constant voltage (4.2V). The charging capacity at 3C was measured with the time point of becoming the completion of charging (cut-off). Next, discharge was started at a constant current (3C), and when the voltage reached 2.7 V, the discharge was completed (cut off), and the discharge capacity at 3C was measured.

  Using the measured values above, calculate the charge rate (%) by calculating the ratio (percent%) of the charge capacity at 3C to the charge capacity at 0.2C at 3C versus the discharge capacity at 0.2C. The discharge rate (%) was calculated by calculating the discharge capacity ratio (percentage%). When both the charge rate and the discharge rate are 80% or more, it can be evaluated that the charge / discharge rate characteristics are good. The measured charge rate and discharge rate values are shown in Table 1, respectively.

<Evaluation of charge / discharge rate characteristics after long-term storage>
1000 g of the electrode binder composition obtained in the above “5.1.2. Preparation of electrode binder composition” was filled in a polybin and stored in a refrigerator set at 2 ° C. for 5 months. An electrode was prepared using the binder composition for an electrode after storage, and the charge / discharge rate characteristic after long-term storage was evaluated in the same manner as in the above <Evaluation of charge / discharge rate characteristic>. The measured charge rate and discharge rate values are shown in Table 1, respectively.

  In the measurement conditions, “1C” indicates a current value at which discharge is completed in one hour after constant current discharge of a cell having a certain electric capacity. For example, “0.1 C” is a current value at which discharge is completed over 10 hours, and 10 C is a current value at which discharge is completed over 0.1 hours.

5.2. Examples 2 to 5 and Comparative Examples 1 to 3
Table 1 shows the same procedure as in Example 1 except that the composition of the monomer and the amount of the emulsifier were appropriately changed in “5.1.1. Preparation of polymer particles (A)” in Example 1 above. An aqueous dispersion containing polymer particles (A) having a composition was prepared, and water was removed under reduced pressure or added according to the solid content concentration of the aqueous dispersion, thereby obtaining an aqueous dispersion having a solid content concentration of 40%. It was. In addition, when the fine particles obtained in Examples 2 to 5 and Comparative Examples 1 to 3 were measured by a differential scanning calorimeter (DSC), only one single glass transition temperature Tg was observed at the temperature described in Table 1. It was done. Despite the use of two types of polymers, the obtained polymer particles (A) show only one Tg, so it can be assumed that the polymer particles (A) are polymer alloy particles.

  Next, in Example 1 “5.1.2. Preparation of binder composition for electrodes”, the amount of component (A) and component (B) was changed to the types and amounts shown in Table 1, and the examples were used. In the same manner as in Example 1, an electrode binder composition was prepared. The obtained binder composition for an electrode was evaluated in the same manner as in “5.1.3. Evaluation of storage stability of binder composition for electrode” in Example 1. The results are also shown in Table 1.

  Furthermore, “5.1.4. Preparation and evaluation of slurry for electrode”, “5.1.5. Production and evaluation of electrode”, “5.1.6. Production and evaluation of electricity storage device” in Example 1 In the same manner as above, slurry for electrodes, electrodes, and electricity storage devices were prepared and evaluated. The results are also shown in Table 1.

5.3. Comparative Example 4
5.3.1. Preparation of polymer particles (A) A separable flask having a capacity of 7 liters was charged with 150 parts by mass of water and 0.2 parts by mass of sodium dodecylbenzenesulfonate, and the inside of the separable flask was sufficiently substituted with nitrogen. On the other hand, in another container, 60 parts by mass of water, ether sulfate type emulsifier (trade name “ADEKA rear soap SR1025”, manufactured by ADEKA Co., Ltd.) as an emulsifier, 0.8 parts by mass in terms of solid content, and 2, 2,2-trifluoroethyl methacrylate (TFEMA) 20 parts by mass, acrylonitrile (AN) 10 parts by mass, methyl methacrylate (MMA) 25 parts by mass, 2-ethylhexyl acrylate (EHA) 40 parts by mass and acrylic acid (AA) 5 parts by mass A monomer emulsion containing a mixture of the above monomers was prepared by adding sufficient parts. Then, the temperature inside the separable flask was started, and when the temperature inside the separable flask reached 60 ° C., 0.5 parts by mass of ammonium persulfate was added as a polymerization initiator. Then, when the temperature inside the separable flask reaches 70 ° C., the addition of the monomer emulsion prepared above is started, and the temperature inside the separable flask is maintained at 70 ° C. The emulsion was added slowly over 3 hours. Thereafter, the temperature inside the separable flask was raised to 85 ° C., and this temperature was maintained for 3 hours to carry out the polymerization reaction. After 3 hours, the separable flask was cooled to stop the reaction, and ammonium water was added to adjust the pH to 7.6 to obtain an aqueous dispersion containing 30% of the polymer particles (A). .

  When the aqueous dispersion obtained above was evaluated in the same manner as in Example 1, the number average particle diameter was 110 nm. Only one glass transition temperature was observed at 8 ° C. Except having used the aqueous dispersion obtained above, it carried out similarly to Example 1, and produced and evaluated the binder composition for electrodes, the slurry for electrodes, the electrode, and the electrical storage device.

5.4. Comparative Examples 5-6
Polymer particles (A) having the number average particle diameters shown in Table 1 in the same manner as in Comparative Example 4 except that the type and amount (parts) of each monomer are as shown in Table 1. Aqueous dispersions containing each were obtained. A binder composition for an electrode, an electrode slurry, an electrode and an electricity storage device were prepared and evaluated in the same manner as in Example 1 except that the aqueous dispersion thus obtained was used.

5.5. Evaluation Results Table 1 shows the electrode binder compositions according to Examples 1 to 5 and Comparative Examples 1 to 6 and the above evaluation results.

Abbreviations of each component in Table 1 have the following meanings.
VDF: vinylidene fluoride, HFP: propylene hexafluoride, TFEMA: 2,2,2-trifluoroethyl methacrylate, TFEA: 2,2,2-trifluoroethyl acrylate, HFIPA: acrylic acid 1,1, 1,3,3,3-hexafluoroisopropyl, MMA: methyl methacrylate, EHA: 2-ethylhexyl acrylate, MAA: methacrylic acid, AA: acrylic acid, DVB: divinylbenzene, TMPTMA: trimethylolpropane trimethacrylate AN: Acrylonitrile

As apparent from Table 1 above, the electrode binder compositions according to the present invention shown in Examples 1 to 5 have good storage stability, and were further prepared using the electrode binder composition according to the present invention. The electrode slurry thus obtained gave an electrode having a low crack rate and excellent adhesion because the binding property between the current collector and the electrode active material layer was good. Moreover, the electrical storage device (lithium ion secondary battery) provided with these electrodes had favorable charge / discharge rate characteristics. Furthermore, an electricity storage device (lithium ion secondary battery) including an electrode produced using the electrode binder composition according to Examples 1 to 5 stored in a refrigerator set at 2 ° C. for 5 months is immediately after preparation. Compared with the case where the binder composition for electrodes was used, charge / discharge rate characteristics almost inferior were obtained.

  On the other hand, since the binder composition shown in Comparative Example 1 is not excellent in storage stability, it is considered that the crack resistance of the electrode deteriorated as a result of aggregation occurring in the electrode slurry. Furthermore, since the binder composition shown in Comparative Example 1 is not excellent in long-term storage stability, an electricity storage device (lithium ion secondary battery) including an electrode prepared from the binder composition after long-term storage is It has been found that the charge / discharge rate characteristics are poor as compared with the case of using the electrode binder composition immediately after preparation.

As described above, it was estimated from the DSC chart that the polymer particles (A) used in Examples 1 to 5 and Comparative Examples 1 to 3 were polymer alloy particles.

  FIG. 1 is a DSC chart of the polymer particles (A) obtained in Example 3. In Example 3, since a monomer is further added to the fine particles of the polymer (Aa) and polymerization is performed in a multistage manner, it is considered that the polymer particles contain at least two types of polymers. However, as is apparent from FIG. 1, two types of Tg derived from these two types of polymers cannot be confirmed, and only one Tg is observed. This indicates that the polymer particles produced as in Example 3 are in a polymer alloy state.

  The present invention is not limited to the above embodiment, and various modifications can be made. The present invention includes configurations that are substantially the same as the configurations described in the embodiments (for example, configurations that have the same functions, methods, and results, or configurations that have the same objects and effects). The present invention also includes a configuration in which a non-essential part of the configuration described in the above embodiment is replaced with another configuration. Furthermore, the present invention includes a configuration that achieves the same effects as the configuration described in the above embodiment or a configuration that can achieve the same object. Furthermore, the present invention includes a configuration obtained by adding a known technique to the configuration described in the above embodiment.

Claims (8)

A binder composition for producing an electrode used in a lithium ion secondary battery ,
A polymer (A), an isothiazoline compound (B), and water (C),
The polymer (A) is
A repeating unit (Ma) derived from at least one fluorine-containing ethylene monomer selected from the group consisting of vinylidene fluoride, tetrafluoroethylene and hexafluoropropylene ;
A repeating unit (Mb) derived from an unsaturated carboxylic acid ester;
Ri Oh fluorine-containing polymer alloy polymer particles having,
The binder composition for lithium ion secondary battery electrodes whose density | concentration of the said isothiazoline type compound (B) in the said binder composition is 50-1,500 ppm. When the differential scanning calorimetry (DSC) is performed on the fluorine-containing polymer alloy polymer particles according to JIS K7121, only one endothermic peak in a temperature range of -50 to + 250 ° C is observed. The binder composition for a lithium ion secondary battery electrode according to 1. The binder composition for a lithium ion secondary battery electrode according to claim 2, wherein the endothermic peak is observed in a temperature range of -30 to + 30 ° C. It said compound (B), is at least one selected from the group consisting of compounds represented by the compound represented by and the following formula by the following general formula (1) (2), according to claim 1 to claim 3 The binder composition for lithium ion secondary battery electrodes as described in any one of these .

(In formula (1), R ¹ represents a hydrogen atom or a hydrocarbon group, and R ² and R ³ each represent a hydrogen atom, a halogen atom or a hydrocarbon group.)

(In formula (2), R ⁴ represents a hydrogen atom or a hydrocarbon group, R ⁵ each independently represents a hydrogen atom or an organic group, and n represents an integer of 0 to ^4. ) The binder composition for a lithium ion secondary battery electrode according to any one of claims 1 to 4 , wherein the fluorine-containing polymer alloy polymer particles have a number average particle diameter of 50 to 400 nm. The slurry for lithium ion secondary battery electrodes containing the binder composition for lithium ion secondary battery electrodes as described in any one of Claims 1 thru | or 5 , and an electrode active material. A method for producing a lithium ion secondary battery electrode comprising: a current collector; and a layer formed by applying and drying the slurry for a lithium ion secondary battery electrode according to claim 6 on the surface of the current collector. . The manufacturing method of a lithium ion secondary battery including the manufacturing method of the lithium ion secondary battery electrode of Claim 7 .

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